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US20220181633A1 - Binder for electricity storage devices - Google Patents

Binder for electricity storage devices Download PDF

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Publication number
US20220181633A1
US20220181633A1 US17/677,964 US202217677964A US2022181633A1 US 20220181633 A1 US20220181633 A1 US 20220181633A1 US 202217677964 A US202217677964 A US 202217677964A US 2022181633 A1 US2022181633 A1 US 2022181633A1
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US
United States
Prior art keywords
group
monomer
binder
general formula
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US17/677,964
Inventor
Kei Kawano
Kazuki Takimoto
Kaho MORI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Fujifilm Wako Pure Chemical Corp
Original Assignee
Fujifilm Corp
Fujifilm Wako Pure Chemical Corp
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Assigned to FUJIFILM WAKO PURE CHEMICAL CORPORATION, FUJIFILM CORPORATION reassignment FUJIFILM WAKO PURE CHEMICAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KAWANO, KEI, MORI, Kaho, Takimoto, Kazuki
Publication of US20220181633A1 publication Critical patent/US20220181633A1/en
Abandoned legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a binder used in an electricity storage device, a slurry composition and an electrode, and an electricity storage device including the electrode.
  • a battery (electricity storage device) used in a mobile terminal such as a notebook computer or a mobile phone, a hybrid car, an electric vehicle, an electrically power assisted bicycle, or the like is rapidly becoming widespread, and is required to be further reduced in size and weight.
  • a lithium ion secondary battery having an advantage of high energy density and light weight is attracting attention as an electricity storage device used in these products.
  • an electrode used for a lithium ion secondary battery or the like contains a collector and an electrode mixture layer formed on the collector.
  • a negative electrode mixture layer which is an electrode mixture layer in a negative electrode, is generally formed in such a manner that a negative electrode active material typified by graphite or silicon, a conductive assistant typified by acetylene black or carbon black, a binder, and the like are dispersed or dissolved in a dispersion medium to obtain a slurry for a negative electrode mixture layer (slurry for an electrode mixture layer), the obtained slurry is coated on a collector, followed by drying, and the negative electrode active material, the conductive assistant, and the like are bound with a binder.
  • the characteristics required for this slurry for an electrode mixture layer include the uniformity in a case where an active material or a conductive assistant is dispersed or dissolved in a dispersion medium. This is because the dispersed state of the active material and the conductive assistant in the slurry for an electrode mixture layer is related to the distributed state of the active material and the conductive assistant in the electrode mixture layer, which affects the physical properties of the electrode and the battery performance.
  • a carbon material having excellent conductivity has a small particle size and a large specific surface area, thus exhibiting a strong cohesive force, which makes it difficult for the carbon material to be uniformly mixed and dispersed in the slurry for an electrode mixture layer.
  • the internal resistance of the electrode cannot be reduced because a uniform conductive network is not formed, and as a result, there arises a problem that the performance of the electrode material cannot be sufficiently brought out. For that reason, improving the dispersibility of the conductive assistant is an important issue.
  • Patent Literature 1 and Patent Literature 2 describe an example in which a surfactant is used as a dispersant in a case where carbon black is dispersed in a solvent.
  • Patent Literature 3 and Patent Literature 4 describe an example in which various additives are added in a case where a conductive assistant is dispersed.
  • Patent Literature 5 and Patent Literature 6 describe an example in which a polymer containing a specific monomer component in a predetermined ratio is used.
  • Patent Literature 7 describes an example in which flexibility of the electrode is improved by adding a composite body of carbon nanotubes.
  • the dispersant described in Patent Literature 3 and Patent Literature 4 is a low-molecular-weight substance and therefore may be eluted from an electrode mixture layer into an electrolytic solution, which may adversely affect the battery performance.
  • the dispersant to be added has poor compatibility with a binder polymer or a solvent, there is a problem that the battery performance is deteriorated.
  • the polymer to which the monomer described in Patent Literature 5 and Patent Literature 6 is added exhibits a main skeleton of the polymer becoming flexible and therefore has a problem that a conductive path between the active materials is lost, resulting from the expansion and contraction of the active materials due to charge and discharge of the battery, and the battery capacity is lowered.
  • a water-dispersible polymer has a low viscosity, there is a problem that the polymer needs to be used in combination with a thickener such as carboxymethyl cellulose.
  • the composite body of carbon nanotubes described in Patent Literature 7 does not contain a binder polymer, the composite body may peel off from a current collecting foil of an electrode in a case where charge and discharge of the battery are repeated, and the battery may not withstand long-term use.
  • the present invention has been made in view of such circumstances, and the present invention provides a binder having excellent dispersibility that solves the problems described above, or a binder capable of imparting excellent flexibility to an electrode, a slurry composition and an electrode using the same, and an electricity storage device provided with the electrode.
  • an electricity storage device having excellent dispersibility of a conductive assistant and capable of maintaining a high capacity for a long period of time can be obtained by using a binder in which a loss tangent tan ⁇ in a linear region of an aqueous dispersion liquid containing specific amounts of a conductive assistant and a binder satisfies tan ⁇ >1 in the strain dispersion measurement in the electricity storage device.
  • a first invention has been completed based on this finding.
  • the first invention encompasses the following inventions [i] to [xi].
  • a binder for an electricity storage device in which a loss tangent tan ⁇ in a linear region of an aqueous dispersion liquid of 0.5% by mass of the binder and 4.6% by mass of a conductive assistant satisfies tan ⁇ >1 in a strain dispersion measurement under measurement conditions of a measurement temperature of 25° C. and a frequency of 1 Hz, and here, the conductive assistant is an acetylene black having an average particle diameter of 30 nm or more and 40 nm or less and a specific surface area of 65 m 2 /g or more and 70 m 2 /g or less (hereinafter, sometimes referred to simply as the binder of the first invention).
  • R 1 represents a hydrogen atom or a methyl group
  • Y 1 represents —O— or —NR 2 —
  • R 2 represents a hydrogen atom or a methyl group
  • a 1 represents a monovalent group having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group.
  • R 1 represents a hydrogen atom or a methyl group
  • Y 1 represents —O— or —NR 2 —
  • R 2 represents a hydrogen atom or a methyl group
  • a 2 represents an alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; or a linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof.
  • a slurry composition for an electricity storage device containing the binder according to any one of the inventions [i] to [viii] (hereinafter, sometimes referred to simply as the slurry composition of the first invention).
  • An electricity storage device including the electrode according to the invention [x] (hereinafter, sometimes referred to simply as the electricity storage device of the first invention).
  • the second invention encompasses the following inventions [xii] to [xxi].
  • a binder for an electricity storage device (hereinafter, sometimes referred to simply as the binder of the second invention), in which the binder contains a salt of a polymer containing structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group and neutralized with a monoamine, a polyvalent amine having an amine value of less than 21, and/or an onium hydroxide.
  • R 1 represents a hydrogen atom or a methyl group
  • Y 1 represents —O— or —NR 2 —
  • R 2 represents a hydrogen atom or a methyl group
  • a 1 represents a monovalent group having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group.
  • R 1 represents a hydrogen atom or a methyl group
  • Y 1 represents —O— or —NR 2 —
  • R 2 represents a hydrogen atom or a methyl group
  • a 2 represents an alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; or a linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof.
  • a slurry composition for an electricity storage device containing the binder according to any one of the inventions [xii] to [xvii] (hereinafter, sometimes referred to simply as the slurry composition of the second invention).
  • binder of the first invention leads to excellent dispersibility of a conductive assistant, which makes it possible to provide an electricity storage device capable of maintaining a high capacity for a long period of time.
  • binder of the second invention for the production of an electrode leads to improved flexibility of the electrode, which makes it possible to provide an electrode having excellent winding properties, and an electricity storage device provided with the electrode.
  • the binder of the first invention is a binder in which a loss tangent tan ⁇ in a linear region of an aqueous dispersion liquid of 0.5% by mass of a binder and 4.6% by mass of a conductive assistant in the strain dispersion measurement under the measurement conditions of a measurement temperature of 25° C. and a frequency of 1 Hz satisfies tan ⁇ >1.
  • the upper limit value of tan ⁇ is not particularly limited and is, for example, 1 ⁇ tan ⁇ 100, preferably 1 ⁇ tan ⁇ 50, and more preferably 1 ⁇ tan ⁇ 10.
  • the “linear region” indicates a region from the time in a case where a measurement is started in the strain dispersion measurement to the time in a case where the structural disorder of a measurement sample is started, and refers to a region in which the elastic modulus obtained in the strain dispersion measurement shows a constant value regardless of the increase in the amount of strain. It should be noted that the region after the start of structural disorder (the range in which the elastic modulus decreases depending on the increase in the amount of strain) is referred to as a non-linear region.
  • the “loss tangent tan ⁇ ” indicates a ratio of a storage elastic modulus G′ and a loss elastic modulus G′′ (loss elastic modulus G′′/storage elastic modulus G′), where the storage elastic modulus G′ is an indicator of elastic properties and the loss elastic modulus G′′ is an indicator of viscous properties. Both the storage elastic modulus G′ and the loss elastic modulus G′′ can be obtained by carrying out the strain dispersion measurement.
  • the “loss tangent tan ⁇ ” may be calculated in such a manner that the storage elastic modulus G′ and the loss elastic modulus G′′ in a case where the amount of strain is increased from 10 ⁇ 2 % to 10 3 % are measured under the measurement conditions of a measurement temperature of 25° C. and a frequency of 1 Hz using a rheometer MCR 102 (dynamic viscoelasticity measuring device, manufactured by Anton Paar GmbH), and the loss elastic modulus G′′/storage elastic modulus G′ is calculated based on the obtained values.
  • Acetylene black having an average particle diameter of 30 nm or more and 40 nm or less and a specific surface area of 65 m 2 /g or more and 70 m 2 /g or less shall be used as the “conductive assistant”.
  • Specific examples of the acetylene black satisfying the average particle diameter conditions and the specific surface area conditions include DENKA BLACK (registered trademark) powder (manufactured by Denka Company Limited, average particle diameter: 35 nm, specific surface area: 68 m 2 /g, representative values posted on the home page of Denka Company Limited).
  • Ion exchange water may be used as the “water” that is a dispersion medium in the “aqueous dispersion liquid”.
  • Specific configurations of the binder of the first invention include a configuration that contains a polymer or a salt thereof containing structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group (hereinafter, sometimes referred to simply as the polymer according to the first invention).
  • the ethylenically unsaturated carboxylic acid monomer (hereinafter, sometimes referred to simply as the monomer of (i)) is a monomer having both an ethylenically unsaturated group and a carboxy group in one molecule. However, the monomer of (i) has one ethylenically unsaturated group, unlike the monomer of (iii) which will be described later. In addition, the monomer of (i) may be an acid anhydride.
  • the monomer of (i) include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, mono(2-acryloyloxyethyl)succinate, mono(2-acryloyloxyethyl)phthalate, and mono(2-acryloyloxyethyl)hexahydrophthalate; and ethylenically unsaturated dicarboxylic acid monomers such as maleic acid, fumaric acid, itaconic acid, maleic acid anhydride, and itaconic anhydride.
  • monocarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, mono(2-acryloyloxyethyl)succinate, mono(2-acryloyloxyethyl)phthalate, and mono(2-acryloyloxyethyl)hexahydrophthalate
  • an ethylenically unsaturated monocarboxylic acid monomer is preferable; acrylic acid or methacrylic acid is more preferable; and acrylic acid is particularly preferable.
  • the monomer of (i) may be used alone or in combination of two or more thereof, and only one type thereof is preferably used.
  • the ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group is a monomer having both a “group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group” and an ethylenically unsaturated group in one molecule, and is not particularly limited as long as it is commonly used in the art.
  • the monomer of (i) and the monomer of (ii) have different structures, and the hydroxy group in the monomer of (ii) does not contain a carboxy group, a sulfo group, and a phosphate group (the OH present in the carboxy group, sulfo group, and phosphate group does not correspond to the hydroxy group in the monomer of (ii)).
  • the monomer of (ii) has one ethylenically unsaturated group, unlike the monomer of (iii) which will be described later.
  • dialkylamino group in the monomer of (ii) examples include a dialkylamino group having 2 to 12 carbon atoms, among which a dialkylamino group having 2 to 8 carbon atoms is preferable.
  • each of the two alkyl groups in the dialkylamino group may be linear, branched, or cyclic and is preferably linear or branched.
  • the two alkyl groups in the dialkylamino group may be the same or different from each other, and the two alkyl groups may be bonded to each other to form a heterocyclic structure.
  • dialkylamino group examples include a dimethylamino group, a diethylamino group, a di(n-propyl)amino group, a diisopropylamino group, a di(n-butyl)amino group, a diisobutylamino group, a morpholino group, and a piperidino group.
  • the monomer of (ii) examples include a monomer having a high solubility in water.
  • the monomer of (ii) is preferably a monomer having a solubility in water at 20° C. of 1 g/L or more; more preferably a monomer having a solubility in water at 20° C. of 100 g/L or more; and particularly preferably a monomer which dissolves in water at an arbitrary ratio.
  • the monomer of (ii) preferably has an SP value of 11.5 (cal/cm 3 ) 1/2 or more.
  • the upper limit value of the SP value of the monomer of (ii) is not particularly limited and is preferably 25 (cal/cm 3 ) 1/2 or less.
  • the SP value (Solubility Parameter) in the present invention is calculated according to the Fedors method, and can be specifically obtained from the following calculation formula.
  • ⁇ represents an SP value (cal/cm 3 ) 1/2
  • ⁇ E coh represents a molar cohesive energy (cal/mol)
  • ⁇ V represents a molar molecular volume (cm 3 /mol).
  • Examples of the ethylenically unsaturated group in the monomer of (ii) include an allyl group, a vinylaryl group, a vinyloxy group, an acryloyl group, and a methacryloyl group, among which the acryloyl group and the methacryloyl group are preferable, and the acryloyl group is more preferable.
  • the monomer of (ii) may be, for example, a monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group, and having an acryloyl group or a methacryloyl group. More specifically, the monomer of (ii) may be, for example, a monomer represented by the following general formula [1].
  • R 1 represents a hydrogen atom or a methyl group
  • Y 1 represents —O— or —NR 2 —
  • R 2 represents a hydrogen atom or a methyl group
  • a 1 represents a monovalent group having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group.
  • R 1 of the general formula [1] is preferably a hydrogen atom.
  • R 2 in —NR 2 — is preferably a hydrogen atom.
  • Y 1 of the general formula Ell is preferably —O— or —NH— and more preferably —O—.
  • dialkylamino group in A 1 of the general formula [1] examples include the same dialkylamino groups in the monomer of (ii).
  • the “group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group” contained in A 1 of the general formula [1] may be only one type or two or more types; and is preferably any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; more preferably any one of a group selected from a hydroxy group, a sulfo group, a phosphate group, or a cyano group; still more preferably any one of a group selected from a hydroxy group, a sulfo group, or a phosphate group; and particularly preferably a hydroxy group.
  • a 1 of the general formula [1] may have at least one “group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group”.
  • a 1 of the general formula [1] preferably has 1 to 3 groups, more preferably 1 or 2 groups, and particularly preferably 1 group among those groups.
  • the “monovalent group” in A 1 of the general formula [1] may be, for example, an alkyl group which may have an ester bond in a chain thereof.
  • alkyl group in a case where the “alkyl group which may have an ester bond in a chain thereof” does not have an ester bond include an alkyl group having 1 to 30 carbon atoms, among which an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is still more preferable.
  • the alkyl group may be linear, branched, or cyclic, and is preferably linear or branched and more preferably linear.
  • a 1 of the general formula [1] may be, for example, an alkyl group which has at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group, and may have an ester bond in a chain thereof.
  • an alkyl group having 1 to 30 carbon atoms and having 1 to 3 groups selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, and a cyano group, and an alkyl group having 3 to 66 carbon atoms and having 1 hydroxy group and 1 to 10 ester bonds in a chain thereof are preferable; an alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group, and a linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof are more preferable; and an alkyl group having 1 to 10 carbon atoms and having 1 to 2 hydroxy groups, an alkyl group having 1 to 10 carbon carbon atom
  • a 1 of the general formula [1] include groups represented by the following general formulae [1-1] to [1-4], among which a group represented by the general formula [1-1] is preferable.
  • a 1-1 and A 1-2 each independently represent an alkylene group having 1 to 10 carbon atoms
  • R 3 represents a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group
  • a represents an integer of 0 to 4
  • b represents an integer of 1 to 5
  • c represents an integer of 1 to 6
  • d represents an integer of 3 to 5
  • e represents an integer of 1 to 3.
  • the alkylene group having 1 to 10 carbon atoms in A 1-1 of the general formula [1-1] is preferably an alkylene group having 1 to 6 carbon atoms and more preferably an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched and more preferably linear.
  • alkylene group examples include a methylene group, an ethylene group, a methylmethylene group, a trimethylene group, a propylene group, an ethylmethylene group, a dimethylmethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, an ethylethylene group, a propylmethylene group, an ethylmethylmethylene group, a pentamethylene group, a 1-methyltetramethylene group, a 1-ethyltrimethylene group, an n-propylethylene group, an n-butylmethylene group, a hexamethylene group, a 1-methylpentamethylene group, a 1-ethyltetramethylene group, a 1-n-propyltrimethylene group, an n-butylethylene group, an n-pentylm
  • a linear or branched alkylene group having 1 to 6 carbon atoms and a cyclic alkylene group having 6 to 8 carbon atoms are preferable; a linear or branched alkylene group having 1 to 4 carbon atoms is more preferable; and a linear or branched alkylene group having 2 to 4 carbon atoms is still more preferable.
  • dialkylamino group in R 3 of the general formula [1-2] examples include the same dialkylamino groups in the monomer of (ii).
  • Specific examples of the group represented by the general formula [1-1] include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, a 3-hydroxy-2-methylpropyl group, a 3-hydroxy-1-methylpropyl group, a 2-hydroxybutyl group, a 2-hydroxy-2-methylpropyl group, a 2-hydroxy-1-methylpropyl group, a 2-hydroxy-1,1-dimethylethyl group, a 1-hydroxybutyl group, a 1-hydroxy-1-methylpropyl group, a 5-hydroxypentyl group, a 4-hydroxypentyl group, a 2-hydroxypentyl group, a 1-hydroxypentyl group, a 6-hydroxyhex
  • a linear or branched hydroxyalkyl group having 1 to 6 carbon atoms and a cyclic hydroxyalkyl group having 6 to 8 carbon atoms are preferable; a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms is more preferable; and a linear or branched hydroxyalkyl group having 2 to 4 carbon atoms is still more preferable.
  • a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, a 2-hydroxybutyl group, a 2-hydroxy-2-methylpropyl group, a 2-hydroxy-1-methylpropyl group, a 1-hydroxybutyl group, a 5-hydroxypentyl group, a 2-hydroxypentyl group, a 1-hydroxypentyl group, a 6-hydroxyhexyl group, a 5-hydroxyhexyl group, a 2-hydroxyhexyl group, a 1-hydroxyhexyl group, a —C 6 H 10 —OH group, and a —CH 2 —C 6 H 10 —CH 2 —OH group are preferable; the hydroxymethyl group, the 2-hydroxyethyl group, the 1-
  • the alkylene group having 1 to 10 carbon atoms in A 1-2 of the general formula [1-2] is the same as the specific examples of the alkylene group having 1 to 10 carbon atoms in A 1 _i of the general formula [1-1], among which a linear or branched alkylene group having 1 to 6 carbon atoms is preferable, and a linear or branched alkylene group having 1 to 4 carbon atoms is more preferable.
  • R 3 of the general formula [1-2] is preferably a sulfo group, a phosphate group, or a cyano group and more preferably a sulfo group or a phosphate group.
  • dialkylaminoalkyl groups having 3 to 12 carbon atoms such as a dimethylaminomethyl group, a 2-(dimethylamino)ethyl group, a 3-(dimethylamino)propyl group, a 4-(dimethylamino)butyl group, a diethylaminomethyl group, a 2-(diethylamino)ethyl group, a 3-(diethylamino)propyl group, a 4-(diethylamino)butyl group, a di(n-propyl)aminomethyl group, a 2-[di(n-propyl)amino] ethyl group, a 3-[di(n-propyl) amino]propyl group, a 4-[di(n-propyl)amino]butyl group, a diisopropylaminomethyl group, a 2-(diiso
  • a 2-(dimethylamino)ethyl group a 2-(diethylamino)ethyl group, a 2-[di(n-propyeamino]ethyl group, a 2-(diisopropylamino)ethyl group, a 2-[di(n-butyl)amino]ethyl group, a 2-(diisobutylamino)ethyl group, a 2-morpholinoethyl group, a 2-piperidinoethyl group, an acetomethyl group, a 2-acetoethyl group, a 1,1-dimethyl-2-acetoethyl group, a sulfomethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 2-sulfopropyl group, a 1-sulfopropyl group, a 4-sulfobutyl group,
  • a and b of the general formula [1-3] are each preferably an integer of 1 to 4 and is preferably 1 or 2 and more preferably 1.
  • Specific examples of the group represented by the general formula [1-3] include a 1,2-dihydroxypropyl group, a 1,3-dihydroxypropyl group, a 2,3-dihydroxypropyl group, a 1,2-dihydroxybutyl group, a 1,3-dihydroxybutyl group, a 1,4-dihydroxybutyl group, a 2,3-dihydroxybutyl group, a 2,4-dihydroxybutyl group, a 3,4-dihydroxybutyl group, a 1,2-dihydroxypentyl group, a 1,3-dihydroxypentyl group, a 1,4-dihydroxypentyl group, a 1,5-hydroxypentyl group, a 2,3-dihydroxypentyl group, a 2,4-dihydroxypentyl group, a 2,5-hydroxypentyl group, a 3,4-dihydroxypentyl group, a 3,5-dihydroxypentyl group, a 4,5-hydroxy
  • c of the general formula [1-4] is preferably 2 or 4 and more preferably 2.
  • d of the general formula [1-4] is preferably 3 or 5 and more preferably 5.
  • e of the general formula [1-4] is preferably 1 or 2.
  • a 1 of the general formula [1] include the same specific examples of the groups represented by the general formulae [1-1] to [1-4], among which a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, a 2-hydroxybutyl group, a 2-hydroxy-2-methylpropyl group, a 2-hydroxy-1-methylpropyl group, a 1-hydroxybutyl group, a 5-hydroxypentyl group, a 6-hydroxyhexyl group, a —CH 2 —C 6 H 10 —CH 2 —OH group, a sulfomethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a
  • a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a 4-hydroxybutyl group, a 2-hydroxybutyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 2-phosphonooxyethyl group, and a 2,3-dihydroxypropyl group are more preferable; and the 2-hydroxyethyl group, the 2-hydroxypropyl group, the 2-hydroxy-1-methylethyl group, and the 4-hydroxybutyl group are particularly preferable.
  • Examples of the combination of A 1 , R 1 , and Y 1 in the general formula [1] include combinations 1 to 12 described in the following table. Among these combinations, combinations 1 to 10 are preferable, combinations 1, 2, 9, and 10 are more preferable, combinations 1, 2, and 9 are still more preferable, and combination 1 is particularly preferable.
  • Preferred specific examples of the monomer represented by the general formula [1] include a monomer represented by the following general formula [2].
  • a 2 represents an alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; or a linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof, and R 1 and Y 1 are as defined hereinbefore.
  • alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group” and the “linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof” of A 2 of the general formula [2] include the same specific examples of the groups represented by the general formulae [1-1] to [1-4], and preferred examples thereof are also the same.
  • a 2 of the general formula [2] is preferably an alkyl group having 1 to 10 carbon atoms and having 1 to 2 hydroxy groups; an alkyl group having 1 to 10 carbon atoms and having one of any one of a group selected from a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; or a linear alkyl group having 5 to 24 carbon atoms and having 1 hydroxy group and 1 to 3 ester bonds in a chain thereof, more preferably a group represented by the general formulae [1-1] to [1-4], and still more preferably a group represented by the general formula [1-1]. More specific examples of A 2 of the general formula [2] include the same preferred specific examples of A 1 of the general formula [1], and preferred examples thereof are also the same.
  • Examples of the combination of A 2 , R 1 , and Y 1 in the general formula [2] include the same combinations of A 1 , R 1 , and Y 1 in the general formula [1], and preferred examples thereof are also the same.
  • monomers represented by the general formula [2] include the following monomers.
  • More preferred specific examples of the monomer represented by the general formula [1] include a monomer represented by the following general formula [3].
  • a 3 represents a linear or branched alkylene group having 1 to 4 carbon atoms, and R 1 is as defined hereinbefore.
  • a 3 of the general formula [3] is preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, and an ethylethylene group, among which the ethylene group, the propylene group, and the tetramethylene group are preferable; and the ethylene group and the tetramethylene group are more preferable.
  • the monomer represented by the general formula [3] include hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, 4-hydroxybutyl methacrylate, and 2-hydroxybutyl methacrylate, among which 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, and 4-hydroxybutyl methacrylate are preferable; 2-hydroxyethyl acrylate,
  • the monomer of (ii) may be used alone or in combination of two or more thereof, and it is preferable to use only one thereof alone or two thereof in combination.
  • the polymer according to the first invention may further contain a structural unit derived from (iii) a monomer having two or more polymerizable unsaturated groups, in addition to the monomer of (i) and the monomer of (ii).
  • the (iii) monomer having two or more polymerizable unsaturated groups (hereinafter, sometimes referred to simply as the monomer of (iii)) has a structure different from that of the monomer of (i) and the monomer of (ii).
  • the polymerizable unsaturated group in the monomer of (iii) include an ethylenically unsaturated group such as a vinyloxy group, an allyl group, a vinylaryl group, an acryloyl group, or a methacryloyl group; an isocyanate group; and a carbodiimide group, among which the ethylenically unsaturated group is preferable; the allyl group, the acryloyl group, and the methacryloyl group are more preferable; and the acryloyl group is particularly preferable.
  • an ethylenically unsaturated group such as a vinyloxy group, an allyl group, a vinylaryl group, an acryloyl group, or a methacryloyl group
  • an isocyanate group such as a ethylenically unsaturated group
  • the allyl group, the acryloyl group, and the methacryloyl group are more preferable
  • Examples of the monomer of (iii) include a monomer represented by the following general formula [11] or [12], among which a monomer represented by the general formula [11] is preferable.
  • R 11 represents a hydrogen atom or a methyl group
  • Y 11 represents —O— or —NR 12 —
  • R 12 represents a hydrogen atom or a methyl group
  • a 11 represents a group represented by the following general formulae [11-1] to [11-3]
  • two R 11 's and two Y 11 's are each the same:
  • R 13 and R 14 each independently represent a hydrogen atom or a methyl group
  • Y 12 represents —O— or —NR 15 —
  • R 15 represents a hydrogen atom or a methyl group
  • a 12 to A 15 each independently represent an alkylene group having 1 to 6 carbon atoms
  • a 16 and A 17 each independently represent an alkylene group having 1 to 6 carbon atoms which may have an ether bond in a chain thereof
  • g represents an integer of 0 to 30
  • h represents an integer of 1 to 3
  • i represents an integer of 0 to 6
  • j represents an integer of 1 to 3
  • two A 16 's, two R 14 's, and two Y 12 's are each the same.
