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WO2018008555A1 - Composition de liant destinée à des électrodes de batterie secondaire non aqueuse, composition de suspension épaisse destinée à des électrodes de batterie secondaire non aqueuse, électrode de batteries secondaires non aqueuses, et batterie secondaire non aqueuse - Google Patents

Composition de liant destinée à des électrodes de batterie secondaire non aqueuse, composition de suspension épaisse destinée à des électrodes de batterie secondaire non aqueuse, électrode de batteries secondaires non aqueuses, et batterie secondaire non aqueuse Download PDF

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Publication number
WO2018008555A1
WO2018008555A1 PCT/JP2017/024192 JP2017024192W WO2018008555A1 WO 2018008555 A1 WO2018008555 A1 WO 2018008555A1 JP 2017024192 W JP2017024192 W JP 2017024192W WO 2018008555 A1 WO2018008555 A1 WO 2018008555A1
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Prior art keywords
polymer
secondary battery
mass
electrode
water
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Ceased
Application number
PCT/JP2017/024192
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English (en)
Japanese (ja)
Inventor
園部　健矢
政憲 渋谷
祐輔 足立
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Zeon Corp
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Zeon Corp
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Priority to JP2018526342A priority Critical patent/JP7067473B2/ja
Publication of WO2018008555A1 publication Critical patent/WO2018008555A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M4/139—Processes of manufacture
    • 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
    • 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 composition for non-aqueous secondary battery electrodes, a slurry composition for non-aqueous secondary battery electrodes, an electrode for non-aqueous secondary batteries, and a non-aqueous secondary battery.
  • Non-aqueous secondary batteries such as lithium ion secondary batteries (hereinafter sometimes simply referred to as “secondary batteries”) have the characteristics of being small and lightweight, having high energy density, and capable of repeated charge and discharge. Yes, it is used for a wide range of purposes. Therefore, in recent years, improvement of battery members such as electrodes has been studied for the purpose of further improving the performance of non-aqueous secondary batteries.
  • an electrode for a secondary battery such as a lithium ion secondary battery is usually provided with a current collector and an electrode mixture layer formed on the current collector.
  • the electrode mixture layer is formed on the current collector by, for example, a slurry-like composition obtained by dispersing an electrode active material and a binder composition containing a polymer serving as a binder in a dispersion medium. It is formed by applying to and drying.
  • the electrode mixture layer formed using the slurry composition is in good contact with the current collector. If the adhesion between the current collector and the electrode mixture layer is low, the current collector and the electrode mixture layer are not sufficiently bonded and fixed, and as a result, battery performance such as cycle characteristics may be deteriorated. It is.
  • Patent Document 1 as a binder composition for an electrode when producing a secondary battery, a monomer group containing a polymerizable monomer of unsaturated carboxylic acids and (meth) acrylamide is polymerized.
  • Patent Document 1 discloses methacrylic acid: (meth) acrylamide: 2 as a specific acrylic aqueous dispersion for electrochemical cells that can improve the adhesion between the electrode mixture layer and the metal current collector.
  • An aqueous dispersion containing organic particles (b) obtained by emulsion polymerization of ester, (meth) acrylamide and / or (meth) acrylonitrile is disclosed.
  • a binder for electrodes at the time of manufacturing a secondary battery it has a structural unit derived from an acid-containing monomer and a structural unit derived from a hydroxyl group-containing monomer, and has a predetermined acid value.
  • Patent Document 2 discloses acrylic water or 2-carboxyethyl acrylate as a specific aqueous binder for an electrode composition that can provide sufficient peel strength (adhesiveness) between an electrode mixture layer and a current collector.
  • An aqueous binder containing a polymer obtained by polymerizing a mixture containing 2-hydroxyethyl acrylate is disclosed.
  • “(meth) acryl” means acryl and / or methacryl
  • “(meth) acrylo” means acrylo and / or methacrylo.
  • the electrode formed using the above conventional binder composition has room for improvement in terms of further increasing the adhesion strength between the electrode mixture layer and the current collector.
  • the slurry composition prepared using the binder composition may be stored until it is used for manufacturing the electrode. Therefore, even when the slurry composition after storage is used, from the viewpoint of further forming the electrode mixture layer and further improving the performance of the secondary battery, the slurry composition used for forming the electrode mixture layer
  • the product is required to have excellent viscosity stability.