  • R 16 to R 22 each independently represent an alkylene group having 1 to 3 carbon atoms.
  • R 11 of the general formula [11] is preferably a hydrogen atom.
  • R 12 in —NR 12 — is preferably a hydrogen atom.
  • Y 11 of the general formula [11] is preferably —O— or —NH— and more preferably —NH—.
  • the alkylene group having 1 to 6 carbon atoms in A 12 and A 13 of the general formula [11-1] is preferably an alkylene group having 1 to 4 carbon atoms and more preferably an alkylene group having 2 to 3 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched and more preferably linear.
  • alkylene group examples include a methylene group, an ethylene group, a methylmethylene group, a trimethylene group, a propylene group, an ethylmethylene group, a dimethylmethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, an ethylethylene group, a propylmethylene group, an ethylmethylmethylene group, a pentamethylene group, a 1-methyltetramethylene group, a 1-ethyltrimethylene group, an n-propylethylene group, an n-butylmethylene group, a hexamethylene group, a 1-methylpentamethylene group, a 1-ethyltetramethylene group, a 1-n-propyltrimethylene group, an n-butylethylene group, an n-pentylm
  • the repeating units may be the same or different. It is preferable that all the repeating units are the same.
  • g pieces of A 13 's in the general formula [11-1] may be the same or different.
  • g in the general formula [11-1] is an integer of 1 or more, it is preferable that A 12 and A 13 in the g-th repeating unit are the same; and it is more preferable that A 12 and A 13 in the g-th repeating unit are the same, and A 13 's in the first to g-1-th repeating units are all the same.
  • the repeating unit in the general formula [11-1] is counted as the first repeating unit, the second repeating unit, . . . from the side adjacent to Au, and the g-th repeating unit is a repeating unit located at the farthest point from A 12 (a repeating unit adjacent to one of Y 11 's in the general formula [11]).
  • g of the general formula [11-1] is preferably an integer of 0 to 15, more preferably an integer of 0 to 10, and still more preferably an integer of 0 to 3.
  • Examples of the combination of A 12 , A 13 , and gin the general formula [11-1] include combinations 1 to 29 described in the following table. Among these combinations, combinations 1, 2, 7 to 13, 15, 17 to 19, 24, and 25 are preferable, and combinations 1, 7 to 10, 12, 15, 17, 18, and 24 are more preferable.
  • the repeating units may be the same or different. It is preferable that all the repeating units are the same.
  • h pieces of R 13 's in the general formula [11-2] may be the same or different. It is preferable that all R 13 's are the same, and it is more preferable that all R 13 's are the same as R 11 's of the general formula [11].
  • Examples of the alkylene group having 1 to 6 carbon atoms in A 14 and A 15 of the general formula [11-2] include the same alkylene groups having 1 to 6 carbon atoms in A 12 and A 13 of the general formula [11-1], among which a linear alkylene group having 1 to 4 carbon atoms is preferable and an ethylene group is more preferable.
  • h pieces of A 15 's in the general formula [11-2] may be the same or different. It is preferable that all A 15 's are the same. In addition, it is preferable that A 14 of the general formula [11-2] and A 15 in the h-th repeating unit are the same, and it is more preferable that A 14 and A 15 in all repeating units are the same. It should be noted that the repeating unit in the general formula [11-2] is counted as the first repeating unit, the second repeating unit, . . . from the side adjacent to A 14 , and the h-th repeating unit is a repeating unit located at the farthest point from A 14 (a repeating unit adjacent to one of Y 11 's in the general formula [11]).
  • e of the general formula [11-2] is preferably 1 or 2.
  • Examples of the combination of A 14 , A 15 , R 13 , and h in the general formula [11-2] include combinations 1 to 12 described in the following table. Among these combinations, combinations 4 to 6 are preferable and combinations 4 and 5 are more preferable.
  • the repeating units may be the same or different. It is preferable that all the repeating units are the same.
  • 2j pieces of R 14 's in the general formula [11-3] may be the same or different. It is preferable that all R 14 's are the same, and it is more preferable that all R 14 's are the same as R 11 's of the general formula [11]. In this regard, two R 14 's existing in the same repeating unit are always the same.
  • R 15 in —NR 15 — is preferably a hydrogen atom.
  • 2j pieces of Y 11 's in the general formula [11-3] may be the same or different. It is preferable that all Y 11 's are the same, and it is more preferable that all Y 11 's are the same as Y 11 's of the general formula [11]. In this regard, two Y 12 's existing in the same repeating unit are always the same.
  • alkylene group having 1 to 6 carbon atoms which may have an ether bond in a chain thereof” in A 16 and A 17 of the general formula [11-3] does not have an ether bond
  • alkylene groups having 1 to 6 carbon atoms in A 12 and A 13 of the general formula [11-1] among which a linear alkylene group having 1 to 4 carbon atoms is preferable and a methylene group is more preferable.
  • 2j pieces of A 16 's and j pieces of A 17 's in the general formula [11-3] may be respectively the same or different.
  • two A 16 's existing in the same repeating unit are always the same.
  • it is preferable that all A 16 's of the general formula [11-3] and A 17 in the j-th repeating unit are the same.
  • the repeating unit in the general formula [11-3] is counted as the first repeating unit, the second repeating unit, . . .
  • the j-th repeating unit is a repeating unit located at the farthest point from —(CH 2 ) i — (a repeating unit adjacent to one of Y 11 's in the general formula [11]).
  • i of the general formula [11-3] is preferably an integer of 0 to 4, more preferably 0 or 1, and still more preferably 0.
  • j of the general formula [11-3] is preferably 1 or 2 and more preferably 1.
  • Examples of the combination of two A 16 's, A 17 , two Y 12 's, two R 14 's, i, and j in the general formula [11-3] include combinations 1 to 20 described in the following table. Among these combinations, combinations 1 to 6 and 11 to 16 are preferable, combinations 1, 2, 11, 12, 13, and 14 are more preferable, and combinations 1, 11, and 13 are particularly preferable. It should be noted that “—CH 2 —O—(CH 2 ) 3 —” in the two A 16 's is such that a left end thereof is bonded to a main chain and a right end thereof is bonded to Y 12 .
  • Examples of the combination of A 11 , two Y 11 's, and two R 11 's in the general formula [11] include combinations 1 to 14 described in the following table.
  • the alkylene group having 1 to 3 carbon atoms in R 16 to R 22 of the general formula [12] may be linear or branched and is preferably linear. Specific examples thereof include a methylene group, an ethylene group, a methylmethylene group, a trimethylene group, a propylene group, an ethylmethylene group, and a dimethylmethylene group, among which the methylene group, the ethylene group, or the trimethylene group is preferable; the methylene group or the trimethylene group is more preferable; and the methylene group is particularly preferable.
  • R 16 to R 22 of the general formula [12] may be the same or different. It is preferable that R 17 to R 19 and R 20 to R 22 are respectively the same, and it is more preferable that all of R 16 to R 22 are the same.
  • Examples of the combination of R 16 to R 22 in the general formula [12] include combinations 1 to 27 described in the following table. Among these combinations, combinations 1 to 3 are preferable, combinations 1 and 3 are more preferable, and combination 1 is particularly preferable.
  • monomers represented by the general formulae [11] and [12] include the following monomers.
  • monomers generally used as a “crosslinking agent” in the art can be appropriately used in addition to the specific examples.
  • the crosslinking agents described in WO2014/065407A, WO2015/163302A, WO2018/143382A, WO2018/143383A, and the like can be used.
  • the content thereof is usually 0.01 mol % or more and 5 mol % or less, preferably 0.05 mol % or more and 2 mol % or less, and more preferably 0.1 mol % or more and 1 mol % or less with respect to the total content of the structural units derived from the monomer of (i) and the monomer of (ii).
  • the monomer of (i), the monomer of (ii), and the monomer of (iii) may all be commercially available or appropriately synthesized by a method known per se.
  • the polymer according to the first invention may appropriately contain a structural unit derived from a monomer commonly used in the art (hereinafter, sometimes referred to simply as another monomer), in addition to the monomer of (i), the monomer of (ii), and the monomer of (iii).
  • the content thereof is usually 0.01 mol % or more and 5 mol % or less, preferably 0.05 mol % or more and 2 mol % or less, and more preferably 0.1 mol % or more and 1 mol % or less with respect to the total content of the structural units derived from the monomer of (i) and the monomer of (ii).
  • the polymer according to the first invention may contain two or more structural units derived from the monomer of (i), the monomer of (ii), and the monomer of (iii), respectively.
  • the polymer according to the first invention is preferably a polymer consisting of structural units derived from one monomer of (i) and one or two monomers of (ii), or a polymer consisting of structural units derived from one monomer of (i), one or two monomers of (ii), and one monomer of (iii); and more preferably a polymer consisting of structural units derived from one monomer of (i), and one or two monomers of (ii) having a solubility in water at 20° C.
  • the polymer according to the first invention is preferably a polymer consisting of structural units derived from one ethylenically unsaturated monocarboxylic acid monomer and one or two monomers represented by the general formula [1], or a polymer consisting of structural units derived from one ethylenically unsaturated monocarboxylic acid monomer, one or two monomers represented by the general formula [1], and one monomer represented by the general formula [11]; more preferably a polymer consisting of structural units derived from one ethylenically unsaturated monocarboxylic acid monomer and one or two monomers represented by the general formula [2], or a polymer consisting of structural units derived from one ethylenically unsaturated monocarboxylic acid monomer, one or two monomers represented by the general formula [2], and one monomer represented by the general formula [11]; and still more preferably a polymer consisting of structural units derived from one acrylic acid or methacrylic acid and one or two monomers
  • the polymer according to the first invention is preferably a polymer consisting of structural units derived from one acrylic acid or methacrylic acid, and one or two selected from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, or 4-hydroxybutyl acrylate, or a polymer consisting of structural units derived from one acrylic acid or methacrylic acid, one or two selected from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, or 4-hydroxybutyl acrylate, and one selected from the more preferred specific example group of the monomer of (iii); and more preferably a polymer consisting of structural units derived from one acrylic acid and 2-hydroxyethyl acrylate and/or 4-hydroxybutyl acrylate, or a polymer consisting of structural units derived from one acrylic acid, 2-hydroxyethyl acrylate and/or 4-hydroxybutyl acrylate, and
  • the polymer according to the first invention is neutralized (in a case where the polymer forms a salt), it is preferable that a part or all of the carboxy group in the structural unit derived from the monomer of (i) and/or the sulfo group or the phosphate group in the structural unit derived from the monomer of (ii) is neutralized.
  • examples of the neutralizing agent used in a case of neutralizing the polymer according to the first invention include an inorganic base such as a hydroxide, a carbonate, or a hydrogen carbonate of an alkali metal or an alkaline earth metal; and an organic base such as a polyvalent amine having an amine value of 21 or more, an ammonium salt, an aliphatic phosphine, an aromatic phosphine, a phosphonium salt, an aliphatic thiol, an aromatic thiol, a thiol derivative, or a sulfonium salt.
  • an inorganic base such as a hydroxide, a carbonate, or a hydrogen carbonate of an alkali metal or an alkaline earth metal
  • an organic base such as a polyvalent amine having an amine value of 21 or more, an ammonium salt, an aliphatic phosphine, an aromatic phosphine, a phosphonium salt, an aliphatic thi
  • the neutralizing agent include a hydroxide of an alkali metal such as sodium hydroxide, lithium hydroxide, or potassium hydroxide; a carbonate of an alkali metal such as sodium carbonate, lithium carbonate, or potassium carbonate; a hydrogen carbonate of an alkali metal such as lithium hydrogen carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate; a hydroxide of an alkaline earth metal such as magnesium hydroxide or calcium hydroxide; a carbonate of an alkaline earth metal such as magnesium carbonate or calcium carbonate; a polyvalent amine having an amine value of 21 or more such as ethylenediamine, 1,2-propanediamine, N-methyl-1,3-propanediamine, bis(2-aminoethyl)amine, tris(2-aminoethyl)amine, or polyethyleneimine; an ammonium salt such as tetrabutylammonium tetrafluoroborate or hexadecyltrimethylammonium hexaflu
  • a hydroxide of an alkali metal and a polyvalent amine having an amine value of 21 or more are preferable; sodium hydroxide, lithium hydroxide, potassium hydroxide, ethylenediamine, 1,2-propanediamine, and N-methyl-1,3-propanediamine, tris(2-aminoethyl)amine, and polyethyleneimine are more preferable; and sodium hydroxide and polyethyleneimine are particularly preferable.
  • the neutralizing agents may be used alone or in combination of two or more thereof. It is preferable to use only one neutralizing agent alone or two neutralizing agents in combination. In particular, it is preferable that only one hydroxide of an alkali metal is used alone; or one hydroxide of an alkali metal and one polyvalent amine having an amine value of 21 or more are used in combination.
  • the “polyvalent amine having an amine value of 21 or more” refers to a polyvalent amine which has two or more basic functional groups such as an amino group and has an amine value of 21 or more, indicating an amount of the basic functional groups in a structure thereof.
  • the amine value in the present invention can be specifically obtained from the calculation formula shown below.
  • the basic functional group in the present invention represents a functional group showing basicity, such as an amino group, an amidino group (amidine structure), a guanidino group (guanidine structure), a pyridino group (pyridine structure), or a phosphazeno group (phosphazene structure).
  • a degree of neutralization is usually 50% or more and 200% or less, preferably 60% or more and 150% or less, and more preferably 70% or more and 100% or less. It should be noted that the degree of neutralization referred to here represents a ratio of the total number of moles of the neutralizing agent to the total number of moles of the carboxy group, the sulfo group, and the phosphate group contained in the polymer according to the first invention.
  • the dispersibility of the conductive assistant is further improved, and the conductive assistant can be more uniformly distributed on the collector, which makes it possible to further improve the electrical characteristics of the electrode.
  • the polymer according to the first invention may be produced by carrying out a polymerization reaction according to a method known per se.
  • the polymer according to the first invention can be produced, for example, by subjecting the monomer of (i) and the monomer of (ii), and if necessary, the monomer of (iii) and/or the another monomer, according to a desired polymer, to a polymerization reaction in the presence of a polymerization initiator.
  • the amounts of the monomer of (i) and the monomer of (ii) used in the polymerization reaction may be appropriately set according to a content ratio (molar ratio) of the structural unit derived from the monomer of (i) to the structural unit derived from the monomer of (ii) in the polymer according to the first invention.
  • the amount of the monomer of (iii) and/or the another monomer used in the polymerization reaction may be appropriately set according to the content in a case where the polymer according to the first invention contains a structural unit derived from the monomer of (iii) and/or the another monomer.
  • the polymerization reaction may be carried out according to a method known per se. Specifically, the reaction may be carried out in a suitable solvent, usually at 30° C. or higher and 200° C. or lower, preferably 60° C. or higher and 150° C. or lower, more preferably 70° C. or higher and 100° C. or lower for usually 0.1 hours or longer and 24 hours or shorter, preferably 1 hour or longer and 10 hours or shorter.
  • a suitable solvent usually at 30° C. or higher and 200° C. or lower, preferably 60° C. or higher and 150° C. or lower, more preferably 70° C. or higher and 100° C. or lower for usually 0.1 hours or longer and 24 hours or shorter, preferably 1 hour or longer and 10 hours or shorter.
  • the polymerization initiator is not particularly limited as long as it is commonly used in the art, and specific examples thereof include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2-methylpropionamidine) dihydrochloride, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, 2,2′-azobis[2-(2-imidazolin-2-yl)propane], 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], ammonium persulfate (ammonium peroxodisulfate), potassium persulfate (potassium peroxodisulfate), benzoyl peroxide, and lauroyl peroxide.
  • the solvent is not particularly limited as long as it is commonly used in the art, and specific examples thereof include water, methanol, N-methyl-2-pyrrolidone (NMP), toluene, 1,4-dioxane, tetrahydrofuran, isopropanol, methyl ethyl ketone, and propylene glycol monomethyl ether acetate, among which water is preferable. These solvent compounds may be used alone or in combination of two or more thereof.
  • the amount of the solvent used is 1 time (equal amount) or more and 20 times or less with respect to the total mass of reactants.
  • the product obtained after the polymerization reaction may be subjected to general post-treatment operations and purification operations commonly carried out in the art. Specifically, for example, filtration, washing, extraction, concentration under reduced pressure, recrystallization, distillation, and column chromatography may be carried out.
  • the polymer according to the first invention obtained by the polymerization reaction may be neutralized according to a method known per se. Specifically, the polymer according to the first invention may be neutralized, for example, by adding the neutralizing agent in an amount such that the polymer according to the first invention has a desired degree of neutralization.
  • the solvent used for neutralization include the same solvents as those used in the polymerization reaction.
  • the polymer or salt thereof according to the first invention is produced as follows.
  • the monomer of (i) and the monomer of (ii) in a molar ratio of 5:95 to 95:5, and if necessary, the monomer of (iii) and/or the another monomer of 0.01 mol % or more and 5 mol % or less with respect to the content of the structural units derived from the monomer of (i) and the monomer of (ii) are dissolved or dispersed in a solvent such as water in an amount equal to or more and 20 times or less the total mass of reactants, in the presence of a polymerization initiator such as 2,2′-azobis(isobutyronitrile) of 0.001 mol % or more and 30 mol % or less with respect to the total mass of the reactants.
  • a solvent such as water in an amount equal to or more and 20 times or less the total mass of reactants
  • a polymerization reaction is carried out at 30° C. or higher and 200° C. or lower for 0.1 hours or longer and 24 hours or shorter to produce the polymer according to the first invention.
  • the neutralizing agent may be added in an amount such that the obtained polymer according to the first invention has a desired degree of neutralization to obtain a salt of the polymer according to the first invention.
  • the binder of the first invention may be contained in a slurry composition of the first invention or an electrode of the first invention which will be described later, in a form dissolved in a solvent.
  • a solution in which the binder is dissolved in a solvent is referred to as a “binder solution”, and in particular, a solution in which the binder of the first invention is dissolved in a solvent is referred to as a “binder solution according to the first invention”.
  • the solvent in the binder solution according to the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include water, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, ⁇ -butyrolactone, toluene, methyl ethyl ketone, ethyl acetate, and dioxane, among which water is preferable.
  • These solvent compounds may be used alone or in combination of two or more thereof. It is preferable to use only one solvent compound alone.
  • the binder solution may be referred to as “the binder aqueous solution according to the first invention”.
  • the content (mass of solid content) of the binder of the first invention in the binder solution according to the first invention may be appropriately set according to a desired concentration of the binder solution according to the first invention, and is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 50% by mass or less.
  • the binder solution according to the first invention may contain various additives commonly used in the art, in addition to the binder of the first invention and a solvent.
  • various additives include a dispersant, a thickener, a metal binder (for example, aminotriazole), a reducing agent (for example, ascorbic acid), a preservative (for example, cetylpyridinium chloride), a rust inhibitor, a fungicide, an antibacterial agent, a deodorant, a leveling agent, a defoamer, a blister inhibitor, an anti-yellowing agent, an antistatic agent, a charge regulator, an electrolyte decomposition inhibitor, an antioxidant, an anti-aging agent, a light stabilizer, an ultraviolet absorber, a thixotropic agent, a freeze stabilizer, a pH adjuster, a lubricant, a rheology control agent, and a film forming aid.
  • a dispersant for example, a thickener, a metal
  • additives may be used alone or in combination of two or more thereof, depending on the purpose.
  • the content of various additives in the binder solution according to the first invention is usually 10% by mass or less, preferably 5% by mass or less, and more preferably 1% by mass or less with respect to the content of the binder of the first invention.
  • the slurry composition of the first invention is a composition for preparing an electrode for an electricity storage device, which contains the binder of the first invention. More specifically, the slurry composition of the first invention is a composition containing an active material and a solvent, and if necessary, a conductive assistant, in addition to the binder of the first invention (or the binder solution according to the first invention).
  • the slurry composition of the first invention may be used for preparing a positive electrode or a negative electrode, and is preferably used for preparing a negative electrode.
  • the content of the binder of the first invention in the slurry composition of the first invention is usually 0.1% by mass or more and 30% by mass or less, preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less with respect to the total mass of the slurry composition of the first invention containing no solvent.
  • the active material in the slurry composition of the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include carbon, silicon, germanium, tin, lead, zinc, aluminum, indium, antimony, bismuth, sodium, magnesium, titanium, and compounds containing these as elements (such as oxides), among which carbon, silicon, or a compound containing silicon as an element is preferable. These active materials may be used alone or in combination of two or more thereof.
  • Examples of the carbon include a graphite-based carbon material (graphite) such as natural graphite, artificial graphite, or expanded graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon, and hard carbon.
  • graphite such as natural graphite, artificial graphite, or expanded graphite is preferable.
  • Examples of the natural graphite include flake graphite and vein graphite.
  • Examples of the artificial graphite include vein graphite, vapor-grown graphite, flake graphite, and fibrous graphite.
  • Examples of the silicon or compound containing silicon as an element include silicon as well as a silicon oxide such as SiO or SiO 2 , and silicon bonded to a metal, SiM (M represents a metal such as magnesium, iron, calcium, cobalt, nickel, boron, copper, manganese, silver, vanadium, cerium, or zinc), among which the silicon or the silicon oxide is preferable, and the silicon is more preferable.
  • SiM represents a metal such as magnesium, iron, calcium, cobalt, nickel, boron, copper, manganese, silver, vanadium, cerium, or zinc
  • the surface of silicon may be partially or completely coated with carbon
  • examples of the surface-coated silicon include carbon-coated silicon, a silicon oxide, and silicon bonded to a metal, among which the carbon-coated silicon or the silicon oxide is preferable and the carbon-coated silicon oxide is more preferable.
  • the active material in the slurry composition of the first invention preferably contains one or more carbons and/or one or more silicons or compounds containing silicon as an element, and more preferably contains one or more carbons and one or more silicons or compounds containing silicon as an element. More specific examples of the active material include an active material containing a mixture of at least one selected from natural graphite, artificial graphite, or expanded graphite and at least one selected from silicon, a silicon oxide, carbon-coated silicon, or a carbon-coated silicon oxide, among which an active material containing natural graphite and a carbon-coated silicon oxide is preferable.
  • the average particle diameter of the active material in the slurry composition of the first invention varies depending on the type of active material used, and is usually 0.001 ⁇ m or more and 100 ⁇ m or less, preferably 0.01 ⁇ m or more and 50 ⁇ m or less, and more preferably 0.1 ⁇ m or more and 30 ⁇ m or less.
  • the content of the active material in the slurry composition of the first invention is usually 30% by mass or more and 99.9% by mass or less, preferably 40% by mass or more and 99% by mass or less, and more preferably 50% by mass or more and 98% by mass or less with respect to the total mass of the slurry composition of the first invention containing no solvent.
  • the conductive assistant in the slurry composition of the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include carbon blacks such as acetylene black, Ketjen black, furnace black, and thermal black; and nanocarbons such as carbon nanotubes and carbon nanohorns, among which the acetylene black and the Ketjen black are preferable and the acetylene black is more preferable.
  • These conductive assistants may be used alone or in combination of two or more thereof.
  • the average particle diameter of the conductive assistant in the slurry composition of the first invention varies depending on the type of the conductive assistant used, and is usually 0.001 ⁇ m or more and 50 ⁇ m or less, preferably 0.01 ⁇ m or more and 10 ⁇ m or less, and more preferably 0.02 ⁇ m or more and 1 ⁇ m or less.
  • the content of the conductive assistant in the slurry composition of the first invention is usually 0.1% by mass or more and 40% by mass or less, preferably 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less with respect to the total mass of the slurry composition of the first invention containing no solvent.
  • the solvent in the slurry composition of the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include water, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, ⁇ -butyrolactone, toluene, methyl ethyl ketone, ethyl acetate, and dioxane, among which water is preferable.
  • NMP N-methyl-2-pyrrolidone
  • dimethylformamide dimethylacetamide
  • methylformamide dimethyl sulfoxide
  • acetonitrile acetonitrile
  • tetrahydrofuran ⁇ -butyrolactone
  • toluene methyl ethyl ketone
  • ethyl acetate ethyl acetate
  • dioxane among which water is prefer
  • the solvent in the slurry composition of the first invention is preferably the same as the solvent in the binder solution according to the first invention.
  • the slurry composition of the first invention may contain a supporting salt, an additive, and the like commonly used in the art, in addition to the binder of the first invention, an active material, a conductive assistant, and a solvent.
  • Examples of the supporting salt include Li(C 2 F 5 SO 2 ) 2 N(LiBETI), LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , and LiCF 3 SO 3 .
  • Examples of the additive include a dispersant, a thickener, a metal binder, a reducing agent, a preservative, a rust inhibitor, a fungicide, an antibacterial agent, a deodorant, a leveling agent, a defoamer, a blister inhibitor, an anti-yellowing agent, an antistatic agent, a charge regulator, an electrolyte decomposition inhibitor, an antioxidant, an anti-aging agent, a light stabilizer, an ultraviolet absorber, a thixotropic agent, a freeze stabilizer, a pH adjuster, a lubricant, a rheology control agent, and a film forming aid. These additives may be used alone or in combination of two or more thereof, depending on the purpose.
  • the slurry composition of the first invention may be prepared according to a method known per se. Specifically, the slurry composition of the first invention can be prepared, for example, by appropriately mixing the binder of the first invention, an active material, and if necessary, a conductive assistant, a supporting salt and/or an additive in a solvent so as to have the above-mentioned contents, according to a desired slurry composition.
  • the electrode of the first invention is an electrode for an electricity storage device consisting of the slurry composition of the first invention. More specifically, the electrode of the first invention is an electrode having an electrode mixture layer derived from the slurry composition of the first invention, which contains the binder of the first invention (or the binder solution according to the first invention), an active material, a solvent, and if necessary, a conductive assistant, a supporting salt and/or an additive, and a collector.
  • the electrode of the first invention can be used as both a negative electrode and a positive electrode, and is preferably used as a positive electrode.
  • the collector in the electrode of the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include a collector made of a conductive material such as platinum, copper, stainless steel (SUS), Hastelloy, aluminum, iron, chromium, nickel, titanium, Inconel, molybdenum, graphite, or carbon, and having a shape such as a plate, a foil (sheet or paper), a mesh, an expanded grid (expanded metal), or a punched metal.
  • the mesh opening, wire diameter, number of meshes, and the like of the collector are not particularly limited, and conventionally known ones can be used.