  • the present invention provides a slurry composition capable of forming an electrode mixture layer having excellent viscosity stability and excellent adhesion to a current collector, and a binder composition capable of preparing the slurry composition.
  • the purpose is to do.
  • an object of this invention is to provide the secondary battery provided with the electrode which has an electrode compound-material layer excellent in adhesiveness with a collector, and the said electrode.
  • the present inventors have intensively studied for the purpose of solving the above problems.
  • the present inventors also provide a binder comprising a polymer containing an ethylenically unsaturated carboxylic acid monomer unit, a (meth) acrylamide monomer unit, and a hydroxyl group-containing vinyl monomer unit within a predetermined range.
  • a binder comprising a polymer containing an ethylenically unsaturated carboxylic acid monomer unit, a (meth) acrylamide monomer unit, and a hydroxyl group-containing vinyl monomer unit within a predetermined range.
  • the binder composition for a non-aqueous secondary battery electrode of the present invention is a binder composition containing a water-soluble polymer
  • the water-soluble polymer contains 1% by mass to 50% by mass of ethylenically unsaturated carboxylic acid monomer units, 10% by mass to 60% by mass of (meth) acrylamide monomer units, and hydroxyl group-containing vinyl. It includes a polymer X containing 5% to 89% by mass of monomer units.
  • a slurry composition capable of forming an electrode mixture layer that is excellent in viscosity stability and excellent in adhesion to a current collector Obtainable.
  • water-soluble means that the mixture obtained by adding 1 part by weight of polymer (corresponding to the solid content) and stirring with respect to 100 parts by weight of ion-exchanged water has a temperature of 20 ° C. When adjusted to one condition within a range of 70 ° C.
  • the “content ratio (mass%) of each monomer unit” can be measured using a nuclear magnetic resonance (NMR) method such as 1 H-NMR.
  • the glass transition temperature of the polymer X is preferably ⁇ 10 ° C. or more and 100 ° C. or less. This is because if the glass transition temperature of the polymer X is within the above range, it is possible to suppress the occurrence of springback of the electrode mixture layer during electrode production. Moreover, it is because it can suppress that the electrode which has the electrode compound-material layer formed using the binder composition expand
  • the “glass transition temperature” can be determined according to JIS K7121.
  • the polymer X further contains 0.001% by mass to 10% by mass of a polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit.
  • polyfunctional ethylenically unsaturated carboxylic acid ester monomer refers to a monomer that is a carboxylic acid ester having two or more ethylenic unsaturated bonds (C ⁇ C) in the molecule. Point to.
  • the degree of swelling of the electrolyte solution of the polymer X is preferably more than 1 time and 3 times or less. If the electrolyte solution swelling degree of the polymer X is within the above range, the electrode having the electrode mixture layer formed using the binder composition can be prevented from expanding and contracting along with charge / discharge of the secondary battery. It is.
  • the “electrolyte swelling degree” can be measured using the measuring method described in the examples of the present specification.
  • the solubility of the polymer X at a temperature of 20 ° C. is preferably 1 g / 100 g-H 2 O or more. If the solubility of the polymer X in water is not less than the above lower limit, for example, a slurry composition using water as a solvent or a dispersion medium can be easily prepared, and an electrode produced using the slurry composition is an electrode. It is because it tends to have a uniform structure excellent in the mixing property of the active material and the binder composition.
  • the “solubility” can be measured according to the method described in the examples of the present specification.
  • the content ratio of the polymer X is 10% by mass to 100% by mass with respect to 100% by mass of the total polymer in the water-soluble polymer. It is preferable that If the ratio of the polymer X in the water-soluble polymer is within the above range, the viscosity stability of the slurry composition can be further improved, and an electrode mixture layer that is more excellent in adhesion to the current collector is formed. Because it can be done.
  • the water-soluble polymer further includes another water-soluble polymer different from the polymer X, and the other water-soluble polymer.
  • the water-soluble polymer further contains other water-soluble polymer having a predetermined composition in addition to the polymer X, an electrode mixture having excellent viscosity stability and excellent adhesion to the current collector This is because a slurry composition capable of forming a layer can be obtained.
  • the binder composition for a non-aqueous secondary battery electrode of the present invention further includes a particulate polymer having at least one of a carboxyl group and a hydroxyl group, and the content of the polymer X is the particulate polymer 100. It is preferable that it is 0.1 to 200 mass parts with respect to the mass part. If the binder composition further contains a predetermined particulate polymer, and the contents of the polymer X and the particulate polymer are within the above range, the viscosity stability of the slurry composition containing the binder composition is improved. This is because the adhesion between the electrode mixture layer formed using the slurry composition and the current collector can be further improved while ensuring.