  • the thickness of the collector is usually 1 ⁇ m or more and 300 ⁇ m or less, and preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • the size of the collector is determined according to the intended use of the battery. In a case where a large electrode used for a large battery is to be prepared, a collector having a large area is used, and in a case where a small electrode is to be prepared, a collector having a small area is used.
  • the electrode of the first invention may be produced according to a method known per se. Specifically, the electrode of the first invention can be prepared, for example, by coating or crimping the slurry composition of the first invention on a collector and drying the slurry composition to form an electrode mixture layer on the collector.
  • the thickness of the electrode mixture layer is usually 1 ⁇ m or more and 1000 ⁇ m or less, preferably 1 ⁇ m or more and 500 ⁇ m or less, and more preferably 1 ⁇ m or more and 300 ⁇ m or less.
  • the amount of the slurry composition of the first invention used may be appropriately set such that the thickness of the electrode mixture layer falls within the above-mentioned range after drying.
  • the slurry composition of the first invention may be coated or crimped on the collector according to a method known per se.
  • a specific coating/crimping method for example, a self-propelled coater, an ink jet method, a doctor blade method, a spray method, a die coating method, or a combination thereof can be used.
  • the doctor blade method, the ink jet method, and the die coating method capable of forming a thin layer are preferable, and the doctor blade method and the die coating method are more preferable.
  • the slurry composition of the first invention may be dried according to a method known per se, and is usually dried by a heat treatment.
  • the drying conditions during heating may be appropriately set according to the coating amount of the slurry composition of the first invention and the volatilization rate of the solvent in the slurry composition of the first invention.
  • the slurry composition may be dried, for example, in air or vacuum, usually at 50° C. or higher and 400° C. or lower, preferably 70° C. or higher and 200° C. or lower, usually for 1 hour or longer and 20 hours or shorter, preferably 3 hours or longer and 15 hours or shorter.
  • the heat treatment may be carried out twice or more by changing the drying conditions.
  • a press treatment may be carried out before and after the drying.
  • the press treatment may be carried out according to a method known per se, and specific press treatment methods include, for example, a calender roll method and a flat plate press, among which the calender roll method is preferable.
  • the electricity storage device of the first invention refers to a device, an element, or the like having the electrode of the first invention and capable of chemically, physically, or physicochemically storing electricity.
  • Specific examples thereof include devices that can be charged and discharged, such as secondary batteries (storage batteries), for example, a secondary battery with multivalent ions such as magnesium ions, a lithium ion secondary battery, a sodium ion secondary battery, a potassium ion secondary battery, a nickel hydrogen storage battery, a nickel cadmium storage battery, and a lead storage battery; and electric double layer capacitors (electric double layer condensers), for example, a lithium ion capacitor.
  • an electricity storage device using lithium ions such as a lithium ion capacitor or a lithium ion secondary battery is preferable, and the lithium ion secondary battery is more preferable.
  • the configuration of the electricity storage device of the first invention may be the same as that of a general electricity storage device commonly used in the art.
  • the electricity storage device is configured such that a positive electrode and a negative electrode are placed facing each other through a separator, and if necessary, impregnated with an electrolytic solution.
  • the electricity storage device of the first invention may be any electricity storage device provided with the electrode of the first invention as the positive electrode and/or the negative electrode.
  • a member constituting the electricity storage device of the first invention other than the electrode of the first invention a member commonly used in the art can be appropriately adopted.
  • the separator in the electricity storage device of the first invention may be a separator that electrically insulates a positive electrode and a negative electrode while allowing ions to pass therethrough, and examples thereof include a glass fiber and a microporous polymer such as porous polyolefin.
  • the porous polyolefin include porous polyethylene, porous polypropylene, and a product in which porous polyethylene and porous polypropylene are superposed to form a multi-layer.
  • the electrolytic solution in the electricity storage device of the first invention is preferably a non-aqueous electrolytic solution containing an electrolyte, an organic solvent, and an additive.
  • the electrolyte varies depending on a desired electricity storage device.
  • the desired electricity storage device is a lithium ion secondary battery
  • examples of the electrolyte include lithium salts such as LiBF 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiCl, LiBr, LiClO 4 , LiBrO 4 , LiIO 4 , LiCH 3 SO 3 , and LiCF 3 SO 3 , among which LiPF 6 is preferable.
  • the content of the electrolyte in the non-aqueous electrolytic solution is usually 0.05 mol/L or more and 15 mol/L or less and preferably 0.1 mol/L or more and 5 mol/L or less.
  • organic solvent in the non-aqueous electrolytic solution examples include ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, ⁇ -butyrolactone (lactones), and sulfolane, among which ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, and dimethyl carbonate are preferable.
  • organic solvents may be used alone or in combination of two or more thereof.
  • the additive in the non-aqueous electrolytic solution include vinylene carbonate, fluorovinylene carbonate, methylvinylene carbonate, fluoromethylvinylene carbonate, ethylvinylene carbonate, propylvinylene carbonate, butylvinylene carbonate, dipropylvinylene carbonate, 4,5-dimethylvinylene carbonate, 4,5-diethylvinylene carbonate, vinylethylene carbonate, divinylethylene carbonate, phenylethylene carbonate, diallyl carbonate, fluoroethylene carbonate, catechol carbonate, 1,3-propane sultone, and butane sultone, among which vinylene carbonate and fluoroethylene carbonate are preferable.
  • These additives may be used alone or in combination of two or more thereof.
  • the content of the additive in the non-aqueous electrolytic solution is usually 0.05% by mass or more and 15% by mass or less and preferably 0.1% by mass or more and 5% by mass or less.
  • the non-aqueous electrolytic solution in the electricity storage device of the first invention may contain additives such as a film forming agent, an overcharge inhibitor, an oxygen scavenger, a dehydrating agent, and a flame retardant, and a coordinating additive such as crown ether, which are commonly used in the art, in addition to an electrolyte and an organic solvent.
  • additives such as a film forming agent, an overcharge inhibitor, an oxygen scavenger, a dehydrating agent, and a flame retardant, and a coordinating additive such as crown ether, which are commonly used in the art, in addition to an electrolyte and an organic solvent.
  • the shape of the electricity storage device of the first invention is not particularly limited.
  • a shape commonly used in the art such as a wound type or a laminated type as an internal shape, and a coin type, a laminated type (pouch type), a square type, or a cylindrical type as an external shape, can be appropriately adopted.
  • the binder according to the second invention contains a salt of a polymer which contains structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group and is neutralized with a monoamine, a polyvalent amine having an amine value of less than 21, and/or an onium hydroxide (hereinafter, sometimes referred to simply as the polymer according to the second invention).
  • a salt of a polymer which contains structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group,
  • each of the monomer of (i) and the monomer of (ii) in the polymer according to the second invention include the same specific examples of each of the monomer of (i) and the monomer of (ii) in the polymer according to the first invention, and preferred specific examples thereof are also the same.
  • the content ratio (molar ratio) of the structural unit derived from the monomer of (i) to the structural unit derived from the monomer of (ii) in the polymer according to the second invention is the same as the content ratio in the polymer according to the first invention.
  • the polymer according to the second invention may further contain a structural unit derived from (iii) a monomer having two or more polymerizable unsaturated groups, in addition to the monomer of (i) and the monomer of (ii).
  • a structural unit derived from (iii) a monomer having two or more polymerizable unsaturated groups in addition to the monomer of (i) and the monomer of (ii).
  • Specific examples of the monomer of (iii) in the polymer according to the second invention include the same specific examples of the monomer of (iii) in the polymer according to the first invention, and preferred specific examples thereof are also the same.
  • the content thereof is the same as the content of the monomer of (iii) in a case where the polymer according to the first invention contains a structural unit derived from the monomer of (iii).
  • the polymer according to the second invention may appropriately contain a structural unit derived from a monomer commonly used in the art, in addition to the monomer of (i), the monomer of (ii), and the monomer of (iii).
  • the monomer is the same as the another monomer in the polymer according to the first invention, and the content thereof is also the same as the content of the another monomer in a case where the polymer according to the first invention contains a structural unit derived from the another monomer.
  • the polymer according to the second invention may contain two or more structural units derived from the monomer of (i), the monomer of (ii), and the monomer of (iii), respectively.
  • Specific examples of the polymer according to the second invention include the same specific examples of the polymer according to the first invention, and preferred specific examples thereof are also the same.
  • the polymer according to the second invention is a salt of a polymer neutralized with a monoamine, a polyvalent amine having an amine value of less than 21, and/or an onium hydroxide (hereinafter, sometimes referred to simply as a neutralizing agent according to the second invention).
  • the polymer according to the second invention is preferably a polymer in which a part or all of carboxy groups in the structural unit derived from the monomer of (i) and/or sulfo groups or phosphate groups in the structural unit derived from the monomer of (ii) are neutralized by the neutralizing agent according to the second invention.
  • the monoamine in the neutralizing agent according to the second invention is a monovalent amine having only one basic functional group.
  • the monoamine include a monoamine having one amino group or a derivative thereof, such as tert-butylamine, amylamine (pentylamine), octylamine, diisopropylethylamine, dibutylamine, triethylamine, benzylamine, aniline, monoethanolamine, N,N-diethylethanolamine, bis(2-cyanoethyl)amine, tris(2-cyanoethyl)amine, 3-aminopropionitrile, 3-methoxypropylamine, 3-aminotriazole, or 3-aminopropyltrimethoxysilane; a monoamine having one amidino group (amidine structure) or a derivative thereof, such as diazabicyclononene; a monoamine having one guanidino group (guanidine structure) or a derivative thereof, such as te
  • monoethanolamine, N,N-diethylethanolamine, 3-methoxypropylamine, and 3-aminotriazole are preferable, and 3-methoxypropylamine and 3-aminotriazole are particularly preferable.
  • the polyvalent amine having an amine value of less than 21 in the neutralizing agent according to the second invention refers to a polyvalent amine which has two or more basic functional groups and has an amine value of less than 21, indicating an amount of the basic functional groups in a structure thereof.
  • a polyvalent amine having a low molecular weight is preferable among the polyvalent amines. Specifically, the polyvalent amine having a molecular weight of 600 or less is preferable.
  • 3,5-diaminotriazole, poly(propylene glycol) bis(2-aminopropyl ether), and O,O′-bis(2-aminopropyl)polypropylene glyco-block-polyethylene glycol-block-polypropylene glycol are preferable, and 3,5-diaminotriazole and O,O′-bis(2-aminopropyl)polypropylene glyco-block-polyethylene glycol-block-polypropylene glycol are particularly preferable.
  • Examples of the onium hydroxide in the neutralizing agent according to the second invention include ammonium hydroxide, phosphonium hydroxide, and sulfonium hydroxide, which may have a substituent.
  • Specific examples thereof include an ammonium hydroxide such as benzyltrimethylammonium hydroxide or tetrabutylammonium hydroxide; a phosphonium hydroxide such as tetrabutylphosphonium hydroxide; and a sulfonium hydroxide such as trimethylsulfonium hydroxide.
  • ammonium hydroxide is preferable, and benzyltrimethylammonium hydroxide or tetrabutylammonium hydroxide is particularly preferable.
  • a conventionally known neutralizing agent may be used in combination, in addition to the neutralizing agent according to the second invention.
  • the neutralizing agent used in combination include inorganic bases such as hydroxides, carbonates, and hydrogen carbonates of alkali metals or alkaline earth metals.
  • Specific examples thereof include a hydroxide of an alkali metal such as sodium hydroxide, lithium hydroxide, or potassium hydroxide; a carbonate of an alkali metal such as sodium carbonate, lithium carbonate, or potassium carbonate; a hydrogen carbonate of an alkali metal such as lithium hydrogen carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate; a hydroxide of an alkaline earth metal such as magnesium hydroxide or calcium hydroxide; and a carbonate of an alkaline earth metal such as magnesium carbonate or calcium carbonate.
  • a hydroxide of an alkali metal is preferable, and sodium hydroxide is particularly preferable.
  • the neutralizing agent to be used in combination only one type thereof may be used in combination with the neutralizing agent according to the second invention, or two or more types thereof may be used in combination with the neutralizing agent according to the second invention. It is preferable to use only one type thereof in combination with the neutralizing agent according to the second invention. In particular, it is preferable to use only one hydroxide of an alkali metal in combination with the neutralizing agent according to the second invention.
  • the degree of neutralization of the polymer according to the second invention is usually 50% or more and 300% or less, preferably 60% or more and 200% or less, and more preferably 70% or more and 150% or less. It should be noted that the degree of neutralization referred to here represents a ratio of the total number of moles of the neutralizing agent according to the second invention to the total number of moles of the carboxy group, the sulfo group, and the phosphate group contained in the polymer according to the second invention. Incorporation of the polymer according to the second invention in the binder of the second invention leads to improved flexibility of an electrode to be produced, which makes it possible to produce an electrode having excellent winding properties.
  • the polymer according to the second invention may be produced by carrying out a polymerization reaction and neutralization according to a method known per se.
  • the polymer according to the second invention may be produced in such a manner that the same polymerization reaction as that of the polymer according to the first invention is carried out, and the polymer obtained by the polymerization reaction is neutralized by adding an amount of the neutralizing agent according to the second invention to obtain a desired degree of neutralization.
  • the solvent used for neutralization include the same solvents as those used in the polymerization reaction of the polymer according to the first invention.
  • the binder of the second invention may be contained in a slurry composition of the second invention or an electrode of the second invention which will be described later, in a form dissolved in a solvent.
  • a solution in which the binder is dissolved in a solvent is referred to as a “binder solution”, and in particular, a solution in which the binder of the second invention is dissolved in a solvent is referred to as a “binder solution according to the second invention”.
  • the solvent in the binder solution according to the second invention examples include the same solvents as those in the binder solution according to the first invention, and preferred examples thereof are also the same. It should be noted that, in a case where the solvent is water, the binder solution may be referred to as “the binder aqueous solution according to the second invention”.
  • the content (mass of solid content) of the binder of the second invention in the binder solution according to the second invention may be appropriately set according to a desired concentration of the binder solution according to the second invention, and is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 50% by mass or less.
  • the binder solution according to the second invention may contain various additives commonly used in the art, in addition to the binder of the second invention and a solvent.
  • the additive include the same various additives in the binder solution according to the first invention, and the content thereof is also the same as the content of the additive in a case where the binder solution according to the first invention contains various additives.
  • the slurry composition of the second invention is a composition for preparing an electrode for an electricity storage device, which contains the binder of the second invention. More specifically, the slurry composition of the second invention is a composition containing an active material and a solvent, and if necessary, a conductive assistant, in addition to the binder of the second invention (or the binder solution according to the second invention).
  • the slurry composition of the second invention may be used for preparing a positive electrode or a negative electrode, and is preferably used for preparing a negative electrode.
  • the content of the binder of the second invention in the slurry composition of the second invention is usually 0.1% by mass or more and 30% by mass or less, preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less with respect to the total mass of the slurry composition of the second invention containing no solvent.
  • Examples of the active material, conductive assistant, and solvent in the slurry composition of the second invention include the same active material, conductive assistant, and solvent in the slurry composition of the first invention, and preferred examples thereof are also the same.
  • the content of the active material, the conductive assistant, and the solvent in the slurry composition of the second invention is the same as the content of the active material, the conductive assistant, and the solvent in the slurry composition of the first invention.
  • the slurry composition of the second invention may contain a supporting salt, an additive, and the like commonly used in the art, in addition to the binder of the second invention, an active material, a conductive assistant, and a solvent.
  • a supporting salt, an additive, and the like commonly used in the art in addition to the binder of the second invention, an active material, a conductive assistant, and a solvent.
  • the supporting salt and additive include the same supporting salt and additive in the slurry composition of the first invention, and the content thereof may be appropriately set according to the amount commonly used in the art.
  • the slurry composition of the second invention may be prepared according to a method known per se. Specifically, the slurry composition of the second invention can be prepared, for example, by appropriately mixing the binder of the second invention, an active material, and if necessary, a conductive assistant, a supporting salt and/or an additive in a solvent so as to have the above-mentioned contents, according to a desired slurry composition.
  • the electrode of the second invention is an electrode for an electricity storage device consisting of the slurry composition of the second invention. More specifically, the electrode of the second invention is an electrode having an electrode mixture layer derived from the slurry composition of the second invention, which contains the binder of the second invention (or the binder solution according to the second invention), an active material, a solvent, and if necessary, a conductive assistant, a supporting salt and/or an additive, and a collector.
  • the electrode of the second invention can be used as both a negative electrode and a positive electrode, and is preferably used as a positive electrode.
  • Examples of the collector in the electrode of the second invention include the same collector as in the electrode of the first invention, and preferred examples thereof are also the same.
  • the electrode of the second invention may be produced by the same production method as the electrode of the first invention.
  • the amount of the slurry composition of the second invention used may be appropriately set such that the thickness of the electrode mixture layer becomes a desired thickness after drying.
  • the coating or crimping of the slurry composition of the second invention on the collector may be carried out in the same manner as in the coating or crimping of the slurry composition of the first invention on the collector.
  • the drying of the slurry composition of the second invention may be carried out in the same manner as in the drying of the slurry composition of the first invention.
  • a press treatment may be carried out before and after the drying.
  • the press treatment may be carried out in the same manner as in the press treatment in the production of the electrode of the first invention.
  • the electricity storage device of the second invention refers to a device, an element, or the like having the electrode of the second invention and capable of chemically, physically, or physicochemically storing electricity.
  • the electricity storage device of the second invention may be the same as the electricity storage device of the first invention, and the preferred one thereof is also the same.
  • the configuration of the electricity storage device of the second invention may be the same as that of the electricity storage device of the first invention.
  • examples of the members constituting the electricity storage device of the second invention other than the electrode of the second invention include the same members as those constituting the electricity storage device of the first invention other than the electrode of the first invention, and preferred examples thereof are also the same.
  • the shape of the electricity storage device of the second invention is not particularly limited.
  • a shape commonly used in the art such as a wound type or a laminated type as an internal shape, and a coin type, a laminated type (pouch type), a square type, or a cylindrical type as an external shape, can be appropriately adopted.
  • a binder aqueous solution 2 (solid content: 10%) was obtained in the same manner as in Example 1, except that ion exchange water was used in an amount of 461 parts by mass instead of 435 parts by mass, acrylic acid was used in an amount of 5.0 parts by mass (0.069 mol) instead of 22 parts by mass, 2-hydroxyethyl acrylate was used in an amount of 45 parts by mass (0.39 mol) instead of 22 parts by mass, N,N-methylenebisacrylamide was used in an amount of 0.20 parts by mass (0.0013 mol) instead of 0.21 parts by mass, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate was used in an amount of 0.31 parts by mass instead of 0.34 parts by mass, and 48% sodium hydroxide aqueous solution was used in an amount of 4.6 parts by mass instead of 20 parts by mass.
  • a binder aqueous solution 3 (solid content: 10%) was obtained in the same manner as in Example 1, except that ion exchange water was used in an amount of 521 parts by mass instead of 435 parts by mass, acrylic acid was used in an amount of 11 parts by mass (0.15 mol) instead of 22 parts by mass, 2-hydroxyethyl acrylate was used in an amount of 44 parts by mass (0.38 mol) instead of 22 parts by mass, N,N-methylenebisacrylamide was used in an amount of 0.27 parts by mass (0.0018 mol) instead of 0.21 parts by mass, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate was used in an amount of 0.42 parts by mass instead of 0.34 parts by mass, and 48% sodium hydroxide aqueous solution was used in an amount of 4.9 parts by mass instead of 20 parts by mass.
  • a binder aqueous solution 5 (solid content: 10%) was obtained in the same manner as in Example 1, except that ion exchange water was used in an amount of 400 parts by mass instead of 435 parts by mass, acrylic acid was used in an amount of 5.0 parts by mass (0.069 mol) instead of 22 parts by mass, 2-hydroxyethyl acrylate was used in an amount of 45 parts by mass (0.39 mol) instead of 22 parts by mass, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate was used in an amount of 0.38 parts by mass instead of 0.34 parts by mass, and 48% sodium hydroxide aqueous solution was used in an amount of 4.6 parts by mass instead of 20 parts by mass, and N,N-methylenebisacrylamide was not used.
  • reaction solution was cooled to room temperature, and 7.3 parts by mass of 48% sodium hydroxide aqueous solution and 0.43 parts by mass of polyethyleneimine aqueous solution (molecular weight: about 10,000, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added to obtain a binder aqueous solution 6 (solid content: 11%).
  • reaction solution was cooled to room temperature, and 4.5 parts by mass of 48% sodium hydroxide aqueous solution and 0.19 parts by mass of polyethyleneimine aqueous solution (molecular weight: about 10,000) were added to obtain a binder aqueous solution 8 (solid content: 11%).
  • Table 1 shows the “binder component corresponding to the monomer of (i)”, the “binder component corresponding to the monomer of (ii)”, the “content ratio (molar ratio) of the structural unit derived from the monomer of (i) to the structural unit derived from the monomer of (ii)”, the “binder component corresponding to the monomer of (iii)”, and the “content (mol %) of structural units derived from the monomer of (iii) with respect to the total content of the structural units derived from the monomer of (i) and the monomer of (ii)” for the binder in each binder aqueous solution.
  • Table 1 also shows the “components of a neutralizing agent” and the “degree of neutralization (%) by the neutralizing agent” for the binder in each binder aqueous solution.
  • a planetary mixer product name: AWATORI RENTARO, Model ARE-310, manufactured by Thinky Corporation
  • 0.92 parts by mass of acetylene black (trade name: DENKA BLACK (registered trademark) powder, average particle diameter: 35 nm, specific surface area: 68 m 2 /g, manufactured by Denka Company Limited) as a conductive assistant
  • 18.1 parts by mass of water as a solvent were mixed and stirred.
  • the obtained aqueous dispersion liquid of the conductive assistant and the binder is referred to as a slurry for measurement.
  • the obtained slurry for measurement was set on a sample table.
  • the slurry for measurement was adjusted to a thickness of 1 mm with a parallel plate (PP50).
  • strain dispersion measurement was carried out using a rheometer (product name: MCR 102, manufactured by Anton Paar GmbH) at a measurement temperature of 25° C., a frequency of 1 Hz, and a strain amount in a range of 10 ⁇ 2 % to 10 3 %.
  • the loss tangent tan ⁇ (loss elastic modulus G′′/storage elastic modulus G′) in the linear region of the slurry for measurement was calculated from the obtained values of the storage elastic modulus G′ and the loss elastic modulus G′′.
  • the following components were weighed: 2.1 g of carbon-coated SiO powder (particle size: 5 ⁇ m, manufactured by Osaka Titanium Technologies Co., Ltd.), 5.0 g of natural graphite (particle size: 20 ⁇ m, manufactured by Hitachi Kasei Kogyo Kabushiki Kaisha), 0.50 g of acetylene black (trade name: DENKA BLACK (registered trademark) powder, manufactured by Denka Company Limited), and 4.0 g of the binder aqueous solution 1 (solid content: 10%) obtained in Example 1. 8.6 g of water was further added thereto.
  • the slurry composition obtained in (1) was coated to a copper collector using a doctor blade so as to have a thickness of 75 ⁇ m. Next, it was first dried in air at 80° C., and then the dried electrode was pressed with a roll press machine such that a volume density was 1.5 g/cm 3 . The pressed electrode was dried under vacuum at 150° C. for 12 hours.
  • a coin cell battery was produced in a glove box filled with argon.
  • VC vinylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • a charge/discharge test was carried out under the following conditions, using the coin cell battery produced in (3).
  • the capacity retention rate (%) after 20 cycles was calculated using the following formula, from the values of the discharge capacity of the negative electrode (the electrode obtained in (2)) after the first charge/discharge and 20 cycles.
  • Capacity retention rate (%) discharge capacity after 20 cycles/discharge capacity after first charge/discharge ⁇ 100
  • Coin cell batteries were produced in the same manner as in Experimental Example 9, except that each of the binder aqueous solutions 2 to 8 obtained in Examples 2 to 8 was used instead of the binder aqueous solution 1, and the capacity retention rate (%) after 20 cycles was calculated in a charge/discharge test.
  • Coin cell batteries were produced in the same manner as in Experimental Example 9, except that each of the binder aqueous solutions 101 to 103 obtained in Comparative Examples 1 to 3 was used instead of the binder aqueous solution 1, and the capacity retention rate (%) after 20 cycles was calculated in a charge/discharge test.
  • Table 2 shows the tan ⁇ values obtained in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 3, and the capacity retention rates obtained in Experimental Examples 9 to 16 and Comparative Experimental Examples 4 to 6.
  • the tan ⁇ of the slurry for measurement was 1 or less, and the capacity retention rate in the charge/discharge test was less than 80%. This is considered to be due to the fact that the dispersibility of the conductive assistant was insufficient with the binder having tan ⁇ 1 under the measurement conditions in the first invention, and therefore the battery using this binder could not sufficiently transmit electrons.
  • Binder aqueous solutions 10 to 34 were obtained in the same manner as in Example 9, except that each of amines shown in Table 3 below was used instead of 4.6 parts by mass of pentylamine.
  • reaction solution was cooled to room temperature, an aqueous solution prepared by adding 40 parts by mass of ion exchange water to 18.5 parts by mass of 48% sodium hydroxide aqueous solution (manufactured by Toagosei Co., Ltd.) was added dropwise, and then an aqueous solution prepared by adding 40 parts by mass of ion exchange water to 3.6 parts by mass of pentylamine (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise to obtain a binder aqueous solution 35 (solid content: 11%).
  • Binder aqueous solutions 36 to 39 were obtained in the same manner as in Example 35, except that each of the amines shown in Table 4 below was used instead of 3.6 parts by mass of pentylamine.
  • Example Concomitant amine name (parts by mass) Amine NaOH weight groups (meq./g)
  • Example 35 Pentylamine 0.73 15 80 87.16 1 11.5
  • Example 36 3-Methoxypropylamine 0.74 15 80 89.14 1 11.2
  • Example 37 3-Aminotriazole 0.70 15 80 84.08 1 11.9
  • Example 38 3,5-Diaminotriazole 0.83 15 80 99.10 2 20.2
  • An electrode for a lithium secondary battery was produced in the same manner as in (1) Preparation of slurry composition and (2) Production of electrode for lithium secondary battery in Experimental Example 9, except that the binder aqueous solution 9 obtained in Example 9 was used instead of the binder aqueous solution 1.
  • the electrode produced in (1) was cut out to a size of 10 mm ⁇ 100 mm and set in a mandrel tester (BEVS1603 cylindrical bending tester). Then, the diameter of the mandrel rod around which the electrode was wound was gradually reduced from 32 mm, and the diameter at which the electrode cracked (mandrel diameter) was measured.
  • the case where the mandrel diameter was 2 mm to 6 mm was evaluated as A; the case where the mandrel diameter was 7 mm to 9 mm was evaluated as B; the case where the mandrel diameter was 10 mm to 12 mm was evaluated as C; and the case where the mandrel diameter was 13 mm or more was evaluated as D.
  • a coin cell battery was produced in a glove box filled with argon.
  • VC vinylene carbonate
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • Table 4 shows the evaluation results obtained in the bend resistance test in Experimental Examples 17 to 42 and the capacity retention rates obtained in the charge/discharge test in Experimental Examples 17 to 42.
  • Table 6 shows the evaluation results obtained in the bend resistance test in Experimental Examples 43 to 47 and the capacity retention rates obtained in the charge/discharge test in Experimental Examples 43 to 47.

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Abstract

The present invention relates to a binder for electricity storage devices containing a salt of a polymer containing structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group and neutralized with a monoamine, a polyvalent amine having an amine value of less than 21, and/or an onium hydroxide; a slurry composition and an electrode, each of which uses this binder; an electricity storage device which is provided with this electrode; and the like.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a Continuation of PCT International Application No. PCT/JP2020/032586, filed on Aug. 28, 2020, which claims priority under 35 U.S.C. § 119(a) to Japanese Patent Application No. 2019-156698, filed on Aug. 29, 2019, Japanese Patent Application No. 2020-057233, filed on Mar. 27, 2020, and Japanese Patent Application No. 2020-125295, filed on Jul. 22, 2020. Each of the above application(s) is hereby expressly incorporated by reference, in its entirety, into the present application.
    • TECHNICAL FIELD
  • The present invention relates to a binder used in an electricity storage device, a slurry composition and an electrode, and an electricity storage device including the electrode.
    • BACKGROUND ART
  • In recent years, a battery (electricity storage device) used in a mobile terminal such as a notebook computer or a mobile phone, a hybrid car, an electric vehicle, an electrically power assisted bicycle, or the like is rapidly becoming widespread, and is required to be further reduced in size and weight. A lithium ion secondary battery having an advantage of high energy density and light weight is attracting attention as an electricity storage device used in these products.
  • Usually, an electrode used for a lithium ion secondary battery or the like contains a collector and an electrode mixture layer formed on the collector. A negative electrode mixture layer, which is an electrode mixture layer in a negative electrode, is generally formed in such a manner that a negative electrode active material typified by graphite or silicon, a conductive assistant typified by acetylene black or carbon black, a binder, and the like are dispersed or dissolved in a dispersion medium to obtain a slurry for a negative electrode mixture layer (slurry for an electrode mixture layer), the obtained slurry is coated on a collector, followed by drying, and the negative electrode active material, the conductive assistant, and the like are bound with a binder.
  • The characteristics required for this slurry for an electrode mixture layer include the uniformity in a case where an active material or a conductive assistant is dispersed or dissolved in a dispersion medium. This is because the dispersed state of the active material and the conductive assistant in the slurry for an electrode mixture layer is related to the distributed state of the active material and the conductive assistant in the electrode mixture layer, which affects the physical properties of the electrode and the battery performance. In particular, among the conductive assistants, a carbon material having excellent conductivity has a small particle size and a large specific surface area, thus exhibiting a strong cohesive force, which makes it difficult for the carbon material to be uniformly mixed and dispersed in the slurry for an electrode mixture layer. In a case where the dispersibility and particle size of the carbon material are not sufficiently controlled, the internal resistance of the electrode cannot be reduced because a uniform conductive network is not formed, and as a result, there arises a problem that the performance of the electrode material cannot be sufficiently brought out. For that reason, improving the dispersibility of the conductive assistant is an important issue.
  • Therefore, various methods for dispersing the conductive assistant in the slurry for an electrode mixture layer have been studied. For example, Patent Literature 1 and Patent Literature 2 describe an example in which a surfactant is used as a dispersant in a case where carbon black is dispersed in a solvent. In addition, Patent Literature 3 and Patent Literature 4 describe an example in which various additives are added in a case where a conductive assistant is dispersed.
  • In addition, various studies have been conducted on an electrode coated with a slurry to improve flexibility of the electrode in order to prevent cracks due to winding and trimming at the time of producing a battery, and expansion and contraction of an active material during repeated charge and discharge of the battery. For example, Patent Literature 5 and Patent Literature 6 describe an example in which a polymer containing a specific monomer component in a predetermined ratio is used. In addition, Patent Literature 7 describes an example in which flexibility of the electrode is improved by adding a composite body of carbon nanotubes.
    • CITATION LIST Patent Literature
    • Patent Literature 1: JP1988-236258A (JP-S63-236258A)
    • Patent Literature 2: JP1996-190912A (JP-H08-190912A)
    • Patent Literature 3: JP2013-206759A
    • Patent Literature 4: JP2012-195243A
    • Patent Literature 5: JP2016-155927A
    • Patent Literature 6: WO2018/003636A
    • Patent Literature 7: JP2016-054113A
    SUMMARY OF INVENTION Technical Problem
  • However, since the surfactant described in Patent Literature 1 and Patent Literature 2 has a weak adsorption force on the surface of the carbon material, the amount of the surfactant added should be increased in order to obtain good dispersion stability. As a result, there is a problem that the amount of the active material that can be contained in the electrode mixture layer is reduced and therefore the battery capacity is lowered. In addition, in a case where the adsorption of the surfactant to the carbon material is insufficient, there is a problem that the aggregation of the carbon material cannot be suppressed and therefore the dispersibility remains insufficient.
  • In addition, the dispersant described in Patent Literature 3 and Patent Literature 4 is a low-molecular-weight substance and therefore may be eluted from an electrode mixture layer into an electrolytic solution, which may adversely affect the battery performance. In addition, in a case where the dispersant to be added has poor compatibility with a binder polymer or a solvent, there is a problem that the battery performance is deteriorated.
  • On the other hand, in terms of electrode flexibility, the polymer to which the monomer described in Patent Literature 5 and Patent Literature 6 is added exhibits a main skeleton of the polymer becoming flexible and therefore has a problem that a conductive path between the active materials is lost, resulting from the expansion and contraction of the active materials due to charge and discharge of the battery, and the battery capacity is lowered. In addition, since a water-dispersible polymer has a low viscosity, there is a problem that the polymer needs to be used in combination with a thickener such as carboxymethyl cellulose.
  • In addition, since the composite body of carbon nanotubes described in Patent Literature 7 does not contain a binder polymer, the composite body may peel off from a current collecting foil of an electrode in a case where charge and discharge of the battery are repeated, and the battery may not withstand long-term use. In addition, it is necessary to increase the formulation amount of carbon nanotubes in order to increase the strength of the composite body sheet, and as a result, there is a problem that the proportion of the active material in the electrode is reduced and the energy density of the battery is lowered.
  • The present invention has been made in view of such circumstances, and the present invention provides a binder having excellent dispersibility that solves the problems described above, or a binder capable of imparting excellent flexibility to an electrode, a slurry composition and an electrode using the same, and an electricity storage device provided with the electrode.
    • Solution to Problem
  • As a result of extensive studies, the present inventors have found that an electricity storage device having excellent dispersibility of a conductive assistant and capable of maintaining a high capacity for a long period of time can be obtained by using a binder in which a loss tangent tan δ in a linear region of an aqueous dispersion liquid containing specific amounts of a conductive assistant and a binder satisfies tan δ>1 in the strain dispersion measurement in the electricity storage device. A first invention has been completed based on this finding.
  • In addition, as a result of extensive studies, the present inventors have found that the flexibility of an electrode is improved, which makes it possible to produce an electrode having excellent winding properties and an electricity storage device provided with the electrode, by using a binder containing a salt of a polymer neutralized by a specific neutralizing agent. A second invention has been completed based on this finding.
  • That is, the first invention encompasses the following inventions [i] to [xi].
  • [i] A binder for an electricity storage device, in which a loss tangent tan δ in a linear region of an aqueous dispersion liquid of 0.5% by mass of the binder and 4.6% by mass of a conductive assistant satisfies tan δ>1 in a strain dispersion measurement under measurement conditions of a measurement temperature of 25° C. and a frequency of 1 Hz, and here, the conductive assistant is an acetylene black having an average particle diameter of 30 nm or more and 40 nm or less and a specific surface area of 65 m2/g or more and 70 m2/g or less (hereinafter, sometimes referred to simply as the binder of the first invention).
  • [ii] The binder according to the invention [i], in which the binder contains a polymer or a salt thereof containing structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group.
  • [iii] The binder according to the invention [ii], in which the monomer of (ii) has a solubility in water at 20° C. of 1 g/L or more.
  • [iv] The binder according to the invention [ii] or [iii], in which the monomer of (ii) has an SP value of 11.5 (cal/cm3)1/2 or more.
  • [v] The binder according to any one of the inventions [ii] to [iv], in which the monomer of (ii) is a monomer represented by the following general formula [1].
  • Figure US20220181633A1-20220609-C00001
  • (In the general formula [1], R1 represents a hydrogen atom or a methyl group, Y1 represents —O— or —NR2—, R2 represents a hydrogen atom or a methyl group, and A1 represents a monovalent group having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group.)
  • [vi] The binder according to any one of the inventions [ii] to [v], in which the monomer of (ii) is a monomer represented by the following general formula [2].
  • Figure US20220181633A1-20220609-C00002
  • (In the general formula [2], R1 represents a hydrogen atom or a methyl group, Y1 represents —O— or —NR2—, R2 represents a hydrogen atom or a methyl group, and A2 represents an alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; or a linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof.)
  • [vii] The binder according to any one of the inventions [ii] to [vi], in which the polymer or the salt thereof further contains a structural unit derived from (iii) a monomer having two or more polymerizable unsaturated groups.
  • [viii] The binder according to any one of the inventions [ii] to [vii], in which the polymer or the salt thereof is neutralized with a hydroxide of an alkali metal and/or a polyvalent amine having an amine value of 21 or more.
  • [ix] A slurry composition for an electricity storage device containing the binder according to any one of the inventions [i] to [viii] (hereinafter, sometimes referred to simply as the slurry composition of the first invention).
  • [x] An electrode for an electricity storage device consisting of the slurry composition according to the invention [ix] (hereinafter, sometimes referred to simply as the electrode of the first invention).
  • [xi] An electricity storage device including the electrode according to the invention [x] (hereinafter, sometimes referred to simply as the electricity storage device of the first invention).
  • In addition, the second invention encompasses the following inventions [xii] to [xxi].
  • [xii] A binder for an electricity storage device (hereinafter, sometimes referred to simply as the binder of the second invention), in which the binder contains a salt of a polymer containing structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group and neutralized with a monoamine, a polyvalent amine having an amine value of less than 21, and/or an onium hydroxide.
  • [xiii] The binder according to the invention [xii], in which the polyvalent amine has a molecular weight of 600 or less.
  • [xiv] The binder according to the invention [xii] or [xiii], in which the monomer of (ii) has a solubility in water at 20° C. of 1 g/L or more.
  • [xv] The binder according to any one of the inventions [xii] to [xiv], in which the monomer of (ii) has an SP value of 11.5 (cal/cm3)1/2 or more.
  • [xvi] The binder according to any one of the inventions [xii] to [xv], in which the monomer of (ii) is a monomer represented by the following general formula [1].
  • Figure US20220181633A1-20220609-C00003
  • (In the general formula [1], R1 represents a hydrogen atom or a methyl group, Y1 represents —O— or —NR2—, R2 represents a hydrogen atom or a methyl group, and A1 represents a monovalent group having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group.)
  • [xvii] The binder according to any one of the inventions [xii] to [xvi], in which the monomer of (ii) is a monomer represented by the following general formula [2].
  • Figure US20220181633A1-20220609-C00004
  • (In the general formula [2], R1 represents a hydrogen atom or a methyl group, Y1 represents —O— or —NR2—, R2 represents a hydrogen atom or a methyl group, and A2 represents an alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; or a linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof.)
  • [xviii] A slurry composition for an electricity storage device containing the binder according to any one of the inventions [xii] to [xvii] (hereinafter, sometimes referred to simply as the slurry composition of the second invention).
  • [xix] An electrode for an electricity storage device consisting of the slurry composition according to the invention [xviii] (hereinafter, sometimes referred to simply as the electrode of the second invention).
  • [xx] An electricity storage device including the electrode according to the invention [xix] (hereinafter, sometimes referred to simply as the electricity storage device of the second invention).
    • Advantageous Effects of Invention
  • Using the binder of the first invention leads to excellent dispersibility of a conductive assistant, which makes it possible to provide an electricity storage device capable of maintaining a high capacity for a long period of time.
  • In addition, using the binder of the second invention for the production of an electrode leads to improved flexibility of the electrode, which makes it possible to provide an electrode having excellent winding properties, and an electricity storage device provided with the electrode.
    • DESCRIPTION OF EMBODIMENTS
  • Binder of First Invention
  • The binder of the first invention is a binder in which a loss tangent tan δ in a linear region of an aqueous dispersion liquid of 0.5% by mass of a binder and 4.6% by mass of a conductive assistant in the strain dispersion measurement under the measurement conditions of a measurement temperature of 25° C. and a frequency of 1 Hz satisfies tan δ>1. The upper limit value of tan δ is not particularly limited and is, for example, 1<tan δ≤100, preferably 1<tan δ≤50, and more preferably 1<tan δ≤10.
  • The “linear region” indicates a region from the time in a case where a measurement is started in the strain dispersion measurement to the time in a case where the structural disorder of a measurement sample is started, and refers to a region in which the elastic modulus obtained in the strain dispersion measurement shows a constant value regardless of the increase in the amount of strain. It should be noted that the region after the start of structural disorder (the range in which the elastic modulus decreases depending on the increase in the amount of strain) is referred to as a non-linear region.
  • The “loss tangent tan δ” indicates a ratio of a storage elastic modulus G′ and a loss elastic modulus G″ (loss elastic modulus G″/storage elastic modulus G′), where the storage elastic modulus G′ is an indicator of elastic properties and the loss elastic modulus G″ is an indicator of viscous properties. Both the storage elastic modulus G′ and the loss elastic modulus G″ can be obtained by carrying out the strain dispersion measurement.
  • Specifically, the “loss tangent tan δ” may be calculated in such a manner that the storage elastic modulus G′ and the loss elastic modulus G″ in a case where the amount of strain is increased from 10−2% to 103% are measured under the measurement conditions of a measurement temperature of 25° C. and a frequency of 1 Hz using a rheometer MCR 102 (dynamic viscoelasticity measuring device, manufactured by Anton Paar GmbH), and the loss elastic modulus G″/storage elastic modulus G′ is calculated based on the obtained values.
  • Acetylene black having an average particle diameter of 30 nm or more and 40 nm or less and a specific surface area of 65 m2/g or more and 70 m2/g or less shall be used as the “conductive assistant”. Specific examples of the acetylene black satisfying the average particle diameter conditions and the specific surface area conditions include DENKA BLACK (registered trademark) powder (manufactured by Denka Company Limited, average particle diameter: 35 nm, specific surface area: 68 m2/g, representative values posted on the home page of Denka Company Limited).
  • Ion exchange water may be used as the “water” that is a dispersion medium in the “aqueous dispersion liquid”.
  • Specific configurations of the binder of the first invention include a configuration that contains a polymer or a salt thereof containing structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group (hereinafter, sometimes referred to simply as the polymer according to the first invention).
  • (i) The ethylenically unsaturated carboxylic acid monomer (hereinafter, sometimes referred to simply as the monomer of (i)) is a monomer having both an ethylenically unsaturated group and a carboxy group in one molecule. However, the monomer of (i) has one ethylenically unsaturated group, unlike the monomer of (iii) which will be described later. In addition, the monomer of (i) may be an acid anhydride.
  • Specific examples of the monomer of (i) include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, mono(2-acryloyloxyethyl)succinate, mono(2-acryloyloxyethyl)phthalate, and mono(2-acryloyloxyethyl)hexahydrophthalate; and ethylenically unsaturated dicarboxylic acid monomers such as maleic acid, fumaric acid, itaconic acid, maleic acid anhydride, and itaconic anhydride. Among these specific examples, an ethylenically unsaturated monocarboxylic acid monomer is preferable; acrylic acid or methacrylic acid is more preferable; and acrylic acid is particularly preferable. It should be noted that the monomer of (i) may be used alone or in combination of two or more thereof, and only one type thereof is preferably used.
  • (ii) The ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group (hereinafter, sometimes referred to simply as the monomer of (ii)) is a monomer having both a “group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group” and an ethylenically unsaturated group in one molecule, and is not particularly limited as long as it is commonly used in the art. However, the monomer of (i) and the monomer of (ii) have different structures, and the hydroxy group in the monomer of (ii) does not contain a carboxy group, a sulfo group, and a phosphate group (the OH present in the carboxy group, sulfo group, and phosphate group does not correspond to the hydroxy group in the monomer of (ii)). In addition, the monomer of (ii) has one ethylenically unsaturated group, unlike the monomer of (iii) which will be described later.
  • Examples of the dialkylamino group in the monomer of (ii) include a dialkylamino group having 2 to 12 carbon atoms, among which a dialkylamino group having 2 to 8 carbon atoms is preferable. In addition, each of the two alkyl groups in the dialkylamino group may be linear, branched, or cyclic and is preferably linear or branched. Further, the two alkyl groups in the dialkylamino group may be the same or different from each other, and the two alkyl groups may be bonded to each other to form a heterocyclic structure. Specific examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a di(n-propyl)amino group, a diisopropylamino group, a di(n-butyl)amino group, a diisobutylamino group, a morpholino group, and a piperidino group.
  • Examples of the monomer of (ii) include a monomer having a high solubility in water. Specifically, the monomer of (ii) is preferably a monomer having a solubility in water at 20° C. of 1 g/L or more; more preferably a monomer having a solubility in water at 20° C. of 100 g/L or more; and particularly preferably a monomer which dissolves in water at an arbitrary ratio.
  • In addition, the monomer of (ii) preferably has an SP value of 11.5 (cal/cm3)1/2 or more. The upper limit value of the SP value of the monomer of (ii) is not particularly limited and is preferably 25 (cal/cm3)1/2 or less. It should be noted that the SP value (Solubility Parameter) in the present invention (first invention and second invention) is calculated according to the Fedors method, and can be specifically obtained from the following calculation formula.

  • Calculation formula: δ=(ΔE coh /ΔV)1/2
  • (In the calculation formula, δ represents an SP value (cal/cm3)1/2, ΔEcoh represents a molar cohesive energy (cal/mol), and ΔV represents a molar molecular volume (cm3/mol).)
  • Examples of the ethylenically unsaturated group in the monomer of (ii) include an allyl group, a vinylaryl group, a vinyloxy group, an acryloyl group, and a methacryloyl group, among which the acryloyl group and the methacryloyl group are preferable, and the acryloyl group is more preferable.
  • The monomer of (ii) may be, for example, a monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group, and having an acryloyl group or a methacryloyl group. More specifically, the monomer of (ii) may be, for example, a monomer represented by the following general formula [1].
  • Figure US20220181633A1-20220609-C00005
  • (In the general formula [1], R1 represents a hydrogen atom or a methyl group, Y1 represents —O— or —NR2—, R2 represents a hydrogen atom or a methyl group, and A1 represents a monovalent group having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group.)
  • R1 of the general formula [1] is preferably a hydrogen atom.
  • In Y1 of the general formula [1], R2 in —NR2— is preferably a hydrogen atom.
  • Y1 of the general formula Ell is preferably —O— or —NH— and more preferably —O—.
  • Examples of the dialkylamino group in A1 of the general formula [1] include the same dialkylamino groups in the monomer of (ii).
  • The “group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group” contained in A1 of the general formula [1] may be only one type or two or more types; and is preferably any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; more preferably any one of a group selected from a hydroxy group, a sulfo group, a phosphate group, or a cyano group; still more preferably any one of a group selected from a hydroxy group, a sulfo group, or a phosphate group; and particularly preferably a hydroxy group. In addition, A1 of the general formula [1] may have at least one “group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group”. Above all, A1 of the general formula [1] preferably has 1 to 3 groups, more preferably 1 or 2 groups, and particularly preferably 1 group among those groups.
  • The “monovalent group” in A1 of the general formula [1] may be, for example, an alkyl group which may have an ester bond in a chain thereof.
  • Examples of the alkyl group in a case where the “alkyl group which may have an ester bond in a chain thereof” does not have an ester bond include an alkyl group having 1 to 30 carbon atoms, among which an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is still more preferable. In addition, the alkyl group may be linear, branched, or cyclic, and is preferably linear or branched and more preferably linear.
  • Examples of the alkyl group in a case where the “alkyl group which may have an ester bond in a chain thereof” has an ester bond include an alkyl group having 3 to 66 carbon atoms, among which an alkyl group having 3 to 36 carbon atoms is preferable, an alkyl group having 5 to 24 carbon atoms is more preferable, and an alkyl group having 7 to 18 carbon atoms is still more preferable. It should be noted that the number of carbon atoms in the alkyl group also contains the number of carbon atoms in the ester bond. In addition, the alkyl group is preferably linear. Further, the number of ester bonds contained in the alkyl group may be, for example, 1 to 10 and is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2.
  • A1 of the general formula [1] may be, for example, an alkyl group which has at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group, and may have an ester bond in a chain thereof. Above all, an alkyl group having 1 to 30 carbon atoms and having 1 to 3 groups selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, and a cyano group, and an alkyl group having 3 to 66 carbon atoms and having 1 hydroxy group and 1 to 10 ester bonds in a chain thereof are preferable; an alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group, and a linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof are more preferable; and an alkyl group having 1 to 10 carbon atoms and having 1 to 2 hydroxy groups, an alkyl group having 1 to 10 carbon atoms and having one of any one of a group selected a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group, and a linear alkyl group having 5 to 24 carbon atoms and having one hydroxy group and 1 to 3 ester bonds in a chain thereof are still more preferable.
  • Specific examples of A1 of the general formula [1] include groups represented by the following general formulae [1-1] to [1-4], among which a group represented by the general formula [1-1] is preferable.
  • Figure US20220181633A1-20220609-C00006
  • (In the general formulae [1-1] to [1-4], A1-1 and A1-2 each independently represent an alkylene group having 1 to 10 carbon atoms, R3 represents a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group, a represents an integer of 0 to 4, b represents an integer of 1 to 5, c represents an integer of 1 to 6, d represents an integer of 3 to 5, and e represents an integer of 1 to 3.)
  • The alkylene group having 1 to 10 carbon atoms in A1-1 of the general formula [1-1] is preferably an alkylene group having 1 to 6 carbon atoms and more preferably an alkylene group having 1 to 4 carbon atoms. In addition, the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched and more preferably linear. Specific examples of the alkylene group include a methylene group, an ethylene group, a methylmethylene group, a trimethylene group, a propylene group, an ethylmethylene group, a dimethylmethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, an ethylethylene group, a propylmethylene group, an ethylmethylmethylene group, a pentamethylene group, a 1-methyltetramethylene group, a 1-ethyltrimethylene group, an n-propylethylene group, an n-butylmethylene group, a hexamethylene group, a 1-methylpentamethylene group, a 1-ethyltetramethylene group, a 1-n-propyltrimethylene group, an n-butylethylene group, an n-pentylmethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, a —C6H10— group, a —CH2—C6H10— group, a —C2H4—C6H10— group, a —C3H6—C6H10— group, a —C4H8—C6H10— group, a —C6H10—CH2— group, a —C6H10—C2H4— group, a —C6H10—C3H6— group, a —C6H10—C4H8— group, a —CH2—C6H10—CH2— group, and a —C2H4—C6H10—C2H4— group. Among these specific examples, a linear or branched alkylene group having 1 to 6 carbon atoms and a cyclic alkylene group having 6 to 8 carbon atoms are preferable; a linear or branched alkylene group having 1 to 4 carbon atoms is more preferable; and a linear or branched alkylene group having 2 to 4 carbon atoms is still more preferable.
  • Examples of the dialkylamino group in R3 of the general formula [1-2] include the same dialkylamino groups in the monomer of (ii).
  • Specific examples of the group represented by the general formula [1-1] include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, a 3-hydroxy-2-methylpropyl group, a 3-hydroxy-1-methylpropyl group, a 2-hydroxybutyl group, a 2-hydroxy-2-methylpropyl group, a 2-hydroxy-1-methylpropyl group, a 2-hydroxy-1,1-dimethylethyl group, a 1-hydroxybutyl group, a 1-hydroxy-1-methylpropyl group, a 5-hydroxypentyl group, a 4-hydroxypentyl group, a 2-hydroxypentyl group, a 1-hydroxypentyl group, a 6-hydroxyhexyl group, a 5-hydroxyhexyl group, a 2-hydroxyhexyl group, a 1-hydroxyhexyl group, a 7-hydroxyheptyl group, a 6-hydroxyheptyl group, a 2-hydroxyheptyl group, a 1-hydroxyheptyl group, a 8-hydroxyoctyl group, a 7-hydroxyoctyl group, a 2-hydroxyoctyl group, a 1-hydroxyoctyl group, a 9-hydroxynonyl group, a 8-hydroxynonyl group, a 2-hydroxynonyl group, a 1-hydroxynonyl group, a 10-hydroxydecyl group, a 9-hydroxydecyl group, a 2-hydroxydecyl group, a 1-hydroxydecyl group, a —C6H10—OH group, a —CH2—C6H10—CH2—OH group, and a —C2H4—C6H10—C2H4—OH group.
  • Among these specific examples, a linear or branched hydroxyalkyl group having 1 to 6 carbon atoms and a cyclic hydroxyalkyl group having 6 to 8 carbon atoms are preferable; a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms is more preferable; and a linear or branched hydroxyalkyl group having 2 to 4 carbon atoms is still more preferable. More specifically, a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, a 2-hydroxybutyl group, a 2-hydroxy-2-methylpropyl group, a 2-hydroxy-1-methylpropyl group, a 1-hydroxybutyl group, a 5-hydroxypentyl group, a 2-hydroxypentyl group, a 1-hydroxypentyl group, a 6-hydroxyhexyl group, a 5-hydroxyhexyl group, a 2-hydroxyhexyl group, a 1-hydroxyhexyl group, a —C6H10—OH group, and a —CH2—C6H10—CH2—OH group are preferable; the hydroxymethyl group, the 2-hydroxyethyl group, the 1-hydroxyethyl group, the 3-hydroxypropyl group, the 2-hydroxypropyl group, the 2-hydroxy-1-methylethyl group, the 1-hydroxypropyl group, the 4-hydroxybutyl group, the 3-hydroxybutyl group, the 2-hydroxybutyl group, the 2-hydroxy-2-methylpropyl group, the 2-hydroxy-1-methylpropyl group, the 1-hydroxybutyl group, the 5-hydroxypentyl group, the 6-hydroxyhexyl group, and the —CH2—C6H10—CH2—OH group are more preferable; the hydroxymethyl group, the 2-hydroxyethyl group, the 3-hydroxypropyl group, the 2-hydroxypropyl group, the 2-hydroxy-1-methylethyl group, the 4-hydroxybutyl group, and the 2-hydroxybutyl group are still more preferable; and the 2-hydroxyethyl group, the 2-hydroxypropyl group, the 2-hydroxy-1-methylethyl group, and the 4-hydroxybutyl groups are particularly preferable.