  • the “particulate polymer” is a polymer having a particle shape at least in the binder composition, and is usually a water-insoluble polymer. Moreover, the particle shape which a particulate polymer has can be confirmed by the laser diffraction method, for example.
  • the slurry composition for non-aqueous secondary battery electrodes of this invention is an electrode active material and one of the non-aqueous two-components mentioned above. And a binder composition for secondary battery electrodes.
  • the slurry composition excellent in viscosity stability can be obtained.
  • the slurry composition which can form the electrode compound-material layer excellent in adhesiveness with a collector can be obtained.
  • the electrode for non-aqueous secondary batteries of this invention is a collector and the slurry composition for non-aqueous secondary battery electrodes mentioned above. It has the electrode compound-material layer formed using the thing, It is characterized by the above-mentioned. Thus, if an electrode compound-material layer is formed using the slurry composition mentioned above, the electrode which has an electrode compound-material layer excellent in adhesiveness with a collector can be obtained.
  • the non-aqueous secondary battery of this invention is equipped with a positive electrode, a negative electrode, a separator, and electrolyte solution, At least of the said positive electrode and negative electrode One of the electrodes is the above-described electrode for a non-aqueous secondary battery.
  • the positive electrode and / or the negative electrode is the above-described electrode for a non-aqueous secondary battery, the current collector and the electrode mixture layer are in good contact with each other in the electrode provided in the secondary battery. Excellent battery characteristics can be imparted to the battery.
  • a slurry composition capable of forming an electrode mixture layer having excellent viscosity stability and adhesion to a current collector, and a binder composition capable of preparing the slurry composition. be able to.
  • an electrode which has an electrode compound-material layer excellent in adhesiveness with a collector, and a secondary battery provided with the said electrode can be provided.
  • the binder composition for non-aqueous secondary battery electrodes of the present invention can be used when preparing a slurry composition for non-aqueous secondary battery electrodes.
  • a slurry composition for a non-aqueous secondary battery electrode prepared using the binder composition for a non-aqueous secondary battery electrode of the present invention is an electrode for a non-aqueous secondary battery such as a lithium ion secondary battery (non-aqueous secondary battery). It can be used when forming the electrode mixture layer of the secondary battery electrode.
  • the non-aqueous secondary battery of the present invention is characterized by using a non-aqueous secondary battery electrode having an electrode mixture layer formed using the slurry composition for a non-aqueous secondary battery electrode of the present invention. To do.
  • the binder composition for non-aqueous secondary battery electrodes of the present invention is characterized by containing a water-soluble polymer containing the polymer X having a predetermined composition.
  • the binder composition for non-aqueous secondary battery electrodes of the present invention may optionally further include other components such as a particulate polymer and a solvent.
  • the binder composition for non-aqueous secondary battery electrodes of this invention contains the polymer X which has a predetermined
  • the binder composition for non-aqueous secondary battery electrodes of the present invention contains the predetermined polymer X, it is collected in the electrode mixture layer formed using the slurry composition containing the binder composition. Excellent adhesion to the electric body can be exhibited.
  • the water-soluble polymer needs to include the polymer X containing each of the predetermined three types of monomer units in a ratio within a predetermined range.
  • the water-soluble polymer may further contain a predetermined other water-soluble polymer different from the polymer X. If the water-soluble polymer does not contain the polymer X having the predetermined composition, the slurry composition containing the binder composition containing the water-soluble polymer cannot exhibit good viscosity stability.
  • the water-soluble polymer does not contain the polymer X having the predetermined composition, when the electrode mixture layer is formed using the slurry composition containing the binder composition containing the water-soluble polymer, Sufficient adhesion cannot be obtained between the electrode mixture layer and the current collector.
  • the polymer X needs to contain an ethylenically unsaturated carboxylic acid monomer unit, a (meth) acrylamide monomer unit, and a hydroxyl group-containing vinyl monomer unit in a proportion within a predetermined range.
  • the polymer X may optionally further contain other monomer units such as a polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit.
  • the ethylenically unsaturated carboxylic acid monomer capable of forming an ethylenically unsaturated carboxylic acid monomer unit usually does not have a hydroxyl group (—OH) other than the hydroxyl group in the carboxyl group.