  • The alkylene group having 1 to 10 carbon atoms in A1-2 of the general formula [1-2] is the same as the specific examples of the alkylene group having 1 to 10 carbon atoms in A1_i of the general formula [1-1], among which a linear or branched alkylene group having 1 to 6 carbon atoms is preferable, and a linear or branched alkylene group having 1 to 4 carbon atoms is more preferable.
  • R3 of the general formula [1-2] is preferably a sulfo group, a phosphate group, or a cyano group and more preferably a sulfo group or a phosphate group.
  • Specific examples of the group represented by the general formula [1-2] include dialkylaminoalkyl groups having 3 to 12 carbon atoms such as a dimethylaminomethyl group, a 2-(dimethylamino)ethyl group, a 3-(dimethylamino)propyl group, a 4-(dimethylamino)butyl group, a diethylaminomethyl group, a 2-(diethylamino)ethyl group, a 3-(diethylamino)propyl group, a 4-(diethylamino)butyl group, a di(n-propyl)aminomethyl group, a 2-[di(n-propyl)amino] ethyl group, a 3-[di(n-propyl) amino]propyl group, a 4-[di(n-propyl)amino]butyl group, a diisopropylaminomethyl group, a 2-(diisopropylamino)ethyl group, a 3-(diisopropylamino)propyl group, a 4-(diisopropylamino)butyl group, a di(n-butyl)aminomethyl group, a 2-[di(n-butyl)amino] ethyl group, a 3-[di(n-butyl)amino]propyl group, a 4-[di(n-butyl)amino]butyl group, a diisobutylaminomethyl group, a 2-(diisobutylamino)ethyl group, a 3-(diisobutylamino)propyl group, a 4-(diisobutylamino)butyl group, a morpholinomethyl group, a 2-morpholinoethyl group, a 3-morpholinopropyl group, a 4-morpholinobutyl group, a piperidinomethyl group, a 2-piperidinoethyl group, a 3-piperidinopropyl group, and a 4-piperidinobutyl group; acetoalkyl groups having 3 to 6 carbon atoms such as an acetomethyl group, a 2-acetoethyl group, a 3-acetopropyl group, a 4-acetobutyl group, and a 1,1-dimethyl-2-acetoethyl group; sulfoalkyl groups having 1 to 6 carbon atoms such as a sulfomethyl group, a 2-sulfoethyl group, a 1-sulfoethyl group, a 3-sulfopropyl group, a 2-sulfopropyl group, a 1-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group, a 2-sulfobutyl group, a 1,1-dimethyl-2-sulfoethylene group, a 1-sulfobutyl group, a 5-sulfopentyl group, and a 6-sulfohexyl group; phosphonooxyalkyl groups having 1 to 6 carbon atoms (alkyl phosphate groups) such as a phosphonooxymethyl group, a 2-phosphonooxyethyl group, a 1-phosphonooxyethyl group, a 3-phosphonooxypropyl group, a 2-phosphonooxypropyl group, a 1-phosphonooxypropyl group, a 4-phosphonooxybutyl group, a 3-phosphonooxybutyl group, a 2-phosphonooxybutyl group, a 1-phosphonooxybutyl group, a 5-phosphonooxypentyl group, and a 6-phosphonooxyhexyl group; and cyanoalkyl groups having 2 to 7 carbon atoms such as a cyanomethyl group, a 2-cyanoethyl group, a 1-cyanoethyl group, a 3-cyanopropyl group, a 2-cyanopropyl group, a 1-cyanopropyl group, a 4-cyanobutyl group, a 3-cyanobutyl group, a 2-cyanobutyl group, a 1-cyanobutyl group, a 5-cyanopentyl group, and a 6-cyanohexyl group.
  • Among these specific examples, a linear or branched sulfoalkyl group having 1 to 4 carbon atoms, a linear phosphonooxyalkyl group having 1 to 4 carbon atoms, and a linear cyanoalkyl group having 2 to 5 carbon atoms more preferable; and the linear or branched sulfoalkyl group having 1 to 4 carbon atoms and the linear phosphonooxyalkyl group having 1 to 4 carbon atoms are more preferable. More specifically, a 2-(dimethylamino)ethyl group, a 2-(diethylamino)ethyl group, a 2-[di(n-propyeamino]ethyl group, a 2-(diisopropylamino)ethyl group, a 2-[di(n-butyl)amino]ethyl group, a 2-(diisobutylamino)ethyl group, a 2-morpholinoethyl group, a 2-piperidinoethyl group, an acetomethyl group, a 2-acetoethyl group, a 1,1-dimethyl-2-acetoethyl group, a sulfomethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 2-sulfopropyl group, a 1-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group, a 2-sulfobutyl group, a 1,1-dimethyl-2-sulfoethylene group, a phosphonooxymethyl group, a 2-phosphonooxyethyl group, a 1-phosphonooxyethyl group, a 3-phosphonooxypropyl group, a 2-phosphonooxypropyl group, a 4-phosphonooxybutyl group, a cyanomethyl group, a 2-cyanoethyl group, a 1-cyanoethyl group, a 3-cyanopropyl group, a 1-cyanopropyl group, a 4-cyanobutyl group, and a 1-cyanobutyl group are preferable; the sulfomethyl group, the 2-sulfoethyl group, the 3-sulfopropyl group, the 4-sulfobutyl group, the 1,1-dimethyl-2-sulfoethylene group, the phosphonooxymethyl group, the 2-phosphonooxyethyl group, the 3-phosphonooxypropyl group, the 4-phosphonooxybutyl group, the cyanomethyl group, the 2-cyanoethyl group, the 3-cyanopropyl group, and the 4-cyanobutyl group are more preferable; and the 2-sulfoethyl group, the 3-sulfopropyl group, and the 2-phosphonooxyethyl group are still more preferable.
  • a and b of the general formula [1-3] are each preferably an integer of 1 to 4 and is preferably 1 or 2 and more preferably 1.
  • Specific examples of the group represented by the general formula [1-3] include a 1,2-dihydroxypropyl group, a 1,3-dihydroxypropyl group, a 2,3-dihydroxypropyl group, a 1,2-dihydroxybutyl group, a 1,3-dihydroxybutyl group, a 1,4-dihydroxybutyl group, a 2,3-dihydroxybutyl group, a 2,4-dihydroxybutyl group, a 3,4-dihydroxybutyl group, a 1,2-dihydroxypentyl group, a 1,3-dihydroxypentyl group, a 1,4-dihydroxypentyl group, a 1,5-hydroxypentyl group, a 2,3-dihydroxypentyl group, a 2,4-dihydroxypentyl group, a 2,5-hydroxypentyl group, a 3,4-dihydroxypentyl group, a 3,5-dihydroxypentyl group, a 4,5-hydroxypentyl group, a 1,2-dihydroxyhexyl group, a 1,3-dihydroxyhexyl group, a 1,4-dihydroxyhexyl group, a 1,5-hydroxyhexyl group, a 1,6-hydroxyhexyl group, a 2,3-dihydroxyhexyl group, a 2,4-dihydroxyhexyl group, a 2,5-hydroxyhexyl group, a 2,6-hydroxyhexyl group, a 3,4-dihydroxyhexyl group, a 3,5-dihydroxyhexyl group, a 3,6-dihydroxyhexyl group, a 4,5-hydroxyhexyl group, a 4,6-hydroxyhexyl group, and a 5,6-hydroxyhexyl group, among which the 2,3-dihydroxypropyl group, the 2,4-dihydroxybutyl group, the 3,4-dihydroxybutyl group, the 2,5-hydroxypentyl group, the 4,5-hydroxypentyl group, the 2,6-hydroxyhexyl group, and the 5,6-hydroxyhexyl group are preferable; the 2,3-dihydroxypropyl group, the 2,4-dihydroxybutyl group, and the 3,4-dihydroxybutyl group are more preferable; and the 2,3-dihydroxypropyl group is still more preferable.
  • c of the general formula [1-4] is preferably 2 or 4 and more preferably 2.
  • d of the general formula [1-4] is preferably 3 or 5 and more preferably 5.
  • e of the general formula [1-4] is preferably 1 or 2.
  • Specific examples of the group represented by the general formula [1-4] include the groups shown below.
  • Figure US20220181633A1-20220609-C00007
  • Among these specific examples, the groups shown below are preferable.
  • Figure US20220181633A1-20220609-C00008
  • Among these specific examples, the groups shown below are more preferable.
  • Figure US20220181633A1-20220609-C00009
  • Preferred specific examples of A1 of the general formula [1] include the same specific examples of the groups represented by the general formulae [1-1] to [1-4], among which a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, a 2-hydroxybutyl group, a 2-hydroxy-2-methylpropyl group, a 2-hydroxy-1-methylpropyl group, a 1-hydroxybutyl group, a 5-hydroxypentyl group, a 6-hydroxyhexyl group, a —CH2—C6H10—CH2—OH group, a sulfomethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a 1,1-dimethyl-2-sulfoethylene group, a phosphonooxymethyl group, a 2-phosphonooxyethyl group, a 3-phosphonooxypropyl group, a 4-phosphonooxybutyl group, a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group, a 4-cyanobutyl group, a 2,3-dihydroxypropyl group, a 2,4-dihydroxybutyl group, a 3,4-dihydroxybutyl group, and the groups shown below are more preferable.
  • Figure US20220181633A1-20220609-C00010
  • Among these preferred specific examples, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-hydroxy-1-methylethyl group, a 4-hydroxybutyl group, a 2-hydroxybutyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 2-phosphonooxyethyl group, and a 2,3-dihydroxypropyl group are more preferable; and the 2-hydroxyethyl group, the 2-hydroxypropyl group, the 2-hydroxy-1-methylethyl group, and the 4-hydroxybutyl group are particularly preferable.
  • Examples of the combination of A1, R1, and Y1 in the general formula [1] include combinations 1 to 12 described in the following table. Among these combinations, combinations 1 to 10 are preferable, combinations 1, 2, 9, and 10 are more preferable, combinations 1, 2, and 9 are still more preferable, and combination 1 is particularly preferable.
  • Combination A1 R1 Y1
    1 Group represented by general formula Hydrogen —O—
    [1-1] atom
    2 Group represented by general formula Methyl —O—
    [1-1] group
    3 Group represented by general formula Hydrogen —O—
    [1-2] atom
    4 Group represented by general formula Methyl —O—
    [1-2] group
    5 Group represented by general formula Hydrogen —O—
    [1-3] atom
    6 Group represented by general formula Methyl —O—
    [1-3] group
    7 Group represented by general formula Hydrogen —O—
    [1-4] atom
    8 Group represented by general formula Methyl —O—
    [1-4] group
    9 Group represented by general formula Hydrogen —NH—
    [1-1] atom
    10 Group represented by general formula Methyl —NH—
    [1-1] group
    11 Group represented by general formula Hydrogen —NH—
    [1-2] atom
    12 Group represented by general formula Methyl —NH—
    [1-2] group
  • Preferred specific examples of the monomer represented by the general formula [1] include a monomer represented by the following general formula [2].
  • Figure US20220181633A1-20220609-C00011
  • (In the general formula [2], A2 represents an alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; or a linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof, and R1 and Y1 are as defined hereinbefore.)
  • Specific examples of the “alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group” and the “linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof” of A2 of the general formula [2] include the same specific examples of the groups represented by the general formulae [1-1] to [1-4], and preferred examples thereof are also the same.
  • A2 of the general formula [2] is preferably an alkyl group having 1 to 10 carbon atoms and having 1 to 2 hydroxy groups; an alkyl group having 1 to 10 carbon atoms and having one of any one of a group selected from a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; or a linear alkyl group having 5 to 24 carbon atoms and having 1 hydroxy group and 1 to 3 ester bonds in a chain thereof, more preferably a group represented by the general formulae [1-1] to [1-4], and still more preferably a group represented by the general formula [1-1]. More specific examples of A2 of the general formula [2] include the same preferred specific examples of A1 of the general formula [1], and preferred examples thereof are also the same.
  • Examples of the combination of A2, R1, and Y1 in the general formula [2] include the same combinations of A1, R1, and Y1 in the general formula [1], and preferred examples thereof are also the same.
  • Specific examples of the monomer represented by the general formula [2] include the following monomers.
  • Figure US20220181633A1-20220609-C00012
    Figure US20220181633A1-20220609-C00013
    Figure US20220181633A1-20220609-C00014
    Figure US20220181633A1-20220609-C00015
    Figure US20220181633A1-20220609-C00016
    Figure US20220181633A1-20220609-C00017
  • Among these specific examples, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 2-(acryloyloxy)ethanesulfonic acid, 3-(acryloyloxy)ethanesulfonic acid, 2-(acryloyloxy)ethyl acid phosphate, 2,3-dihydroxypropyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 2-(methacryloyloxy)ethanesulfonic acid, 3-(methacryloyloxy)ethanesulfonic acid, 2-(methacryloyloxy)ethyl acid phosphate, and 2,3-dihydroxypropyl methacrylate are preferable.
  • More preferred specific examples of the monomer represented by the general formula [1] include a monomer represented by the following general formula [3].
  • Figure US20220181633A1-20220609-C00018
  • (In the general formula [3], A3 represents a linear or branched alkylene group having 1 to 4 carbon atoms, and R1 is as defined hereinbefore.)
  • A3 of the general formula [3] is preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, and an ethylethylene group, among which the ethylene group, the propylene group, and the tetramethylene group are preferable; and the ethylene group and the tetramethylene group are more preferable.
  • Specific examples of the monomer represented by the general formula [3] include hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, 4-hydroxybutyl methacrylate, and 2-hydroxybutyl methacrylate, among which 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, and 4-hydroxybutyl methacrylate are preferable; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, and 4-hydroxybutyl acrylate are more preferable; and 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly preferable.
  • It should be noted that the monomer of (ii) may be used alone or in combination of two or more thereof, and it is preferable to use only one thereof alone or two thereof in combination.
  • The content ratio (molar ratio) of the structural unit derived from the monomer of (i) to the structural unit derived from the monomer of (ii) in the polymer according to the first invention is usually the monomer of (i):the monomer of (ii)=5:95 to 95:5, preferably 10:90 to 90:10, and more preferably 15:85 to 85:15. It should be noted that, in a case where two or more types of the monomer of (i) and/or the monomer of (ii) are used in combination, a ratio of the total number of moles of the structural unit derived from the monomer of (i) to the total number of moles of the structural unit derived from the monomer of (ii) may be the above-mentioned content ratio.
  • The polymer according to the first invention may further contain a structural unit derived from (iii) a monomer having two or more polymerizable unsaturated groups, in addition to the monomer of (i) and the monomer of (ii).
  • The (iii) monomer having two or more polymerizable unsaturated groups (hereinafter, sometimes referred to simply as the monomer of (iii)) has a structure different from that of the monomer of (i) and the monomer of (ii).
  • Specific examples of the polymerizable unsaturated group in the monomer of (iii) include an ethylenically unsaturated group such as a vinyloxy group, an allyl group, a vinylaryl group, an acryloyl group, or a methacryloyl group; an isocyanate group; and a carbodiimide group, among which the ethylenically unsaturated group is preferable; the allyl group, the acryloyl group, and the methacryloyl group are more preferable; and the acryloyl group is particularly preferable.
  • Examples of the monomer of (iii) include a monomer represented by the following general formula [11] or [12], among which a monomer represented by the general formula [11] is preferable.
  • Figure US20220181633A1-20220609-C00019
  • {In the general formula [11], R11 represents a hydrogen atom or a methyl group, Y11 represents —O— or —NR12—, R12 represents a hydrogen atom or a methyl group, A11 represents a group represented by the following general formulae [11-1] to [11-3], and two R11's and two Y11's are each the same:
  • Figure US20220181633A1-20220609-C00020
  • (In the general formulae [11-1] to [11-3], R13 and R14 each independently represent a hydrogen atom or a methyl group, Y12 represents —O— or —NR15—, R15 represents a hydrogen atom or a methyl group, A12 to A15 each independently represent an alkylene group having 1 to 6 carbon atoms, A16 and A17 each independently represent an alkylene group having 1 to 6 carbon atoms which may have an ether bond in a chain thereof, g represents an integer of 0 to 30, h represents an integer of 1 to 3, i represents an integer of 0 to 6, j represents an integer of 1 to 3, and two A16's, two R14's, and two Y12's are each the same.).}
  • Figure US20220181633A1-20220609-C00021
  • (In the general formula [12], R16 to R22 each independently represent an alkylene group having 1 to 3 carbon atoms.)
  • R11 of the general formula [11] is preferably a hydrogen atom.
  • In Y11 of the general formula [11], R12 in —NR12— is preferably a hydrogen atom.
  • Y11 of the general formula [11] is preferably —O— or —NH— and more preferably —NH—.
  • The alkylene group having 1 to 6 carbon atoms in A12 and A13 of the general formula [11-1] is preferably an alkylene group having 1 to 4 carbon atoms and more preferably an alkylene group having 2 to 3 carbon atoms. In addition, the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched and more preferably linear. Specific examples of the alkylene group include a methylene group, an ethylene group, a methylmethylene group, a trimethylene group, a propylene group, an ethylmethylene group, a dimethylmethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, an ethylethylene group, a propylmethylene group, an ethylmethylmethylene group, a pentamethylene group, a 1-methyltetramethylene group, a 1-ethyltrimethylene group, an n-propylethylene group, an n-butylmethylene group, a hexamethylene group, a 1-methylpentamethylene group, a 1-ethyltetramethylene group, a 1-n-propyltrimethylene group, an n-butylethylene group, an n-pentylmethylene group, and a —C6H10— group, among which a linear or branched alkylene group having 1 to 4 carbon atoms is preferable; and a methylene group, an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group are more preferable.
  • In g pieces of repeating units in the general formula [11-1], the repeating units may be the same or different. It is preferable that all the repeating units are the same. In addition, g pieces of A13's in the general formula [11-1] may be the same or different. In a case where g in the general formula [11-1] is an integer of 1 or more, it is preferable that A12 and A13 in the g-th repeating unit are the same; and it is more preferable that A12 and A13 in the g-th repeating unit are the same, and A13's in the first to g-1-th repeating units are all the same. It should be noted that the repeating unit in the general formula [11-1] is counted as the first repeating unit, the second repeating unit, . . . from the side adjacent to Au, and the g-th repeating unit is a repeating unit located at the farthest point from A12 (a repeating unit adjacent to one of Y11's in the general formula [11]).
  • g of the general formula [11-1] is preferably an integer of 0 to 15, more preferably an integer of 0 to 10, and still more preferably an integer of 0 to 3.
  • Examples of the combination of A12, A13, and gin the general formula [11-1] include combinations 1 to 29 described in the following table. Among these combinations, combinations 1, 2, 7 to 13, 15, 17 to 19, 24, and 25 are preferable, and combinations 1, 7 to 10, 12, 15, 17, 18, and 24 are more preferable.
  • Combination A12 A13 g
    1 Methylene group (None) 0
    2 Methylene group Methylene group 1
    3 Methylene group Methylene groups in all of two repeating units 2
    4 Methylene group Ethylene group in first repeating unit and methylene 2
    group in second repeating unit
    5 Methylene group Methylene groups in all of three repeating units 3
    6 Methylene group Ethylene groups in first and second repeating units 3
    and methylene group in third repeating unit
    7 Ethylene group (None) 0
    8 Ethylene group Ethylene group 1
    9 Ethylene group Ethylene groups in all of two repeating units 2
    10 Ethylene group Ethylene groups in all of three repeating units 3
    11 Ethylene group Ethylene groups in all of d pieces of repeating units 4~30
    12 Trimethylene group (None) 0
    13 Trimethylene group Trimethylene group 1
    14 Trimethylene group Trimethylene groups in all of two repeating units 2
    15 Trimethylene group Ethylene group in first repeating unit and 2
    trimethylene group in second repeating unit
    16 Trimethylene group Trimethylene groups in all of three repeating units 3
    17 Trimethylene group Ethylene groups in first and second repeating units 3
    and trimethylene group in third repeating unit
    18 Propylene group (None) 0
    19 Propylene group Propylene group 1
    20 Propylene group Propylene groups in all of two repeating units 2
    21 Propylene group Ethylene group in first repeating unit and propylene 2
    group in second repeating unit
    22 Propylene group Propylene groups in all of three repeating units 3
    23 Propylene group Ethylene groups in first and second repeating units 3
    and propylene group in third repeating unit
    24 Tetramethylene (None) 0
    group
    25 Tetramethylene Tetramethylene group 1
    group
    26 Tetramethylene Tetramethylene groups in all of two repeating units 2
    group
    27 Tetramethylene Ethylene group in first repeating unit and 2
    group tetramethylene group in second repeating unit
    28 Tetramethylene Tetramethylene groups in all of three repeating units 3
    group
    29 Tetramethylene Ethylene groups in first and second repeating units 3
    group and tetramethylene group in third repeating unit
  • In h pieces of repeating units in the general formula [11-2], the repeating units may be the same or different. It is preferable that all the repeating units are the same. In addition, h pieces of R13's in the general formula [11-2] may be the same or different. It is preferable that all R13's are the same, and it is more preferable that all R13's are the same as R11's of the general formula [11].
  • Examples of the alkylene group having 1 to 6 carbon atoms in A14 and A15 of the general formula [11-2] include the same alkylene groups having 1 to 6 carbon atoms in A12 and A13 of the general formula [11-1], among which a linear alkylene group having 1 to 4 carbon atoms is preferable and an ethylene group is more preferable.
  • h pieces of A15's in the general formula [11-2] may be the same or different. It is preferable that all A15's are the same. In addition, it is preferable that A14 of the general formula [11-2] and A15 in the h-th repeating unit are the same, and it is more preferable that A14 and A15 in all repeating units are the same. It should be noted that the repeating unit in the general formula [11-2] is counted as the first repeating unit, the second repeating unit, . . . from the side adjacent to A14, and the h-th repeating unit is a repeating unit located at the farthest point from A14 (a repeating unit adjacent to one of Y11's in the general formula [11]).
  • e of the general formula [11-2] is preferably 1 or 2.
  • Examples of the combination of A14, A15, R13, and h in the general formula [11-2] include combinations 1 to 12 described in the following table. Among these combinations, combinations 4 to 6 are preferable and combinations 4 and 5 are more preferable.
  • Combination A14 A15 R13 h
    1 Methylene group Methylene groups in Hydrogen atoms 1
    2 Methylene group all of e pieces of in all of e pieces 2
    3 Methylene group repeating units of repeating 3
    4 Ethylene group Ethylene groups in all units or Methyl 1
    5 Ethylene group of e pieces of groups in all of 2
    6 Ethylene group repeating units e pieces of 3
    7 Trimethylene group Trimethylene groups repeating units 1
    8 Trimethylene group in all of e pieces of 2
    9 Trimethylene group repeating units 3
    10 Tetramethylene group Tetramethylene groups 1
    11 Tetramethylene group in all of e pieces of 2
    12 Tetramethylene group repeating units 3
  • In j pieces of repeating units in the general formula [11-3], the repeating units may be the same or different. It is preferable that all the repeating units are the same. In addition, 2j pieces of R14's in the general formula [11-3] may be the same or different. It is preferable that all R14's are the same, and it is more preferable that all R14's are the same as R11's of the general formula [11]. In this regard, two R14's existing in the same repeating unit are always the same.
  • In Y12 of the general formula [11-3], R15 in —NR15— is preferably a hydrogen atom.
  • 2j pieces of Y11's in the general formula [11-3] may be the same or different. It is preferable that all Y11's are the same, and it is more preferable that all Y11's are the same as Y11's of the general formula [11]. In this regard, two Y12's existing in the same repeating unit are always the same.
  • Specific examples of the case where the “alkylene group having 1 to 6 carbon atoms which may have an ether bond in a chain thereof” in A16 and A17 of the general formula [11-3] does not have an ether bond include the same alkylene groups having 1 to 6 carbon atoms in A12 and A13 of the general formula [11-1], among which a linear alkylene group having 1 to 4 carbon atoms is preferable and a methylene group is more preferable.
  • Specific examples of the case where the “alkylene group having 1 to 6 carbon atoms which may have an ether bond in a chain thereof” in A16 and A17 of the general formula [11-3] has an ether bond include —CH2—O—CH2—, —CH2—O—(CH2)2—, —CH2—O—(CH2)3—, —CH2—O—(CH2)4—, —CH2—O—(CH2)5—, —(CH2)2—O—CH2—, —(CH2)2—O—(CH2)2—, —(CH2)2—O—(CH2)3—, —(CH2)2—O—(CH2)4—, —(CH2)3—O—CH2—, —(CH2)3—O—(CH2)2—, —(CH2)3—O—(CH2)3—, —(CH2)4—O—CH2—, —(CH2)4—O—(CH2)2—, and —(CH2)5—O—CH2—, among which a linear alkylene group having 2 to 4 carbon atoms and having an ether bond in a chain thereof is preferable, and —CH2—O—CH2— or —CH2—O—(CH2)3— is more preferable.
  • 2j pieces of A16's and j pieces of A17's in the general formula [11-3] may be respectively the same or different. In this regard, two A16's existing in the same repeating unit are always the same. In addition, it is preferable that all A16's of the general formula [11-3] and A17 in the j-th repeating unit are the same. It should be noted that the repeating unit in the general formula [11-3] is counted as the first repeating unit, the second repeating unit, . . . from the side adjacent to —(CH2)i—, and the j-th repeating unit is a repeating unit located at the farthest point from —(CH2)i— (a repeating unit adjacent to one of Y11's in the general formula [11]).
  • i of the general formula [11-3] is preferably an integer of 0 to 4, more preferably 0 or 1, and still more preferably 0.
  • j of the general formula [11-3] is preferably 1 or 2 and more preferably 1.
  • Examples of the combination of two A16's, A17, two Y12's, two R14's, i, and j in the general formula [11-3] include combinations 1 to 20 described in the following table. Among these combinations, combinations 1 to 6 and 11 to 16 are preferable, combinations 1, 2, 11, 12, 13, and 14 are more preferable, and combinations 1, 11, and 13 are particularly preferable. It should be noted that “—CH2—O—(CH2)3—” in the two A16's is such that a left end thereof is bonded to a main chain and a right end thereof is bonded to Y12.
  • Combination Two A16's A17 Two Y12's Two R14's i j
    1 Methylene group Methylene group —O— Hydrogen 1 1
    2 Ethylene group Ethylene group —O— atoms in all 2 1
    3 Trimethylene group Trimethylene group —O— of g pieces 3 1
    4 Tetramethylene group Tetramethylene group —O— of repeating 4 1
    5 —CH2—O—(CH2)3— —CH2—O—(CH2)3— —O— units or 0 1
    6 —CH2—O—(CH2)3— —CH2—O—(CH2)3— —O— methyl 1 1
    7 Methylene group Methylene group —NH— groups in all 1 1
    8 Ethylene group Ethylene group —NH— of g pieces 2 1
    9 Trimethylene group Trimethylene group —NH— of repeating 3 1
    10 Tetramethylene group Tetramethylene group —NH— units 4 1
    11 —CH2—O—(CH2)3— —CH2—O—(CH2)3— —NH— 0 1
    12 —CH2—O—(CH2)3— —CH2—O—(CH2)3— —NH— 1 1
    13 Methylene group —CH2—O—CH2— in first repeating unit and —O— in all of 1 2
    methylene group in second repeating unit two repeating
    units
    14 Ethylene group —CH2—O—CH2— in first repeating unit and 2 2
    ethylene group in second repeating unit
    15 Trimethylene group —CH2—O—CH2— in first repeating unit and 3 2
    trimethylene group in second repeating unit
    16 Tetramethylene group —CH2—O—CH2— in first repeating unit and 4 2
    tetramethylene group in second repeating unit
    17 Methylene group —CH2—O—CH2— in first repeating unit and —NH— in all of 1 2
    methylene group in second repeating unit two repeating
    units
    18 Ethylene group —CH2—O—CH2— in first repeating unit and 2 2
    ethylene group in second repeating unit
    19 Trimethylene group —CH2—O—CH2— in first repeating unit and 3 2
    trimethylene group in second repeating unit
    20 Tetramethylene group —CH2—O—CH2— in first repeating unit and 4 2
    tetramethylene group in second repeating unit
  • Examples of the combination of A11, two Y11's, and two R11's in the general formula [11] include combinations 1 to 14 described in the following table.
  • Two
    Combination A11 Y11's Two R11's
    1 Combinations 1 to 29 of groups —O— Hydrogen atom
    2 represented by general formula —O— Methyl group
    3 [11-1] —NH— Hydrogen atom
    4 —NH— Methyl group
    5 Combinations 1 to 12 of groups —NH— Hydrogen atom
    6 represented by general formula —NH— Methyl group
    [11-2]
    7 Combinations 1 to 6 of groups —O— Hydrogenatom
    8 represented by general formula —O— Methyl group
    [11-3]
    9 Combinations 7 to 12 of groups —NH— Hydrogen atom
    10 represented by general formula —NH— Methyl group
    [11-3]
    11 Combinations 13 to 16 of —O— Hydrogen atom
    12 groups represented by general —O— Methyl group
    formula [11-3]
    13 Combinations 17 to 20 of —NH— Hydrogen atom
    14 groups represented by general —NH— Methyl group
    formula [11-3]
  • The alkylene group having 1 to 3 carbon atoms in R16 to R22 of the general formula [12] may be linear or branched and is preferably linear. Specific examples thereof include a methylene group, an ethylene group, a methylmethylene group, a trimethylene group, a propylene group, an ethylmethylene group, and a dimethylmethylene group, among which the methylene group, the ethylene group, or the trimethylene group is preferable; the methylene group or the trimethylene group is more preferable; and the methylene group is particularly preferable.
  • R16 to R22 of the general formula [12] may be the same or different. It is preferable that R17 to R19 and R20 to R22 are respectively the same, and it is more preferable that all of R16 to R22 are the same.
  • Examples of the combination of R16 to R22 in the general formula [12] include combinations 1 to 27 described in the following table. Among these combinations, combinations 1 to 3 are preferable, combinations 1 and 3 are more preferable, and combination 1 is particularly preferable.
  • Combination R16 R17 to R19 R29 to R22
    1 Methylene group Methylene group for all Methylene group for all
    2 Methylene group Methylene group for all Ethylene group for all
    3 Methylene group Methylene group for all Trimethylene group for all
    4 Methylene group Ethylene group for all Methylene group for all
    5 Methylene group Ethylene group for all Ethylene group for all
    6 Methylene group Ethylene group for all Trimethylene group for all
    7 Methylene group Trimethylene group for all Methylene group for all
    8 Methylene group Trimethylene group for all Ethylene group for all
    9 Methylene group Trimethylene group for all Trimethylene group for all
    10 Ethylene group Methylene group for all Methylene group for all
    11 Ethylene group Methylene group for all Ethylene group for all
    12 Ethylene group Methylene group for all Trimethylene group for all
    13 Ethylene group Ethylene group for all Methylene group for all
    14 Ethylene group Ethylene group for all Ethylene group for all
    15 Ethylene group Ethylene group for all Trimethylene group for all
    16 Ethylene group Trimethylene group for all Methylene group for all
    17 Ethylene group Trimethylene group for all Ethylene group for all
    18 Ethylene group Trimethylene group for all Trimethylene group for all
    19 Trimethylene group Methylene group for all Methylene group for all
    20 Trimethylene group Methylene group for all Ethylene group for all
    21 Trimethylene group Methylene group for all Trimethylene group for all
    22 Trimethylene group Ethylene group for all Methylene group for all
    23 Trimethylene group Ethylene group for all Ethylene group for all
    24 Trimethylene group Ethylene group for all Trimethylene group for all
    25 Trimethylene group Trimethylene group for all Methylene group for all
    26 Trimethylene group Trimethylene group for all Ethylene group for all
    27 Trimethylene group Trimethylene group for all Trimethylene group for all
  • Specific examples of the monomers represented by the general formulae [11] and [12] include the following monomers.
  • Figure US20220181633A1-20220609-C00022
    Figure US20220181633A1-20220609-C00023
    Figure US20220181633A1-20220609-C00024
    Figure US20220181633A1-20220609-C00025
    Figure US20220181633A1-20220609-C00026
    Figure US20220181633A1-20220609-C00027
    Figure US20220181633A1-20220609-C00028
    Figure US20220181633A1-20220609-C00029
    Figure US20220181633A1-20220609-C00030
    Figure US20220181633A1-20220609-C00031
    Figure US20220181633A1-20220609-C00032
    Figure US20220181633A1-20220609-C00033
  • Among the above specific examples, the following monomers are preferable.
  • Figure US20220181633A1-20220609-C00034
    Figure US20220181633A1-20220609-C00035
    Figure US20220181633A1-20220609-C00036
    Figure US20220181633A1-20220609-C00037
    Figure US20220181633A1-20220609-C00038
    Figure US20220181633A1-20220609-C00039
    Figure US20220181633A1-20220609-C00040
  • Among the above preferred specific examples, methylene diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylene diacrylate, propylene diacrylate, tetramethylene diacrylate, N,N′-methylene bisacrylamide, N,N′-ethylene bisacrylamide, N,N′-(4,7,10-trioxytridecamethylene)bisacrylamide, N,N′,N″-triacryloyldiethylenetriamine, N,N′,N″,N′″-tetraacryloyltriethylenetetramine, N-[tris(3-acrylamidepropoxymethyl)methyl]acrylamide, methylene dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylene dimethacrylate, propylene dimethacrylate, tetramethylene dimethacrylate, N,N′-methylenebismethacrylamide, N,N′-ethylenebismethacrylamide, N,N′-(4,7,10-trioxytridecamethylene)bismethacrylamide, N,N′,N″-trimethacryloyldiethylenetriamine, N,N′,N″,N′″-tetramethacryloyltriethylenetetramine, N-[tris(3-methacrylamidepropoxymethyl)methyl]methacrylamide, and pentaerythritol triallyl ether are more preferable. It should be noted that these more preferred specific examples will be referred to as “a more preferred specific example group of the monomer of (iii)”.
  • As the monomer of (iii), monomers generally used as a “crosslinking agent” in the art can be appropriately used in addition to the specific examples. For example, the crosslinking agents described in WO2014/065407A, WO2015/163302A, WO2018/143382A, WO2018/143383A, and the like can be used.
  • In a case where the polymer according to the first invention contains a structural unit derived from the monomer of (iii), the content thereof is usually 0.01 mol % or more and 5 mol % or less, preferably 0.05 mol % or more and 2 mol % or less, and more preferably 0.1 mol % or more and 1 mol % or less with respect to the total content of the structural units derived from the monomer of (i) and the monomer of (ii).
  • The monomer of (i), the monomer of (ii), and the monomer of (iii) may all be commercially available or appropriately synthesized by a method known per se.
  • The polymer according to the first invention may appropriately contain a structural unit derived from a monomer commonly used in the art (hereinafter, sometimes referred to simply as another monomer), in addition to the monomer of (i), the monomer of (ii), and the monomer of (iii). In a case where the polymer according to the first invention contains a structural unit derived from the another monomer, the content thereof is usually 0.01 mol % or more and 5 mol % or less, preferably 0.05 mol % or more and 2 mol % or less, and more preferably 0.1 mol % or more and 1 mol % or less with respect to the total content of the structural units derived from the monomer of (i) and the monomer of (ii).
  • In addition, the polymer according to the first invention may contain two or more structural units derived from the monomer of (i), the monomer of (ii), and the monomer of (iii), respectively.
  • The polymer according to the first invention is preferably a polymer consisting of structural units derived from one monomer of (i) and one or two monomers of (ii), or a polymer consisting of structural units derived from one monomer of (i), one or two monomers of (ii), and one monomer of (iii); and more preferably a polymer consisting of structural units derived from one monomer of (i), and one or two monomers of (ii) having a solubility in water at 20° C. of 1 g/L or more, a polymer consisting of structural units derived from one monomer of (i), and one or two monomers of (ii) having an SP value of 11.5 (cal/cm3)1/2 or more, a polymer consisting of structural units derived from one monomer of (i), one or two monomers of (ii) having a solubility in water at 20° C. of 1 g/L or more, and one monomer of (iii), or a polymer consisting of structural units derived from one monomer of (i), one or two monomers of (ii) having an SP value of 11.5 (cal/cm3)1/2 or more, and one monomer of (iii).
  • More specifically, the polymer according to the first invention is preferably a polymer consisting of structural units derived from one ethylenically unsaturated monocarboxylic acid monomer and one or two monomers represented by the general formula [1], or a polymer consisting of structural units derived from one ethylenically unsaturated monocarboxylic acid monomer, one or two monomers represented by the general formula [1], and one monomer represented by the general formula [11]; more preferably a polymer consisting of structural units derived from one ethylenically unsaturated monocarboxylic acid monomer and one or two monomers represented by the general formula [2], or a polymer consisting of structural units derived from one ethylenically unsaturated monocarboxylic acid monomer, one or two monomers represented by the general formula [2], and one monomer represented by the general formula [11]; and still more preferably a polymer consisting of structural units derived from one acrylic acid or methacrylic acid and one or two monomers represented by the general formula [3], or a polymer consisting of structural units derived from one acrylic acid or methacrylic acid, one or two monomers represented by the general formula [3], and one monomer represented by the general formula [11].
  • Still more specifically, the polymer according to the first invention is preferably a polymer consisting of structural units derived from one acrylic acid or methacrylic acid, and one or two selected from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, or 4-hydroxybutyl acrylate, or a polymer consisting of structural units derived from one acrylic acid or methacrylic acid, one or two selected from 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-1-methylethyl acrylate, or 4-hydroxybutyl acrylate, and one selected from the more preferred specific example group of the monomer of (iii); and more preferably a polymer consisting of structural units derived from one acrylic acid and 2-hydroxyethyl acrylate and/or 4-hydroxybutyl acrylate, or a polymer consisting of structural units derived from one acrylic acid, 2-hydroxyethyl acrylate and/or 4-hydroxybutyl acrylate, and one selected from the more preferred specific example group of the monomer of (iii).
  • In a case where the polymer according to the first invention is neutralized (in a case where the polymer forms a salt), it is preferable that a part or all of the carboxy group in the structural unit derived from the monomer of (i) and/or the sulfo group or the phosphate group in the structural unit derived from the monomer of (ii) is neutralized. In addition, examples of the neutralizing agent used in a case of neutralizing the polymer according to the first invention include an inorganic base such as a hydroxide, a carbonate, or a hydrogen carbonate of an alkali metal or an alkaline earth metal; and an organic base such as a polyvalent amine having an amine value of 21 or more, an ammonium salt, an aliphatic phosphine, an aromatic phosphine, a phosphonium salt, an aliphatic thiol, an aromatic thiol, a thiol derivative, or a sulfonium salt. Specific examples of the neutralizing agent include a hydroxide of an alkali metal such as sodium hydroxide, lithium hydroxide, or potassium hydroxide; a carbonate of an alkali metal such as sodium carbonate, lithium carbonate, or potassium carbonate; a hydrogen carbonate of an alkali metal such as lithium hydrogen carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate; a hydroxide of an alkaline earth metal such as magnesium hydroxide or calcium hydroxide; a carbonate of an alkaline earth metal such as magnesium carbonate or calcium carbonate; a polyvalent amine having an amine value of 21 or more such as ethylenediamine, 1,2-propanediamine, N-methyl-1,3-propanediamine, bis(2-aminoethyl)amine, tris(2-aminoethyl)amine, or polyethyleneimine; an ammonium salt such as tetrabutylammonium tetrafluoroborate or hexadecyltrimethylammonium hexafluorophosphate; an aliphatic phosphine such as trimethylphosphine; an aromatic phosphine such as triphenylphosphine; a phosphonium salt such as tetraethylphosphonium hexafluorophosphate, or 1H-benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate; an aliphatic thiol such as 1-butanethiol; an aromatic thiol such as phenylmethanethiol or thiophene; a thiol derivative such as 2-hydroxyethyl mercaptan; and a sulfonium salt such as 1,3-benzodithiolylium tetrafluoroborate or dimethylphenacylsulfonium tetrafluoroborate. Among these specific examples, a hydroxide of an alkali metal and a polyvalent amine having an amine value of 21 or more are preferable; sodium hydroxide, lithium hydroxide, potassium hydroxide, ethylenediamine, 1,2-propanediamine, and N-methyl-1,3-propanediamine, tris(2-aminoethyl)amine, and polyethyleneimine are more preferable; and sodium hydroxide and polyethyleneimine are particularly preferable. The neutralizing agents may be used alone or in combination of two or more thereof. It is preferable to use only one neutralizing agent alone or two neutralizing agents in combination. In particular, it is preferable that only one hydroxide of an alkali metal is used alone; or one hydroxide of an alkali metal and one polyvalent amine having an amine value of 21 or more are used in combination.
  • It should be noted that the “polyvalent amine having an amine value of 21 or more” refers to a polyvalent amine which has two or more basic functional groups such as an amino group and has an amine value of 21 or more, indicating an amount of the basic functional groups in a structure thereof. The amine value in the present invention (first invention and second invention) can be specifically obtained from the calculation formula shown below. It should be noted that the basic functional group in the present invention (first invention and second invention) represents a functional group showing basicity, such as an amino group, an amidino group (amidine structure), a guanidino group (guanidine structure), a pyridino group (pyridine structure), or a phosphazeno group (phosphazene structure).

  • Calculation formula: amine value (meq./g)=number of basic functional groups/molecular weight
  • (provided that, in a case of a high molecular weight substance, the calculation shall be carried out with the molecular weight as the molecular weight per monomer unit and the number of basic functional groups as the number of basic functional groups per monomer unit.)
  • In a case where the polymer according to the first invention is neutralized, a degree of neutralization is usually 50% or more and 200% or less, preferably 60% or more and 150% or less, and more preferably 70% or more and 100% or less. It should be noted that the degree of neutralization referred to here represents a ratio of the total number of moles of the neutralizing agent to the total number of moles of the carboxy group, the sulfo group, and the phosphate group contained in the polymer according to the first invention. In a case where the binder of the first invention contains a salt of the polymer according to the first invention, the dispersibility of the conductive assistant is further improved, and the conductive assistant can be more uniformly distributed on the collector, which makes it possible to further improve the electrical characteristics of the electrode.
  • The polymer according to the first invention may be produced by carrying out a polymerization reaction according to a method known per se. Specifically, the polymer according to the first invention can be produced, for example, by subjecting the monomer of (i) and the monomer of (ii), and if necessary, the monomer of (iii) and/or the another monomer, according to a desired polymer, to a polymerization reaction in the presence of a polymerization initiator.
  • The amounts of the monomer of (i) and the monomer of (ii) used in the polymerization reaction may be appropriately set according to a content ratio (molar ratio) of the structural unit derived from the monomer of (i) to the structural unit derived from the monomer of (ii) in the polymer according to the first invention. In addition, the amount of the monomer of (iii) and/or the another monomer used in the polymerization reaction may be appropriately set according to the content in a case where the polymer according to the first invention contains a structural unit derived from the monomer of (iii) and/or the another monomer.
  • The polymerization reaction may be carried out according to a method known per se. Specifically, the reaction may be carried out in a suitable solvent, usually at 30° C. or higher and 200° C. or lower, preferably 60° C. or higher and 150° C. or lower, more preferably 70° C. or higher and 100° C. or lower for usually 0.1 hours or longer and 24 hours or shorter, preferably 1 hour or longer and 10 hours or shorter.
  • The polymerization initiator is not particularly limited as long as it is commonly used in the art, and specific examples thereof include 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2-methylpropionamidine) dihydrochloride, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, 2,2′-azobis[2-(2-imidazolin-2-yl)propane], 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], ammonium persulfate (ammonium peroxodisulfate), potassium persulfate (potassium peroxodisulfate), benzoyl peroxide, and lauroyl peroxide. These polymerization initiator compounds may be used alone or in combination of two or more thereof. The amount of the polymerization initiator used is usually 0.001 mol % or more and 30 mol % or less with respect to the total mass of reactants.
  • The solvent is not particularly limited as long as it is commonly used in the art, and specific examples thereof include water, methanol, N-methyl-2-pyrrolidone (NMP), toluene, 1,4-dioxane, tetrahydrofuran, isopropanol, methyl ethyl ketone, and propylene glycol monomethyl ether acetate, among which water is preferable. These solvent compounds may be used alone or in combination of two or more thereof. The amount of the solvent used is 1 time (equal amount) or more and 20 times or less with respect to the total mass of reactants.
  • If necessary, the product obtained after the polymerization reaction may be subjected to general post-treatment operations and purification operations commonly carried out in the art. Specifically, for example, filtration, washing, extraction, concentration under reduced pressure, recrystallization, distillation, and column chromatography may be carried out.
  • In a case where the polymer according to the first invention is neutralized, the polymer according to the first invention obtained by the polymerization reaction may be neutralized according to a method known per se. Specifically, the polymer according to the first invention may be neutralized, for example, by adding the neutralizing agent in an amount such that the polymer according to the first invention has a desired degree of neutralization. Examples of the solvent used for neutralization include the same solvents as those used in the polymerization reaction.
  • Specifically, the polymer or salt thereof according to the first invention is produced as follows.
  • That is, the monomer of (i) and the monomer of (ii) in a molar ratio of 5:95 to 95:5, and if necessary, the monomer of (iii) and/or the another monomer of 0.01 mol % or more and 5 mol % or less with respect to the content of the structural units derived from the monomer of (i) and the monomer of (ii) are dissolved or dispersed in a solvent such as water in an amount equal to or more and 20 times or less the total mass of reactants, in the presence of a polymerization initiator such as 2,2′-azobis(isobutyronitrile) of 0.001 mol % or more and 30 mol % or less with respect to the total mass of the reactants. Then, a polymerization reaction is carried out at 30° C. or higher and 200° C. or lower for 0.1 hours or longer and 24 hours or shorter to produce the polymer according to the first invention. In addition, if necessary, the neutralizing agent may be added in an amount such that the obtained polymer according to the first invention has a desired degree of neutralization to obtain a salt of the polymer according to the first invention.
  • Binder Solution
  • The binder of the first invention may be contained in a slurry composition of the first invention or an electrode of the first invention which will be described later, in a form dissolved in a solvent. In the first invention, a solution in which the binder is dissolved in a solvent is referred to as a “binder solution”, and in particular, a solution in which the binder of the first invention is dissolved in a solvent is referred to as a “binder solution according to the first invention”.
  • The solvent in the binder solution according to the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include water, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, γ-butyrolactone, toluene, methyl ethyl ketone, ethyl acetate, and dioxane, among which water is preferable. These solvent compounds may be used alone or in combination of two or more thereof. It is preferable to use only one solvent compound alone. It should be noted that, in a case where the solvent is water, the binder solution may be referred to as “the binder aqueous solution according to the first invention”.
  • The content (mass of solid content) of the binder of the first invention in the binder solution according to the first invention may be appropriately set according to a desired concentration of the binder solution according to the first invention, and is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 50% by mass or less.
  • The binder solution according to the first invention may contain various additives commonly used in the art, in addition to the binder of the first invention and a solvent. Examples of various additives include a dispersant, a thickener, a metal binder (for example, aminotriazole), a reducing agent (for example, ascorbic acid), a preservative (for example, cetylpyridinium chloride), a rust inhibitor, a fungicide, an antibacterial agent, a deodorant, a leveling agent, a defoamer, a blister inhibitor, an anti-yellowing agent, an antistatic agent, a charge regulator, an electrolyte decomposition inhibitor, an antioxidant, an anti-aging agent, a light stabilizer, an ultraviolet absorber, a thixotropic agent, a freeze stabilizer, a pH adjuster, a lubricant, a rheology control agent, and a film forming aid. These additives may be used alone or in combination of two or more thereof, depending on the purpose. The content of various additives in the binder solution according to the first invention is usually 10% by mass or less, preferably 5% by mass or less, and more preferably 1% by mass or less with respect to the content of the binder of the first invention.
  • Slurry Composition of First Invention
  • The slurry composition of the first invention is a composition for preparing an electrode for an electricity storage device, which contains the binder of the first invention. More specifically, the slurry composition of the first invention is a composition containing an active material and a solvent, and if necessary, a conductive assistant, in addition to the binder of the first invention (or the binder solution according to the first invention). The slurry composition of the first invention may be used for preparing a positive electrode or a negative electrode, and is preferably used for preparing a negative electrode.
  • The content of the binder of the first invention in the slurry composition of the first invention is usually 0.1% by mass or more and 30% by mass or less, preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less with respect to the total mass of the slurry composition of the first invention containing no solvent.
  • The active material in the slurry composition of the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include carbon, silicon, germanium, tin, lead, zinc, aluminum, indium, antimony, bismuth, sodium, magnesium, titanium, and compounds containing these as elements (such as oxides), among which carbon, silicon, or a compound containing silicon as an element is preferable. These active materials may be used alone or in combination of two or more thereof.
  • Examples of the carbon include a graphite-based carbon material (graphite) such as natural graphite, artificial graphite, or expanded graphite, carbon black, activated carbon, carbon fiber, coke, soft carbon, and hard carbon. Among these specific examples, graphite such as natural graphite, artificial graphite, or expanded graphite is preferable. Examples of the natural graphite include flake graphite and vein graphite. Examples of the artificial graphite include vein graphite, vapor-grown graphite, flake graphite, and fibrous graphite.
  • Examples of the silicon or compound containing silicon as an element include silicon as well as a silicon oxide such as SiO or SiO2, and silicon bonded to a metal, SiM (M represents a metal such as magnesium, iron, calcium, cobalt, nickel, boron, copper, manganese, silver, vanadium, cerium, or zinc), among which the silicon or the silicon oxide is preferable, and the silicon is more preferable. In addition, the surface of silicon may be partially or completely coated with carbon, and examples of the surface-coated silicon include carbon-coated silicon, a silicon oxide, and silicon bonded to a metal, among which the carbon-coated silicon or the silicon oxide is preferable and the carbon-coated silicon oxide is more preferable.
  • The active material in the slurry composition of the first invention preferably contains one or more carbons and/or one or more silicons or compounds containing silicon as an element, and more preferably contains one or more carbons and one or more silicons or compounds containing silicon as an element. More specific examples of the active material include an active material containing a mixture of at least one selected from natural graphite, artificial graphite, or expanded graphite and at least one selected from silicon, a silicon oxide, carbon-coated silicon, or a carbon-coated silicon oxide, among which an active material containing natural graphite and a carbon-coated silicon oxide is preferable.
  • The average particle diameter of the active material in the slurry composition of the first invention varies depending on the type of active material used, and is usually 0.001 μm or more and 100 μm or less, preferably 0.01 μm or more and 50 μm or less, and more preferably 0.1 μm or more and 30 μm or less.
  • The content of the active material in the slurry composition of the first invention is usually 30% by mass or more and 99.9% by mass or less, preferably 40% by mass or more and 99% by mass or less, and more preferably 50% by mass or more and 98% by mass or less with respect to the total mass of the slurry composition of the first invention containing no solvent.
  • The conductive assistant in the slurry composition of the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include carbon blacks such as acetylene black, Ketjen black, furnace black, and thermal black; and nanocarbons such as carbon nanotubes and carbon nanohorns, among which the acetylene black and the Ketjen black are preferable and the acetylene black is more preferable. These conductive assistants may be used alone or in combination of two or more thereof.
  • The average particle diameter of the conductive assistant in the slurry composition of the first invention varies depending on the type of the conductive assistant used, and is usually 0.001 μm or more and 50 μm or less, preferably 0.01 μm or more and 10 μm or less, and more preferably 0.02 μm or more and 1 μm or less.
  • The content of the conductive assistant in the slurry composition of the first invention is usually 0.1% by mass or more and 40% by mass or less, preferably 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less with respect to the total mass of the slurry composition of the first invention containing no solvent.
  • The solvent in the slurry composition of the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include water, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, γ-butyrolactone, toluene, methyl ethyl ketone, ethyl acetate, and dioxane, among which water is preferable. These solvent compounds may be used alone or in combination of two or more thereof. It is preferable to use only one solvent compound alone. In addition, in a case where the binder of the first invention is contained in the slurry composition of the first invention in the form of a binder solution, the solvent in the slurry composition of the first invention is preferably the same as the solvent in the binder solution according to the first invention.
  • The slurry composition of the first invention may contain a supporting salt, an additive, and the like commonly used in the art, in addition to the binder of the first invention, an active material, a conductive assistant, and a solvent.
  • Examples of the supporting salt include Li(C2F5SO2)2N(LiBETI), LiPF6, LiBF4, LiClO4, LiAsF6, and LiCF3SO3. Examples of the additive include a dispersant, a thickener, a metal binder, a reducing agent, a preservative, a rust inhibitor, a fungicide, an antibacterial agent, a deodorant, a leveling agent, a defoamer, a blister inhibitor, an anti-yellowing agent, an antistatic agent, a charge regulator, an electrolyte decomposition inhibitor, an antioxidant, an anti-aging agent, a light stabilizer, an ultraviolet absorber, a thixotropic agent, a freeze stabilizer, a pH adjuster, a lubricant, a rheology control agent, and a film forming aid. These additives may be used alone or in combination of two or more thereof, depending on the purpose. The contents of the supporting salt and the additive may be appropriately set according to the amounts commonly used in the art.