  • the ethylenically unsaturated carboxylic acid monomer include ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof, and derivatives thereof.
  • an ethylenically unsaturated carboxylic acid monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
  • examples of ethylenically unsaturated monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic. Acid, ⁇ -diaminoacrylic acid and the like.
  • examples of the ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
  • Examples of acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, diacrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, and the like.
  • Examples of the ethylenically unsaturated dicarboxylic acid derivative include methylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, and fluoromaleic acid.
  • the ethylenically unsaturated carboxylic acid monomer is preferably ethylenically unsaturated monocarboxylic acid and ethylenically unsaturated dicarboxylic acid, more preferably acrylic acid, methacrylic acid and itaconic acid, Acrylic acid and methacrylic acid are more preferred.
  • acrylic acid is more preferable as the ethylenically unsaturated carboxylic acid monomer from the viewpoint of suppressing the degree of swelling of the resulting polymer with respect to the electrolytic solution.
  • the polymer X needs to contain 1 to 50 mass% of ethylenically unsaturated carboxylic acid monomer units in 100 mass% of all monomer units.
  • the content of the ethylenically unsaturated carboxylic acid monomer unit is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less, 25% by mass. % Or less is more preferable.
  • an electrode mixture layer is formed using a slurry composition containing a binder composition containing the polymer X This is because the electrode mixture layer can exhibit excellent adhesion (high peel strength) with the current collector.
  • the content rate of the ethylenically unsaturated carboxylic acid monomer unit in the polymer X is not more than the above upper limit, the viscosity stability of the slurry composition prepared using the binder composition containing the polymer X This is because the storage stability of the slurry composition and the handleability during formation of the electrode mixture layer can be improved.
  • the polymer X can be prepared easily.
  • the (meth) acrylamide monomer unit is formed using a (meth) acrylamide monomer which is acrylamide and / or methacrylamide.
  • the polymer X needs to contain a (meth) acrylamide monomer unit in the ratio of 10 to 60 mass% in 100 mass% of all monomer units.
  • the content ratio of the (meth) acrylamide monomer unit is preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 50% by mass or less, and 40% by mass or less. It is more preferable that If the content ratio of the (meth) acrylamide monomer unit in the polymer X is not less than the above lower limit, components such as an electrode active material and a conductive material are well dispersed in the slurry composition containing the binder composition, and the slurry This is because the viscosity stability of the composition is excellent.
  • the content ratio of the (meth) acrylamide monomer unit in the polymer X is not more than the above upper limit, it is excellent in the slurry composition by suppressing the viscosity of the slurry composition containing the binder composition from being excessively lowered. This is because the viscosity stability can be exhibited, and the storage stability of the slurry composition and the handleability when forming the electrode mixture layer can be improved. Furthermore, if the content ratio of the (meth) acrylamide monomer unit in the polymer X is within the above range, the polymer X can be easily prepared.
  • the hydroxyl group-containing vinyl monomer capable of forming a hydroxyl group-containing vinyl monomer unit is a hydroxyl group (—OH) and a vinyl group (—CH ⁇ CH 2 ) or an isopropenyl group (—C
  • a monofunctional compound having (CH 3 ) ⁇ CH 2 ) and having one ethylenically unsaturated bond (C ⁇ C) in the molecule is a monofunctional compound having (CH 3 ) ⁇ CH 2 ) and having one ethylenically unsaturated bond (C ⁇ C) in the molecule.
  • hydroxyl group-containing vinyl monomer examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-hydroxymethylacrylamide (N-methylolacrylamide), Examples thereof include N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide and the like. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • hydroxyl group-containing vinyl monomer 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-methylol acrylamide and N-hydroxyethyl acrylamide are preferable. More preferred are ethyl acrylate and 2-hydroxyethyl methacrylate.
  • the compound exemplified as the hydroxyl group-containing vinyl monomer capable of forming the hydroxyl group-containing vinyl monomer unit is an ethylenic compound capable of forming the above-described ethylenically unsaturated carboxylic acid monomer unit. It is not included in the unsaturated carboxylic acid monomer.
  • the polymer X needs to contain a hydroxyl group containing vinyl monomer unit in the ratio of 5 to 89 mass% in 100 mass% of all monomer units.