  • The slurry composition of the first invention may be prepared according to a method known per se. Specifically, the slurry composition of the first invention can be prepared, for example, by appropriately mixing the binder of the first invention, an active material, and if necessary, a conductive assistant, a supporting salt and/or an additive in a solvent so as to have the above-mentioned contents, according to a desired slurry composition.
  • Electrode of First Invention
  • The electrode of the first invention is an electrode for an electricity storage device consisting of the slurry composition of the first invention. More specifically, the electrode of the first invention is an electrode having an electrode mixture layer derived from the slurry composition of the first invention, which contains the binder of the first invention (or the binder solution according to the first invention), an active material, a solvent, and if necessary, a conductive assistant, a supporting salt and/or an additive, and a collector. The electrode of the first invention can be used as both a negative electrode and a positive electrode, and is preferably used as a positive electrode.
  • The collector in the electrode of the first invention is not particularly limited as long as it is commonly used in the art, and specific examples thereof include a collector made of a conductive material such as platinum, copper, stainless steel (SUS), Hastelloy, aluminum, iron, chromium, nickel, titanium, Inconel, molybdenum, graphite, or carbon, and having a shape such as a plate, a foil (sheet or paper), a mesh, an expanded grid (expanded metal), or a punched metal. The mesh opening, wire diameter, number of meshes, and the like of the collector are not particularly limited, and conventionally known ones can be used. The thickness of the collector is usually 1 μm or more and 300 μm or less, and preferably 5 μm or more and 30 μm or less. The size of the collector is determined according to the intended use of the battery. In a case where a large electrode used for a large battery is to be prepared, a collector having a large area is used, and in a case where a small electrode is to be prepared, a collector having a small area is used.
  • The electrode of the first invention may be produced according to a method known per se. Specifically, the electrode of the first invention can be prepared, for example, by coating or crimping the slurry composition of the first invention on a collector and drying the slurry composition to form an electrode mixture layer on the collector. The thickness of the electrode mixture layer is usually 1 μm or more and 1000 μm or less, preferably 1 μm or more and 500 μm or less, and more preferably 1 μm or more and 300 μm or less.
  • In the production of the electrode of the first invention, the amount of the slurry composition of the first invention used may be appropriately set such that the thickness of the electrode mixture layer falls within the above-mentioned range after drying.
  • In the production of the electrode of the first invention, the slurry composition of the first invention may be coated or crimped on the collector according to a method known per se. As a specific coating/crimping method, for example, a self-propelled coater, an ink jet method, a doctor blade method, a spray method, a die coating method, or a combination thereof can be used. Among these specific examples, the doctor blade method, the ink jet method, and the die coating method capable of forming a thin layer are preferable, and the doctor blade method and the die coating method are more preferable.
  • In the production of the electrode of the first invention, the slurry composition of the first invention may be dried according to a method known per se, and is usually dried by a heat treatment. The drying conditions during heating (necessity of vacuum, drying time, and drying temperature) may be appropriately set according to the coating amount of the slurry composition of the first invention and the volatilization rate of the solvent in the slurry composition of the first invention. As a specific drying method, the slurry composition may be dried, for example, in air or vacuum, usually at 50° C. or higher and 400° C. or lower, preferably 70° C. or higher and 200° C. or lower, usually for 1 hour or longer and 20 hours or shorter, preferably 3 hours or longer and 15 hours or shorter. In addition, the heat treatment may be carried out twice or more by changing the drying conditions.
  • In the production of the electrode of the first invention, if necessary, a press treatment may be carried out before and after the drying. The press treatment may be carried out according to a method known per se, and specific press treatment methods include, for example, a calender roll method and a flat plate press, among which the calender roll method is preferable.
  • Electricity Storage Device of First Invention
  • The electricity storage device of the first invention refers to a device, an element, or the like having the electrode of the first invention and capable of chemically, physically, or physicochemically storing electricity. Specific examples thereof include devices that can be charged and discharged, such as secondary batteries (storage batteries), for example, a secondary battery with multivalent ions such as magnesium ions, a lithium ion secondary battery, a sodium ion secondary battery, a potassium ion secondary battery, a nickel hydrogen storage battery, a nickel cadmium storage battery, and a lead storage battery; and electric double layer capacitors (electric double layer condensers), for example, a lithium ion capacitor. Among these specific examples, an electricity storage device using lithium ions such as a lithium ion capacitor or a lithium ion secondary battery is preferable, and the lithium ion secondary battery is more preferable.
  • The configuration of the electricity storage device of the first invention may be the same as that of a general electricity storage device commonly used in the art. Specifically, for example, the electricity storage device is configured such that a positive electrode and a negative electrode are placed facing each other through a separator, and if necessary, impregnated with an electrolytic solution. The electricity storage device of the first invention may be any electricity storage device provided with the electrode of the first invention as the positive electrode and/or the negative electrode. As a member constituting the electricity storage device of the first invention other than the electrode of the first invention, a member commonly used in the art can be appropriately adopted.
  • The separator in the electricity storage device of the first invention may be a separator that electrically insulates a positive electrode and a negative electrode while allowing ions to pass therethrough, and examples thereof include a glass fiber and a microporous polymer such as porous polyolefin. Specific examples of the porous polyolefin include porous polyethylene, porous polypropylene, and a product in which porous polyethylene and porous polypropylene are superposed to form a multi-layer.
  • The electrolytic solution in the electricity storage device of the first invention is preferably a non-aqueous electrolytic solution containing an electrolyte, an organic solvent, and an additive. The electrolyte varies depending on a desired electricity storage device. For example, in a case where the desired electricity storage device is a lithium ion secondary battery, examples of the electrolyte include lithium salts such as LiBF4, LiPF6, LiAsF6, LiSbF6, LiAlCl4, LiCl, LiBr, LiClO4, LiBrO4, LiIO4, LiCH3SO3, and LiCF3SO3, among which LiPF6 is preferable. These lithium salts may be used alone or in combination of two or more thereof. The content of the electrolyte in the non-aqueous electrolytic solution is usually 0.05 mol/L or more and 15 mol/L or less and preferably 0.1 mol/L or more and 5 mol/L or less.
  • Specific examples of the organic solvent in the non-aqueous electrolytic solution include ethylene carbonate, dimethyl carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone (lactones), and sulfolane, among which ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, and dimethyl carbonate are preferable. These organic solvents may be used alone or in combination of two or more thereof.
  • Specific examples of the additive in the non-aqueous electrolytic solution include vinylene carbonate, fluorovinylene carbonate, methylvinylene carbonate, fluoromethylvinylene carbonate, ethylvinylene carbonate, propylvinylene carbonate, butylvinylene carbonate, dipropylvinylene carbonate, 4,5-dimethylvinylene carbonate, 4,5-diethylvinylene carbonate, vinylethylene carbonate, divinylethylene carbonate, phenylethylene carbonate, diallyl carbonate, fluoroethylene carbonate, catechol carbonate, 1,3-propane sultone, and butane sultone, among which vinylene carbonate and fluoroethylene carbonate are preferable. These additives may be used alone or in combination of two or more thereof. The content of the additive in the non-aqueous electrolytic solution is usually 0.05% by mass or more and 15% by mass or less and preferably 0.1% by mass or more and 5% by mass or less.
  • The non-aqueous electrolytic solution in the electricity storage device of the first invention may contain additives such as a film forming agent, an overcharge inhibitor, an oxygen scavenger, a dehydrating agent, and a flame retardant, and a coordinating additive such as crown ether, which are commonly used in the art, in addition to an electrolyte and an organic solvent.
  • The shape of the electricity storage device of the first invention is not particularly limited. A shape commonly used in the art, such as a wound type or a laminated type as an internal shape, and a coin type, a laminated type (pouch type), a square type, or a cylindrical type as an external shape, can be appropriately adopted.
  • Binder of Second Invention
  • The binder according to the second invention contains a salt of a polymer which contains structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group and is neutralized with a monoamine, a polyvalent amine having an amine value of less than 21, and/or an onium hydroxide (hereinafter, sometimes referred to simply as the polymer according to the second invention).
  • Specific examples of each of the monomer of (i) and the monomer of (ii) in the polymer according to the second invention include the same specific examples of each of the monomer of (i) and the monomer of (ii) in the polymer according to the first invention, and preferred specific examples thereof are also the same. In addition, the content ratio (molar ratio) of the structural unit derived from the monomer of (i) to the structural unit derived from the monomer of (ii) in the polymer according to the second invention is the same as the content ratio in the polymer according to the first invention.
  • The polymer according to the second invention may further contain a structural unit derived from (iii) a monomer having two or more polymerizable unsaturated groups, in addition to the monomer of (i) and the monomer of (ii). Specific examples of the monomer of (iii) in the polymer according to the second invention include the same specific examples of the monomer of (iii) in the polymer according to the first invention, and preferred specific examples thereof are also the same. In addition, in a case where the polymer according to the second invention contains a structural unit derived from the monomer of (iii), the content thereof is the same as the content of the monomer of (iii) in a case where the polymer according to the first invention contains a structural unit derived from the monomer of (iii).
  • The polymer according to the second invention may appropriately contain a structural unit derived from a monomer commonly used in the art, in addition to the monomer of (i), the monomer of (ii), and the monomer of (iii). The monomer is the same as the another monomer in the polymer according to the first invention, and the content thereof is also the same as the content of the another monomer in a case where the polymer according to the first invention contains a structural unit derived from the another monomer.
  • In addition, the polymer according to the second invention may contain two or more structural units derived from the monomer of (i), the monomer of (ii), and the monomer of (iii), respectively.
  • Specific examples of the polymer according to the second invention include the same specific examples of the polymer according to the first invention, and preferred specific examples thereof are also the same.
  • The polymer according to the second invention is a salt of a polymer neutralized with a monoamine, a polyvalent amine having an amine value of less than 21, and/or an onium hydroxide (hereinafter, sometimes referred to simply as a neutralizing agent according to the second invention). The polymer according to the second invention is preferably a polymer in which a part or all of carboxy groups in the structural unit derived from the monomer of (i) and/or sulfo groups or phosphate groups in the structural unit derived from the monomer of (ii) are neutralized by the neutralizing agent according to the second invention.
  • The monoamine in the neutralizing agent according to the second invention is a monovalent amine having only one basic functional group. Specific examples of the monoamine include a monoamine having one amino group or a derivative thereof, such as tert-butylamine, amylamine (pentylamine), octylamine, diisopropylethylamine, dibutylamine, triethylamine, benzylamine, aniline, monoethanolamine, N,N-diethylethanolamine, bis(2-cyanoethyl)amine, tris(2-cyanoethyl)amine, 3-aminopropionitrile, 3-methoxypropylamine, 3-aminotriazole, or 3-aminopropyltrimethoxysilane; a monoamine having one amidino group (amidine structure) or a derivative thereof, such as diazabicyclononene; a monoamine having one guanidino group (guanidine structure) or a derivative thereof, such as tetramethylguanidine or diazabicycloundecene; a monoamine having one pyridino group (pyridine structure) or a derivative thereof, such as pyridine; and a monoamine having one phosphazeno group (phosphazene structure) or a derivative thereof, such as hexafluorocyclotriphosphazene or hexachlorocyclotriphosphazene. Among these specific examples, monoethanolamine, N,N-diethylethanolamine, 3-methoxypropylamine, and 3-aminotriazole are preferable, and 3-methoxypropylamine and 3-aminotriazole are particularly preferable.
  • The polyvalent amine having an amine value of less than 21 in the neutralizing agent according to the second invention refers to a polyvalent amine which has two or more basic functional groups and has an amine value of less than 21, indicating an amount of the basic functional groups in a structure thereof. A polyvalent amine having a low molecular weight is preferable among the polyvalent amines. Specifically, the polyvalent amine having a molecular weight of 600 or less is preferable. Specific examples thereof include 3,5-diaminotriazole, 4-dimethylaminopyridine, poly(propylene glycol) bis(2-aminopropyl ether) (JEFFAMINE (registered trademark) D-400), and O,O′-bis(2-aminopropyl)polypropylene glyco-block-polyethylene glycol-block-polypropylene glycol (JEFFAMINE (registered trademark) ED-600). Among these specific examples, 3,5-diaminotriazole, poly(propylene glycol) bis(2-aminopropyl ether), and O,O′-bis(2-aminopropyl)polypropylene glyco-block-polyethylene glycol-block-polypropylene glycol are preferable, and 3,5-diaminotriazole and O,O′-bis(2-aminopropyl)polypropylene glyco-block-polyethylene glycol-block-polypropylene glycol are particularly preferable.
  • Examples of the onium hydroxide in the neutralizing agent according to the second invention include ammonium hydroxide, phosphonium hydroxide, and sulfonium hydroxide, which may have a substituent. Specific examples thereof include an ammonium hydroxide such as benzyltrimethylammonium hydroxide or tetrabutylammonium hydroxide; a phosphonium hydroxide such as tetrabutylphosphonium hydroxide; and a sulfonium hydroxide such as trimethylsulfonium hydroxide. Among these specific examples, ammonium hydroxide is preferable, and benzyltrimethylammonium hydroxide or tetrabutylammonium hydroxide is particularly preferable.
  • Among the specific examples of the neutralizing agent according to the second invention, 3-methoxypropylamine, 3-aminotriazole, 3,5-diaminotriazole, poly(propylene glycol) bis(2-aminopropyl ether) (JEFFAMINE (registered trademark) D-400), O,O′-bis(2-aminopropyl)polypropylene glyco-block-polyethylene glycol-block-polypropylene glycol (JEFFAMINE (registered trademark) ED-600), or tetrabutylammonium hydroxide is preferable; 3-methoxypropylamine, 3-aminotriazole, 3,5-diaminotriazole, poly(propylene glycol) bis(2-aminopropyl ether) (JEFFAMINE (registered trademark) D-400), or O,O′-bis(2-aminopropyl)polypropylene glyco-block-polyethylene glycol-block-polypropylene glycol (JEFFAMINE (registered trademark) ED-600) is more preferable; and 3,5-diaminotriazole or O,O′-bis(2-aminopropyl)polypropylene glyco-block-polyethylene glycol-block-polypropylene glycol (JEFFAMINE (registered trademark) ED-600) is particularly preferable. The neutralizing agent according to the second invention may be used alone or in combination of two or more thereof. It is preferable to use only one neutralizing agent alone.
  • In addition, a conventionally known neutralizing agent may be used in combination, in addition to the neutralizing agent according to the second invention. Examples of the neutralizing agent used in combination include inorganic bases such as hydroxides, carbonates, and hydrogen carbonates of alkali metals or alkaline earth metals. Specific examples thereof include a hydroxide of an alkali metal such as sodium hydroxide, lithium hydroxide, or potassium hydroxide; a carbonate of an alkali metal such as sodium carbonate, lithium carbonate, or potassium carbonate; a hydrogen carbonate of an alkali metal such as lithium hydrogen carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate; a hydroxide of an alkaline earth metal such as magnesium hydroxide or calcium hydroxide; and a carbonate of an alkaline earth metal such as magnesium carbonate or calcium carbonate. Among these specific examples, a hydroxide of an alkali metal is preferable, and sodium hydroxide is particularly preferable. With regard to the neutralizing agent to be used in combination, only one type thereof may be used in combination with the neutralizing agent according to the second invention, or two or more types thereof may be used in combination with the neutralizing agent according to the second invention. It is preferable to use only one type thereof in combination with the neutralizing agent according to the second invention. In particular, it is preferable to use only one hydroxide of an alkali metal in combination with the neutralizing agent according to the second invention.
  • The degree of neutralization of the polymer according to the second invention is usually 50% or more and 300% or less, preferably 60% or more and 200% or less, and more preferably 70% or more and 150% or less. It should be noted that the degree of neutralization referred to here represents a ratio of the total number of moles of the neutralizing agent according to the second invention to the total number of moles of the carboxy group, the sulfo group, and the phosphate group contained in the polymer according to the second invention. Incorporation of the polymer according to the second invention in the binder of the second invention leads to improved flexibility of an electrode to be produced, which makes it possible to produce an electrode having excellent winding properties.
  • The polymer according to the second invention may be produced by carrying out a polymerization reaction and neutralization according to a method known per se. Specifically, for example, the polymer according to the second invention may be produced in such a manner that the same polymerization reaction as that of the polymer according to the first invention is carried out, and the polymer obtained by the polymerization reaction is neutralized by adding an amount of the neutralizing agent according to the second invention to obtain a desired degree of neutralization. Examples of the solvent used for neutralization include the same solvents as those used in the polymerization reaction of the polymer according to the first invention.
  • Binder Solution
  • The binder of the second invention may be contained in a slurry composition of the second invention or an electrode of the second invention which will be described later, in a form dissolved in a solvent. In the second invention, a solution in which the binder is dissolved in a solvent is referred to as a “binder solution”, and in particular, a solution in which the binder of the second invention is dissolved in a solvent is referred to as a “binder solution according to the second invention”.
  • Examples of the solvent in the binder solution according to the second invention include the same solvents as those in the binder solution according to the first invention, and preferred examples thereof are also the same. It should be noted that, in a case where the solvent is water, the binder solution may be referred to as “the binder aqueous solution according to the second invention”.
  • The content (mass of solid content) of the binder of the second invention in the binder solution according to the second invention may be appropriately set according to a desired concentration of the binder solution according to the second invention, and is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 50% by mass or less.
  • The binder solution according to the second invention may contain various additives commonly used in the art, in addition to the binder of the second invention and a solvent. Examples of the additive include the same various additives in the binder solution according to the first invention, and the content thereof is also the same as the content of the additive in a case where the binder solution according to the first invention contains various additives.
  • Slurry Composition of Second Invention
  • The slurry composition of the second invention is a composition for preparing an electrode for an electricity storage device, which contains the binder of the second invention. More specifically, the slurry composition of the second invention is a composition containing an active material and a solvent, and if necessary, a conductive assistant, in addition to the binder of the second invention (or the binder solution according to the second invention). The slurry composition of the second invention may be used for preparing a positive electrode or a negative electrode, and is preferably used for preparing a negative electrode.
  • The content of the binder of the second invention in the slurry composition of the second invention is usually 0.1% by mass or more and 30% by mass or less, preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less with respect to the total mass of the slurry composition of the second invention containing no solvent.
  • Examples of the active material, conductive assistant, and solvent in the slurry composition of the second invention include the same active material, conductive assistant, and solvent in the slurry composition of the first invention, and preferred examples thereof are also the same. In addition, the content of the active material, the conductive assistant, and the solvent in the slurry composition of the second invention is the same as the content of the active material, the conductive assistant, and the solvent in the slurry composition of the first invention.
  • The slurry composition of the second invention may contain a supporting salt, an additive, and the like commonly used in the art, in addition to the binder of the second invention, an active material, a conductive assistant, and a solvent. Examples of the supporting salt and additive include the same supporting salt and additive in the slurry composition of the first invention, and the content thereof may be appropriately set according to the amount commonly used in the art.
  • The slurry composition of the second invention may be prepared according to a method known per se. Specifically, the slurry composition of the second invention can be prepared, for example, by appropriately mixing the binder of the second invention, an active material, and if necessary, a conductive assistant, a supporting salt and/or an additive in a solvent so as to have the above-mentioned contents, according to a desired slurry composition.
  • Electrode of Second Invention
  • The electrode of the second invention is an electrode for an electricity storage device consisting of the slurry composition of the second invention. More specifically, the electrode of the second invention is an electrode having an electrode mixture layer derived from the slurry composition of the second invention, which contains the binder of the second invention (or the binder solution according to the second invention), an active material, a solvent, and if necessary, a conductive assistant, a supporting salt and/or an additive, and a collector. The electrode of the second invention can be used as both a negative electrode and a positive electrode, and is preferably used as a positive electrode.
  • Examples of the collector in the electrode of the second invention include the same collector as in the electrode of the first invention, and preferred examples thereof are also the same.
  • The electrode of the second invention may be produced by the same production method as the electrode of the first invention.
  • In the production of the electrode of the second invention, the amount of the slurry composition of the second invention used may be appropriately set such that the thickness of the electrode mixture layer becomes a desired thickness after drying.
  • In the production of the electrode of the second invention, the coating or crimping of the slurry composition of the second invention on the collector may be carried out in the same manner as in the coating or crimping of the slurry composition of the first invention on the collector.
  • In the production of the electrode of the second invention, the drying of the slurry composition of the second invention may be carried out in the same manner as in the drying of the slurry composition of the first invention.
  • In the production of the electrode of the second invention, if necessary, a press treatment may be carried out before and after the drying. The press treatment may be carried out in the same manner as in the press treatment in the production of the electrode of the first invention.
  • Electricity Storage Device of Second Invention
  • The electricity storage device of the second invention refers to a device, an element, or the like having the electrode of the second invention and capable of chemically, physically, or physicochemically storing electricity. Specifically, for example, the electricity storage device of the second invention may be the same as the electricity storage device of the first invention, and the preferred one thereof is also the same.
  • The configuration of the electricity storage device of the second invention may be the same as that of the electricity storage device of the first invention. In addition, examples of the members constituting the electricity storage device of the second invention other than the electrode of the second invention include the same members as those constituting the electricity storage device of the first invention other than the electrode of the first invention, and preferred examples thereof are also the same.
  • The shape of the electricity storage device of the second invention is not particularly limited. A shape commonly used in the art, such as a wound type or a laminated type as an internal shape, and a coin type, a laminated type (pouch type), a square type, or a cylindrical type as an external shape, can be appropriately adopted.
  • Hereinafter, the present invention (first invention and second invention) will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these examples.
    • EXAMPLES Example 1
  • To a 1000 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 435 parts by mass of ion exchange water, 22 parts by mass (0.31 mol) of acrylic acid (manufactured by Toagosei Co., Ltd.), 22 parts by mass (0.19 mol) of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Ltd.), and 0.21 parts by mass (0.0014 mol) of N,N-methylenebisacrylamide (manufactured by FUJIFILM Wako Pure Chemical Corporation), followed by heating under a nitrogen stream until the internal temperature reached 77° C. Next, 0.34 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate (trade name: VA-057, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added thereto, and the obtained solution was reacted at 77° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and 20 parts by mass of 48% sodium hydroxide aqueous solution (manufactured by Toagosei Co., Ltd.) were added to obtain a binder aqueous solution 1 (solid content: 10%).
    • Example 2
  • A binder aqueous solution 2 (solid content: 10%) was obtained in the same manner as in Example 1, except that ion exchange water was used in an amount of 461 parts by mass instead of 435 parts by mass, acrylic acid was used in an amount of 5.0 parts by mass (0.069 mol) instead of 22 parts by mass, 2-hydroxyethyl acrylate was used in an amount of 45 parts by mass (0.39 mol) instead of 22 parts by mass, N,N-methylenebisacrylamide was used in an amount of 0.20 parts by mass (0.0013 mol) instead of 0.21 parts by mass, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate was used in an amount of 0.31 parts by mass instead of 0.34 parts by mass, and 48% sodium hydroxide aqueous solution was used in an amount of 4.6 parts by mass instead of 20 parts by mass.
    • Example 3
  • A binder aqueous solution 3 (solid content: 10%) was obtained in the same manner as in Example 1, except that ion exchange water was used in an amount of 521 parts by mass instead of 435 parts by mass, acrylic acid was used in an amount of 11 parts by mass (0.15 mol) instead of 22 parts by mass, 2-hydroxyethyl acrylate was used in an amount of 44 parts by mass (0.38 mol) instead of 22 parts by mass, N,N-methylenebisacrylamide was used in an amount of 0.27 parts by mass (0.0018 mol) instead of 0.21 parts by mass, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate was used in an amount of 0.42 parts by mass instead of 0.34 parts by mass, and 48% sodium hydroxide aqueous solution was used in an amount of 4.9 parts by mass instead of 20 parts by mass.
    • Example 4
  • To a 1000 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 460 parts by mass of ion exchange water, 36 parts by mass (0.50 mol) of acrylic acid, 9 parts by mass (0.11 mol) of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Ltd.), and 0.20 parts by mass (0.00078 mol) of pentaerythritol triallyl ether (manufactured by FUJIFILM Wako Pure Chemical Corporation), followed by heating under a nitrogen stream until the internal temperature reached 77° C. Next, 0.084 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate were added thereto, and the obtained solution was reacted at 77° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and 32 parts by mass of 50% sodium hydroxide aqueous solution (manufactured by Toagosei Co., Ltd.) were added to obtain a binder aqueous solution 4 (solid content: 10%).
    • Example 5
  • A binder aqueous solution 5 (solid content: 10%) was obtained in the same manner as in Example 1, except that ion exchange water was used in an amount of 400 parts by mass instead of 435 parts by mass, acrylic acid was used in an amount of 5.0 parts by mass (0.069 mol) instead of 22 parts by mass, 2-hydroxyethyl acrylate was used in an amount of 45 parts by mass (0.39 mol) instead of 22 parts by mass, 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate was used in an amount of 0.38 parts by mass instead of 0.34 parts by mass, and 48% sodium hydroxide aqueous solution was used in an amount of 4.6 parts by mass instead of 20 parts by mass, and N,N-methylenebisacrylamide was not used.
    • Example 6
  • To a 1000 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 720 parts by mass of ion exchange water, 9.0 parts by mass (0.12 mol) of acrylic acid, and 81 parts by mass (0.70 mol) of 2-hydroxyethyl acrylate, followed by heating under a nitrogen stream until the internal temperature reached 77° C. Next, 0.69 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate were added thereto, and the obtained solution was reacted at 77° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and 7.3 parts by mass of 48% sodium hydroxide aqueous solution and 0.43 parts by mass of polyethyleneimine aqueous solution (molecular weight: about 10,000, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added to obtain a binder aqueous solution 6 (solid content: 11%).
    • Example 7
  • To a 1000 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 350 parts by mass of ion exchange water, 5.0 parts by mass (0.069 mol) of acrylic acid, 40 parts by mass (0.34 mol) of 2-hydroxyethyl acrylate, and 5.0 parts by mass (0.035 mol) of 4-hydroxybutyl acrylate, followed by heating under a nitrogen stream until the internal temperature reached 77° C. Next, 0.38 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate were added thereto, and the obtained solution was reacted at 77° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and 4.5 parts by mass of 48% sodium hydroxide aqueous solution were added to obtain a binder aqueous solution 7 (solid content: 11%).
    • Example 8
  • To a 1000 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 320 parts by mass of ion exchange water, 4.0 parts by mass (0.056 mol) of acrylic acid, 32 parts by mass (0.28 mol) of 2-hydroxyethyl acrylate, and 4.0 parts by mass (0.028 mol) of 4-hydroxybutyl acrylate, followed by heating under a nitrogen stream until the internal temperature reached 77° C. Next, 0.31 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate were added thereto, and the obtained solution was reacted at 77° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and 4.5 parts by mass of 48% sodium hydroxide aqueous solution and 0.19 parts by mass of polyethyleneimine aqueous solution (molecular weight: about 10,000) were added to obtain a binder aqueous solution 8 (solid content: 11%).