  • the content ratio of the hydroxyl group-containing vinyl monomer unit is preferably 10% by mass or more, more preferably 15% by mass or more, preferably 70% by mass or less, and 50% by mass or less. It is more preferable that When the content ratio of the hydroxyl group-containing vinyl monomer unit in the polymer X is not less than the above lower limit, when the electrode mixture layer is formed using the slurry composition containing the binder composition containing the polymer X In addition, the electrode composite material layer can exhibit excellent adhesion (high peel strength) to the current collector.
  • the slurry composition including the binder composition containing the polymer X exhibits good viscosity stability. This is because the storage stability of the slurry composition and the handleability during formation of the electrode mixture layer can be improved. Furthermore, if the content ratio of the hydroxyl group-containing vinyl monomer unit in the polymer X is within the above range, the polymer X can be easily prepared.
  • polyfunctional ethylenically unsaturated carboxylic acid ester monomer for example, 2-hydroxy-3-acryloyloxypropyl methacrylate (701A), polyethylene glycol # 200 diacrylate (A-200), polyethylene glycol # 400 diacrylate (A-400), polyethylene glycol # 600 diacrylate (A-600) Polyethylene glycol # 1000 diacrylate (A-1000), propoxylated ethoxylated bisphenol A diacrylate (A-B1206PE), ethoxylated bisphenol A diacrylate (ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4), 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (A-BPEF), propoxylated bisphenol A diacrylate (A-BPP) 3), tricyclodecane dimethanol diacrylate (A-DCP), 1,10-decanediol diacrylate (A-DOD-
  • the names in the parentheses are product names available from Shin-Nakamura Chemical Co., Ltd.
  • the polyfunctional ethylenically unsaturated carboxylic acid ester is used from the viewpoint of achieving good crosslinkability while ensuring high viscosity stability of the slurry composition and high adhesion to the current collector of the electrode mixture layer.
  • the number of ethylenically unsaturated bonds (functional number) of the monomer is preferably 2 or more and 6 or less (2 functions to 6 functions), and preferably 2 or more and 4 or less (2 functions to 4 functions). More preferred.
  • the content ratio of the polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit is 100 mass of all monomer units. % Is preferably 0.001% by mass or more, more preferably 0.1% by mass or more, more preferably 10% by mass or less, and even more preferably 5% by mass or less. More preferably, it is at most mass%.
  • the polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit having a plurality of ethylenically unsaturated bonds in the molecule usually has crosslinkability.
  • a slurry composition including a binder composition containing the polymer X is used. This is because the adhesion (peel strength) between the electrode mixture layer and the current collector when the electrode mixture layer is formed can be increased. Moreover, it is because the favorable viscosity stability of a slurry composition can be ensured by making the content rate of the polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit in the polymer X below the above upper limit. .
  • the monomer unit other than the polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit that can be further contained in the polymer X is not particularly limited, for example, a methyl acrylate monomer unit Methyl methacrylate monomer units, ethyl acrylate monomer units, ethyl methacrylate monomer units, and monomer units obtained by introducing fluorine-containing substituents such as trifluoromethyl groups into these monomer units Can be mentioned.
  • the content ratio of other monomer units other than the polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit in the polymer X can be 0% by mass, and more than 0% by mass. 20 mass% or less, preferably 10 mass% or less, more preferably 1 mass% or less. If the content ratio of other monomer units other than the polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit in the polymer X exceeds 0% by mass, the electrolyte solution swelling degree of the binder composition is excessively large. This is because it can be suppressed.
  • a slurry composition containing a binder composition is used. It is because the spring back mentioned later can be suppressed, maintaining favorable adhesiveness with the electrical power collector of the formed electrode compound-material layer.
  • the polymer X preferably has a glass transition temperature of ⁇ 10 ° C. or higher, more preferably 0 ° C. or higher, still more preferably 10 ° C. or higher, and usually 130 ° C. or lower. It is preferably at most 0 ° C, more preferably at most 70 ° C, still more preferably at most 60 ° C. If the glass transition temperature of the polymer X is equal to or higher than the above lower limit, the electrode mixture layer formed using the slurry composition containing the polymer X is suppressed from expanding with charge / discharge of the secondary battery, This is because the swelling of the electrode can be prevented.
  • the term “spring back” means a phenomenon in which the elastic deformation of the electrode body recovers its shape (elastic recovery) when the electrode body such as the electrode mixture layer is released after being pressed.