    • Comparative Example 1
  • To a 1000 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 420 parts by mass of ion exchange water, 40 parts by mass (0.59 mol) of acrylic acid, and 0.24 parts by mass (0.0016 mol) of N,N-methylenebisacrylamide, followed by heating under a nitrogen stream until the internal temperature reached 77° C. Next, 0.30 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate were added thereto, and the obtained solution was reacted at 77° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and 37 parts by mass of 48% sodium hydroxide aqueous solution were added to obtain a binder aqueous solution 101 (solid content: 10%).
    • Comparative Example 2
  • To a 200 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 135 parts by mass of ion exchange water and 15 parts by mass (0.13 mol) of 2-hydroxyethyl acrylate, followed by heating under a nitrogen stream until the internal temperature reached 75° C. Next, 0.054 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate were added thereto, and the obtained solution was reacted at 75° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature to obtain a binder aqueous solution 102 (solid content: 10%).
    • Comparative Example 3
  • To a 1000 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 575 parts by mass of ion exchange water, 45 parts by mass (0.62 mol) of acrylic acid, 11 parts by mass (0.056 mol) of 2-acryloyloxyethyl acid phosphate (trade name: LIGHT ACRYLATE P-1A (N), manufactured by Kyoeisha Chemical Co., Ltd.), and 0.18 parts by mass (0.00097 mol) of diethylene glycol diallyl ether (manufactured by FUJIFILM Wako Pure Chemical Corporation), followed by heating under a nitrogen stream until the internal temperature reached 77° C. Next, 0.10 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate were added thereto, and the obtained solution was reacted at 77° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and 41 parts by mass of 48% sodium hydroxide aqueous solution were added to obtain a binder aqueous solution 103 (solid content: 10%).
  • With regard to the binder aqueous solutions 1 to 8 obtained in Examples 1 to 8 and the binder aqueous solutions 101 to 103 obtained in Comparative Examples 1 to 3, Table 1 shows the “binder component corresponding to the monomer of (i)”, the “binder component corresponding to the monomer of (ii)”, the “content ratio (molar ratio) of the structural unit derived from the monomer of (i) to the structural unit derived from the monomer of (ii)”, the “binder component corresponding to the monomer of (iii)”, and the “content (mol %) of structural units derived from the monomer of (iii) with respect to the total content of the structural units derived from the monomer of (i) and the monomer of (ii)” for the binder in each binder aqueous solution. In addition, Table 1 also shows the “components of a neutralizing agent” and the “degree of neutralization (%) by the neutralizing agent” for the binder in each binder aqueous solution.
  • TABLE 1
    Neutralizing agent
    Content Degree of Degree of
    Monomer ratio Content of neutralization neutralization
    Monomer of (ii) (i):(ii) Monomer monomer Neutralizing of neutralizing Neutralizing of neutralizing
    of (i) (ii)-1 (ii)-2 (molar ratio) of (iii) of (iii) agent 1 agent 1 agent 2 agent 2
    Binder aqueous AA 2HEA — 62:38 MBAA 0.28 mol % NaOH 80% — —
    solution 1
    (Example 1)
    Binder aqueous AA 2HEA — 15:85 MBAA 0.28 mol % NaOH 80% — —
    solution 2
    (Example 2)
    Binder aqueous AA 2HEA — 28:72 MBAA 0.34 mol % NaOH 80% — —
    solution 3
    (Example 3)
    Binder aqueous AA 4HBA — 82:18 PETE 0.13 mol % NaOH 80% — —
    solution 4
    (Example 4)
    Binder aqueous AA 2HEA — 15:85 — — NaOH 80% — —
    solution 5
    (Example 5)
    Binder aqueous AA 2HEA — 15:85 — — NaOH 72% PEI 8%
    solution 6
    (Example 6)
    Binder aqueous AA 2HEA 4HBA 16:84 — — NaOH 80% — —
    solution 7
    (Example 7)
    Binder aqueous AA 2HEA 4HBA 16:84 — — NaOH 72% PEI 8%
    solution 8
    (Example 8)
    Binder aqueous AA — — 100:0  MBAA 0.27 mol % NaOH 80% — —
    solution 101
    (Comparative
    Example 1)
    Binder aqueous — 2HEA —  0:100 — — — — — —
    solution 102
    (Comparative
    Example 2)
    Binder aqueous AA 2AOEP — 92:8  DGDA 0.14 mol % NaOH 80% — —
    solution 103
    (Comparative
    Example 3)
    AA: acrylic acid,
    2HEA: 2-hydroxyethyl acrylate,
    4HBA: 4-hydroxybutyl acrylate
    MBAA: N,N-methylenebisacrylamide,
    PETE: pentaerythritol triallyl ether
    PEI: polyethyleneimine
    2AOEP: 2-(acryloyloxy)ethyl acid phosphate,
    DGDA: diethylene glycol diallyl ether
    • Experimental Example 1
  • (1) Sample Preparation
  • Using a planetary mixer (product name: AWATORI RENTARO, Model ARE-310, manufactured by Thinky Corporation), 0.92 parts by mass of acetylene black (trade name: DENKA BLACK (registered trademark) powder, average particle diameter: 35 nm, specific surface area: 68 m2/g, manufactured by Denka Company Limited) as a conductive assistant, 1.0 parts by mass of the binder aqueous solution 1 (solid content: 10%) obtained in Example 1, and 18.1 parts by mass of water as a solvent were mixed and stirred. The obtained aqueous dispersion liquid of the conductive assistant and the binder is referred to as a slurry for measurement.
  • (2) Measuring Method of Loss Tangent Tan δ
  • The obtained slurry for measurement was set on a sample table. The slurry for measurement was adjusted to a thickness of 1 mm with a parallel plate (PP50). Then, strain dispersion measurement was carried out using a rheometer (product name: MCR 102, manufactured by Anton Paar GmbH) at a measurement temperature of 25° C., a frequency of 1 Hz, and a strain amount in a range of 10−2% to 103%. The loss tangent tan δ (loss elastic modulus G″/storage elastic modulus G′) in the linear region of the slurry for measurement was calculated from the obtained values of the storage elastic modulus G′ and the loss elastic modulus G″.
    • Experimental Examples 2 to 8
  • Slurries for measurement were prepared in the same manner as in Experimental Example 1, except that each of the binder aqueous solutions 2 to 8 obtained in Examples 2 to 8 was used instead of the binder aqueous solution 1, and then the loss tangent tan δ was calculated.
    • Comparative Experimental Examples 1 to 3
  • Slurries for measurement were prepared in the same manner as in Experimental Example 1, except that each of the binder aqueous solutions 101 to 103 obtained in Comparative Examples 1 to 3 was used instead of the binder aqueous solution 1, and then the loss tangent tan δ was calculated.
    • Experimental Example 9
  • (1) Preparation of Slurry Composition
  • The following components were weighed: 2.1 g of carbon-coated SiO powder (particle size: 5 μm, manufactured by Osaka Titanium Technologies Co., Ltd.), 5.0 g of natural graphite (particle size: 20 μm, manufactured by Hitachi Kasei Kogyo Kabushiki Kaisha), 0.50 g of acetylene black (trade name: DENKA BLACK (registered trademark) powder, manufactured by Denka Company Limited), and 4.0 g of the binder aqueous solution 1 (solid content: 10%) obtained in Example 1. 8.6 g of water was further added thereto. These components were mixed and stirred using a planetary mixer (product name: AWATORI RENTARO, Model ARE-310, manufactured by Thinky Corporation) at a rotation speed of 2000 rpm for 30 minutes. The obtained mixture was used as a slurry composition.
  • (2) Production of Electrode for Lithium Secondary Battery
  • The slurry composition obtained in (1) was coated to a copper collector using a doctor blade so as to have a thickness of 75 μm. Next, it was first dried in air at 80° C., and then the dried electrode was pressed with a roll press machine such that a volume density was 1.5 g/cm3. The pressed electrode was dried under vacuum at 150° C. for 12 hours.
  • (3) Production of Coin Cell Battery
  • A coin cell battery was produced in a glove box filled with argon. Here, a coin cell battery consisting of the electrode obtained in (2), a lithium foil electrode, a solution of 2% by mass of vinylene carbonate (VC) added to ethylene carbonate (EC)/dimethyl carbonate (DMC) (volume ratio=1:1) containing 1 M LiPF6, and a separator was assembled.
  • (4) Charge/Discharge Test
  • A charge/discharge test was carried out under the following conditions, using the coin cell battery produced in (3).
      • Counter electrode: lithium foil
      • Electrolytic solution: 1M LiPF6 EC/DMC mixed solution (volume ratio=1:1)+VC 2% by mass
      • Measuring device: ABE1024-5V 0.1A-4 charge/discharge test device (manufactured by ElectroField Co., Ltd.)
      • Charge/discharge conditions
  • First Cycle
  • Charge constant current constant voltage 0.1 C 0.02 V 15 hours termination
  • Discharge constant current 0.1 C 1.5 V termination
  • After Second Cycle
  • Charge constant current constant voltage 0.5 C 0.02 V 3 hours termination
  • Discharge constant current 0.5 C 1.5 V termination
  • The capacity retention rate (%) after 20 cycles was calculated using the following formula, from the values of the discharge capacity of the negative electrode (the electrode obtained in (2)) after the first charge/discharge and 20 cycles.
  • Capacity retention rate (%)=discharge capacity after 20 cycles/discharge capacity after first charge/discharge×100
    • Experimental Examples 10 to 16
  • Coin cell batteries were produced in the same manner as in Experimental Example 9, except that each of the binder aqueous solutions 2 to 8 obtained in Examples 2 to 8 was used instead of the binder aqueous solution 1, and the capacity retention rate (%) after 20 cycles was calculated in a charge/discharge test.
  • Comparative Experimental Examples 4 to 6
  • Coin cell batteries were produced in the same manner as in Experimental Example 9, except that each of the binder aqueous solutions 101 to 103 obtained in Comparative Examples 1 to 3 was used instead of the binder aqueous solution 1, and the capacity retention rate (%) after 20 cycles was calculated in a charge/discharge test.
  • Table 2 shows the tan δ values obtained in Experimental Examples 1 to 8 and Comparative Experimental Examples 1 to 3, and the capacity retention rates obtained in Experimental Examples 9 to 16 and Comparative Experimental Examples 4 to 6.
  • TABLE 2
    Capacity
    Experimental Example Binder aqueous solution (Example) tanδ retention rate (%)
    Experimental Example 1•9 Binder aqueous solution 1 (Example 1) 1.83 84
    Experimental Example 2•10 Binder aqueous solution 2 (Example 2) 1.20 84
    Experimental Example 3•11 Binder aqueous solution 3 (Example 3) 1.05 83
    Experimental Example 4•12 Binder aqueous solution 4 (Example 4) 1.40 84
    Experimental Example 5•13 Binder aqueous solution 5 (Example 5) 1.50 89
    Experimental Example 6•14 Binder aqueous solution 6 (Example 6) 1.30 94
    Experimental Example 7•15 Binder aqueous solution 7 (Example 7) 1.71 94
    Experimental Example 8•16 Binder aqueous solution 8 (Example 8) 2.18 94
    Comparative Experimental Binder aqueous solution 101 (Comparative 0.054 72
    Example 1•4 Example 1)
    Comparative Experimental Binder aqueous solution 102 (Comparative 0.15 49
    Example 2•5 Example 2)
    Comparative Experimental Binder aqueous solution 103 (Comparative 0.83 58
    Example 3•6 Example 3)
  • From Table 2, in a case of the binder aqueous solutions 1 to 8 obtained in Examples 1 to 8, the tan δ of the slurry for measurement showed a value larger than 1, and the capacity retention rate in the charge/discharge test was 80% or more. This is considered to be due to the fact that the binder having tan δ>1 under the measurement conditions in the first invention was excellent in the dispersibility of the conductive assistant, and therefore the battery using this binder was able to maintain good battery characteristics even after 20 cycles of charge and discharge.
  • On the other hand, in a case of the binder aqueous solutions 101 to 103 obtained in Comparative Examples 1 to 3, the tan δ of the slurry for measurement was 1 or less, and the capacity retention rate in the charge/discharge test was less than 80%. This is considered to be due to the fact that the dispersibility of the conductive assistant was insufficient with the binder having tan δ≤1 under the measurement conditions in the first invention, and therefore the battery using this binder could not sufficiently transmit electrons.
    • Example 9
  • To a 1000 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 280 parts by mass of ion exchange water, 4 parts by mass (0.06 mol) of acrylic acid (manufactured by Toagosei Co., Ltd.), and 36 parts by mass (0.76 mol) of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Ltd.), followed by heating under a nitrogen stream until the internal temperature reached 77° C. Next, 0.31 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate (trade name: VA-057, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added thereto, and the obtained solution was reacted at 77° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and an aqueous solution prepared by adding 40 parts by mass of ion exchange water to 4.6 parts by mass of pentylamine (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise to obtain a binder aqueous solution 9 (solid content: 14%).
    • Examples 10 to 34
  • Binder aqueous solutions 10 to 34 were obtained in the same manner as in Example 9, except that each of amines shown in Table 3 below was used instead of 4.6 parts by mass of pentylamine.
  • TABLE 3
    Amount Number
    used Degree of of basic Amine
    (parts neutralization Molecular functional value
    Example Amine name by mass) (%) weight groups (meq./g)
    Example 9 Pentylamine 4.60 95  87.16 1 11.5
    Example 10 Octylamine 6.82 95 129.24 1 7.7
    Example 11 Dibutylamine 6.82 95 129.24 1 7.7
    Example 12 Benzylamine 5.65 95 107.15 1 9.3
    Example 13 Aniline 4.91 95  93.13 1 10.7
    Example 14 Ethanolamine 3.22 95  61.08 1 16.4
    Example 15 N,N-diethylethanolamine 6.18 95 117.19 1 8.5
    Example 16 Benzyltrimethylammonium hydroxide 8.82 95 167.25 1 6.0
    Example 17 Tetrabutylammonium hydroxide 13.68 95 259.47 1 3.9
    Example 18 Tetrabutylphosphonium hydroxide 14.58 95 276.44 1 3.6
    Example 19 Diazabicycloundecene 8.03 95 152.24 1 6.6
    Example 20 Diisopropylethylamine 6.82 95 129.30 1 7.7
    Example 21 Tris(2-cyanoethyl)amine 9.29 95 176.22 1 5.7
    Example 22 Bis(2-cyanoethyl)amine 6.49 95 123.16 1 8.1
    Example 23 3-Aminopropionitrile 3.70 95  70.09 1 14.3
    Example 24 3-Methoxypropylamine 4.70 95  89.14 1 11.2
    Example 25 3-Aminotriazole 4.43 95  84.08 1 11.9
    Example 26 3,5-Diaminotriazole 5.23 95  99.10 2 20.2
    Example 27 4-Dimethylaminopyridine 6.44 95 122.17 2 16.4
    Example 28 JEFFAMINE (registered trademark) D-400 11.80 95 (400)   2 4.5
    Example 29 JEFFAMINE (registered trademark) ED-600 16.13 95 (600)   2 3.3
    Example 30 Polyethyleneimine 2.27 95 43.07 ※per 1 23.2
    monomer unit
    Example 31 Ethylenediamine 1.58 95  60.10 2 33.3
    Example 32 1,2-Propanediamine 1.95 95  74.12 2 27.0
    Example 33 N-Methyl-1,3-propanediamine 2.32 95  88.15 2 22.7
    Example 34 Tris(2-aminoethyl)amine 1.93 95 146.23 4 27.4
    • Example 35
  • To a 1000 mL separable flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen introduction pipe were added 320 parts by mass of ion exchange water, 20 parts by mass (0.28 mol) of acrylic acid (manufactured by Toagosei Co., Ltd.), 20 parts by mass (0.43 mol) of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Ltd.), and 0.19 parts by mass (0.0013 mol) of N,N-methylenebisacrylamide (manufactured by FUJIFILM Wako Pure Chemical Corporation), followed by heating under a nitrogen stream until the internal temperature reached 77° C. Next, 0.31 parts by mass of 2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate (trade name: VA-057, manufactured by FUJIFILM Wako Pure Chemical Corporation) were added thereto, and the obtained solution was reacted at 77° C. for 4 hours. After the reaction was complete, the reaction solution was cooled to room temperature, an aqueous solution prepared by adding 40 parts by mass of ion exchange water to 18.5 parts by mass of 48% sodium hydroxide aqueous solution (manufactured by Toagosei Co., Ltd.) was added dropwise, and then an aqueous solution prepared by adding 40 parts by mass of ion exchange water to 3.6 parts by mass of pentylamine (manufactured by FUJIFILM Wako Pure Chemical Corporation) was added dropwise to obtain a binder aqueous solution 35 (solid content: 11%).
    • Examples 36 to 39
  • Binder aqueous solutions 36 to 39 were obtained in the same manner as in Example 35, except that each of the amines shown in Table 4 below was used instead of 3.6 parts by mass of pentylamine.
  • TABLE 4
    Number of
    Degree of basic Amine
    Amount used neutralization (%) Molecular functional value
    Example Concomitant amine name (parts by mass) Amine NaOH weight groups (meq./g)
    Example 35 Pentylamine 0.73 15 80 87.16 1 11.5
    Example 36 3-Methoxypropylamine 0.74 15 80 89.14 1 11.2
    Example 37 3-Aminotriazole 0.70 15 80 84.08 1 11.9
    Example 38 3,5-Diaminotriazole 0.83 15 80 99.10 2 20.2
    Example 39 JEFFAMINE (registered trademark) ED-600 2.55 15 80 (600)    2 3.3
    • Experimental Example 17
  • (1) Preparation of Slurry Composition and Production of Electrode for Lithium Secondary Battery
  • An electrode for a lithium secondary battery was produced in the same manner as in (1) Preparation of slurry composition and (2) Production of electrode for lithium secondary battery in Experimental Example 9, except that the binder aqueous solution 9 obtained in Example 9 was used instead of the binder aqueous solution 1.
  • (2) Bend Resistance Test
  • The electrode produced in (1) was cut out to a size of 10 mm×100 mm and set in a mandrel tester (BEVS1603 cylindrical bending tester). Then, the diameter of the mandrel rod around which the electrode was wound was gradually reduced from 32 mm, and the diameter at which the electrode cracked (mandrel diameter) was measured. The case where the mandrel diameter was 2 mm to 6 mm was evaluated as A; the case where the mandrel diameter was 7 mm to 9 mm was evaluated as B; the case where the mandrel diameter was 10 mm to 12 mm was evaluated as C; and the case where the mandrel diameter was 13 mm or more was evaluated as D.
  • (3) Production of Coin Cell Battery
  • A coin cell battery was produced in a glove box filled with argon. Here, a coin cell battery consisting of the electrode obtained in (1), a lithium foil electrode, a solution of 2% by mass of vinylene carbonate (VC) added to ethylene carbonate (EC)/dimethyl carbonate (DMC) (volume ratio=1:1) containing 1 M LiPF6, and a separator was assembled.
  • (4) Charge/Discharge Test
  • A charge/discharge test was carried out using the coin cell battery produced in (3), under the same conditions as those described in (4) Charge/discharge test of Experimental Example 9.
    • Experimental Examples 18 to 42
  • The bend resistance test and the charge/discharge test were carried out in the same manner as in Experimental Example 17, except that each of the binder aqueous solutions 10 to 34 obtained in Examples 10 to 34 was used instead of the binder aqueous solution 9.
  • Table 4 shows the evaluation results obtained in the bend resistance test in Experimental Examples 17 to 42 and the capacity retention rates obtained in the charge/discharge test in Experimental Examples 17 to 42.
  • TABLE 5
    Amine Mandrel Capacity
    Experimental value diameter retention
    Example Example Amine name (meq./g) evaluation rate (%)
    Experimental Example 9 Pentylamine 9.9 B 94
    Example 17
    Experimental Example 10 Octylamine 7.7 B 92
    Example 18
    Experimental Example 11 Dibutylamine 7.7 B 91
    Example 19
    Experimental Example 12 Benzylamine 9.3 B 90
    Example 20
    Experimental Example 13 Aniline 10.7 B 89
    Example 21
    Experimental Example 14 Ethanolamine 16.4 A 91
    Example 22
    Experimental Example 15 N,N-diethylethanolamine 8.5 A 91
    Example 23
    Experimental Example 16 Benzyltrimethylammonium hydroxide 6.0 A 85
    Example 24
    Experimental Example 17 Tetrabutylammonium hydroxide 3.9 A 84
    Example 25
    Experimental Example 18 Tetrabutylphosphonium hydroxide 3.6 A 82
    Example 26
    Experimental Example 19 Diazabicycloundecene 6.6 B 90
    Example 27
    Experimental Example 20 Diisopropylethylamine 7.7 A 92
    Example 28
    Experimental Example 21 Tris(2-cyanoethyl)amine 5.7 B 97
    Example 29
    Experimental Example 22 Bis(2-cyanoethyl)amine 8.1 B 97
    Example 30
    Experimental Example 23 3-Aminopropionitrile 14.3 C 98
    Example 31
    Experimental Example 24 3-Methoxypropylamine 11.2 A 93
    Example 32
    Experimental Example 25 3-Aminotriazole 11.9 A 97
    Example 33
    Experimental Example 26 3,5-Diaminotriazole 20.2 A 98
    Example 34
    Experimental Example 27 4-Dimethylaminopyridine 16.4 B 90
    Example 35
    Experimental Example 28 JEFFAMINE D-400 4.5 A 96
    Example 36
    Experimental Example 29 JEFFAMINE ED-600 3.3 A 87
    Example 37
    Experimental Example 30 Polyethyleneimine 23.2 D 95
    Example 38
    Experimental Example 31 Ethylenediamine 33.3 D 86
    Example 39
    Experimental Example 32 1,2-Propanediamine 27.0 D 86
    Example 40
    Experimental Example 33 N-Methyl-1,3-propanediamine 22.7 D 84
    Example 41
    Experimental Example 34 Tris(2-aminoethyl)amine 27.4 D 86
    Example 42
    • Experimental Examples 43 to 47
  • The bend resistance test and the charge/discharge test were carried out in the same manner as in Experimental Example 17, except that each of the binder aqueous solutions 35 to 39 obtained in Examples 35 to 39 was used instead of the binder aqueous solution 9.
  • Table 6 shows the evaluation results obtained in the bend resistance test in Experimental Examples 43 to 47 and the capacity retention rates obtained in the charge/discharge test in Experimental Examples 43 to 47.
  • TABLE 6
    Capacity
    Amine Mandrel retention
    Experimental value diameter rate
    Example Example Concomitant amine name (meq./g) evaluation (%)
    Experimental Example 35 Pentylamine 11.5 B 94
    Example 43
    Experimental Example 36 3-Methoxypropylamine 11.2 A 93
    Example 44
    Experimental Example 37 3-Aminotriazole 11.9 A 92
    Example 45
    Experimental Example 38 3,5-Diaminotriazole 20.2 A 93
    Example 46
    Experimental Example 39 JEFFAMINE 3.3 A 86
    Example 47 (registered trademark) ED-600
  • From Table 5, in a case of the electrodes (Experimental Examples 17 to 34) using the binder aqueous solutions 9 to 29 obtained in Examples 9 to 29, the mandrel diameter evaluation was A to C, the bend resistance was high, and the capacity retention rate was 80% or more. It is considered that the hydrophobic group of the amine used for neutralization lowered the glass transition point of the binder to make the binder flexible, thereby increasing the bend resistance. In addition, it is considered that good battery characteristics were maintained since the structure was similar to that of the first invention.
  • In addition, from Table 6, in a case of the electrodes (Experimental Examples 43 to 47) using the binder aqueous solutions 35 to 39 obtained in Examples 35 to 39, the mandrel diameter evaluation was A to B, the bend resistance was high, and the capacity retention rate was 85% or more. Therefore, it is considered that the bend resistance was improved because the effect of reducing the glass transition point of the binder is exhibited as in the electrodes of Experimental Examples 17 to 34, even in a case where the molar ratios of the monomer of (i) to the monomer of (ii) and the presence or absence of the crosslinking structure are different.
  • On the other hand, in a case of the electrodes (Experimental Examples 38 to 42) using the binder aqueous solutions 30 to 34 obtained in Examples 30 to 34, the mandrel diameter evaluation was D and the bend resistance was deteriorated. It is considered that polyvalent amines having a high amine value had a short distance between the neutralizing amines, and therefore the binder became rigid, the electrode became hard, and the bend resistance deteriorated.

Claims (11)

1. A binder for electricity storage devices, comprising:
a salt of a polymer containing structural units derived from (i) an ethylenically unsaturated carboxylic acid monomer and (ii) an ethylenically unsaturated monomer having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group, wherein the salt of the polymer is neutralized with a monoamine, a polyvalent amine having an amine value of less than 21, and/or an onium hydroxide.
2. The binder according to claim 1, wherein the polyvalent amine has a molecular weight of 600 or less.
3. The binder according to claim 1, wherein the monomer of (ii) has a solubility in water at 20° C. of 1 g/L or more.
4. The binder according to claim 1, wherein the monomer of (ii) has an SP value of 11.5 (cal/cm3)1/2 or more.
5. The binder according to claim 1, wherein the monomer of (ii) is a monomer represented by the following general formula [1]:
Figure US20220181633A1-20220609-C00041
in the general formula [1], R1 represents a hydrogen atom or a methyl group, Y1 represents —O— or —NR2—, R2 represents a hydrogen atom or a methyl group, and A1 represents a monovalent group having at least one group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group.
6. The binder according to claim 1, wherein the monomer of (ii) is a monomer represented by the following general formula [2]:
Figure US20220181633A1-20220609-C00042
in the general formula [2], R1 represents a hydrogen atom or a methyl group, Y1 represents —O— or —NR2—, R2 represents a hydrogen atom or a methyl group, and A2 represents an alkyl group having 1 to 10 carbon atoms and having 1 to 3 of any one of a group selected from a hydroxy group, a dialkylamino group, an acetyl group, a sulfo group, a phosphate group, or a cyano group; or a linear alkyl group having 3 to 36 carbon atoms and having 1 hydroxy group and 1 to 5 ester bonds in a chain thereof.
7. The binder according to claim 1, wherein the salt of the polymer further contains a structural unit derived from (iii) a monomer having two or more polymerizable unsaturated groups.
8. The binder according to claim 1, wherein, in a case where the polymer contains a structural unit(s) derived from a monomer(s) other than the monomers (i) and (ii), a total content of the structural unit(s) derived from the monomer(s) other than the monomers (i) and (ii) in the polymer is 10 mol % or less with respect to a total content of the structural units derived from the monomers (i) and (ii) in the polymer.
9. A slurry composition for electricity storage devices, comprising the binder according to claim 1.
10. An electrode for electricity storage devices, comprising the slurry composition according to claim 9.
11. An electricity storage device comprising the electrode according to claim 10.
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