  • the electrode mixture layer is spring-backed, the thickness of the electrode mixture layer and the electrode is not sufficiently reduced, and a sufficiently high density electrode cannot be obtained.
  • “spring back” can be evaluated based on the electrode mixture layer density measured according to the examples of the present specification.
  • the degree of swelling of the polymer X with respect to the electrolytic solution is preferably 3 times or less, more preferably 2 times or less, still more preferably 1.5 times or less, and 1.2 times or less. More preferably, it is usually more than 1 time. If the degree of swelling of the electrolyte solution of the polymer X is less than or equal to the above upper limit, the electrode mixture layer formed using the slurry composition containing the polymer X is further suppressed from expanding with charge / discharge of the secondary battery. This is because the swelling of the electrode can be further prevented.
  • the polymer X preferably has a solubility in 100 g of water at a temperature of 20 ° C. of 1 g / 100 g-H 2 O or more, more preferably 7 g / 100 g-H 2 O or more, and 10 g / 100 g-H. 2 O or more is more preferable, and 20 g / 100 g-H 2 O or more is more preferable. If the solubility of the polymer X in water is equal to or higher than the lower limit, the polymer X can satisfactorily coat the electrode active material in the electrode mixture layer, and therefore when the manufactured secondary battery is charged, This is because metal deposition on the electrode having the electrode mixture layer can be suppressed. Further, as a result, the battery characteristics of the secondary battery such as cycle characteristics can be improved.
  • the content ratio of the polymer X in the water-soluble polymer is preferably 10% by mass or more, and more preferably 30% by mass or more with respect to 100% by mass of the total polymer in the water-soluble polymer. More preferably, it is more preferably 40% by mass or more, still more preferably 70% by mass or more, and can be 100% by mass. That is, the polymer X can be used as it is as a water-soluble polymer. If the content ratio of the polymer X in the water-soluble polymer is set to the above lower limit or more, the binder composition containing the water-soluble polymer is used, the viscosity stability is excellent, and the adhesion to the current collector is improved. This is because a slurry composition capable of forming an excellent electrode mixture layer can be obtained more easily.
  • the polymer X can be obtained, for example, by polymerizing a monomer composition obtained by mixing the above-described components and an arbitrary polymerization solvent by a known method by an arbitrary polymerization method.
  • the solution containing the polymer X and the polymerization solvent obtained by polymerizing the monomer composition may be used as it is for the preparation of the binder composition, solvent substitution, addition of optional components, etc. You may use for preparation of a binder composition after performing.
  • the polymerization method of the polymer X is not limited, and for example, any method such as solution polymerization method such as aqueous solution polymerization method, slurry polymerization method, suspension polymerization method, bulk polymerization method, emulsion polymerization method, etc. May be used.
  • addition polymerization such as ionic polymerization, radical polymerization, and living radical polymerization
  • polymerization initiators such as ionic polymerization, radical polymerization, and living radical polymerization
  • polymerization accelerators, emulsifiers, dispersants, chain transfer agents, etc. can be used, and the amount used is also generally used.
  • an aqueous solution polymerization method using water as the polymerization solvent is preferable because the operation for removing the solvent is unnecessary, the safety of the solvent is high, and there is no problem of mixing of the surfactant.
  • the pH of the aqueous solution should be adjusted to 7 or more and 9 or less after polymerization. Is preferred. This is because if the aqueous solution obtained is neutralized and adjusted to a pH in the above range, the viscosity stability of the slurry composition is easily improved.
  • the polymerization initiator that can be used for the preparation of the polymer X is not particularly limited, and examples thereof include known polymerization initiators such as sodium persulfate, ammonium persulfate, and potassium persulfate. Of these, potassium persulfate is preferably used.
  • a polymerization initiator may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the polymerization accelerator is not particularly limited, and a known reducing polymerization accelerator such as tetramethylethylenediamine can be used.
  • a polymerization accelerator may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the water-soluble polymer may further contain another water-soluble polymer different from the polymer X (other than the polymer X).
  • the other water-soluble polymer that can be included in the water-soluble polymer preferably includes any of a natural polymer, a semi-synthetic polymer, and a synthetic polymer.
  • water-soluble polymers for example, thickening polysaccharides, alginic acid and salts thereof (for example, sodium alginate), natural polymers such as starch; carboxymethyl cellulose and salts thereof
  • a semi-synthetic polymer obtained by chemically treating a natural polymer as a raw material a synthetic polymer such as polyacrylic acid such as polyvinylpyrrolidone, crosslinked polyacrylic acid and non-crosslinked polyacrylic acid; be able to.
  • the other water-soluble polymer is preferably a semi-synthetic polymer, a synthetic polymer, Carboxymethyl cellulose, a salt of carboxymethyl cellulose, and polyacrylic acid are more preferable.
  • the other water-soluble polymer is mixed with polymer X in advance to form a binder composition, and then the slurry composition is prepared. It may be used; it may be mixed with the polymer X together with the electrode active material or the like when preparing the slurry composition without being previously mixed with the polymer X.
  • the content rate of another water-soluble polymer is 0 with respect to 100 mass% of all the polymers in a water-soluble polymer. It can be more than mass%, preferably 90 mass% or less, more preferably 70 mass% or less, and still more preferably 60 mass% or less.
  • the particulate polymer that the binder composition for nonaqueous secondary battery electrodes of the present invention may optionally contain has at least one of a carboxyl group and a hydroxyl group (a hydroxyl group other than a hydroxyl group in the carboxyl group). Moreover, it is preferable that a particulate polymer has a carboxyl group and a hydroxyl group. Here, both the carboxyl group and hydroxyl group of the particulate polymer are hydrophilic groups. As described above, in the present invention, the particulate polymer is usually water-insoluble.
  • the particulate polymer usually has a particle shape in an aqueous binder composition containing water as a solvent or a dispersion medium and an aqueous slurry composition. Further, the particulate polymer may be present while maintaining the particle shape in the electrode mixture layer, or may be present with any non-particle shape.
  • the particulate polymer is not particularly limited, and any polymer such as a conjugated diene polymer, an acrylic polymer, or an unsaturated carboxylic acid polymer can be used.
  • the conjugated diene polymer is a polymer containing a conjugated diene monomer unit.
  • a specific example of the conjugated diene polymer is not particularly limited, and is a copolymer containing an aromatic vinyl monomer unit such as a styrene-butadiene copolymer (SBR) and an aliphatic conjugated diene monomer unit. Examples thereof include polymers, butadiene rubber (BR), isoprene rubber, acrylic rubber (NBR) (a copolymer containing acrylonitrile units and butadiene units), and hydrides thereof.
  • SBR styrene-butadiene copolymer
  • NBR acrylic rubber
  • a copolymer containing an aromatic vinyl monomer unit and an aliphatic conjugated diene monomer unit is an aromatic vinyl monomer and an aliphatic conjugated diene unit capable of forming an aromatic vinyl monomer unit.
  • An aliphatic conjugated diene monomer capable of forming a monomer unit and a carboxyl group-containing monomer and / or a hydroxyl group-containing monomer can be polymerized by any method.
  • a copolymer containing an aromatic vinyl monomer unit and an aliphatic conjugated diene monomer unit may optionally contain other carboxyl group-containing monomer and / or hydroxyl group-containing monomer. You may prepare using a monomer further.
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, vinyl toluene, divinylbenzene and the like. These may be used alone or in combination of two or more. Among these, styrene is preferable as the aromatic vinyl monomer.
  • Aliphatic conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, And chain conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like. These may be used alone or in combination of two or more. Among these, 1,3-butadiene is preferable as the aliphatic conjugated diene monomer.
  • carboxyl group-containing monomer examples include the above-mentioned “ethylenically unsaturated carboxylic acid monomer unit”. And the same monomers as the “ethylenically unsaturated carboxylic acid monomer capable of forming“. These may be used alone or in combination of two or more. Among these, itaconic acid is preferable as the carboxyl group-containing monomer.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl Acrylate, 2-hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di- (ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like can be mentioned. These may be used alone or in combination of two or more. Among these, 2-hydroxyethyl acrylate is preferable as the hydroxyl group-containing monomer.
  • the other monomer used for preparing the copolymer containing the aromatic vinyl monomer unit and the aliphatic conjugated diene monomer unit include monomers copolymerizable with the above-described monomers.
  • fluorine-containing monomers such as fluorine-containing (meth) acrylic acid ester monomers; sulfate group-containing monomers such as acrylamide-2-methylpropanesulfonic acid; Amide group-containing monomers such as acrylamide and methacrylamide; crosslinkable monomers (crosslinkable monomers) such as allyl glycidyl ether, allyl (meth) acrylate, and N-methylolacrylamide; olefins such as ethylene and propylene Halogen-containing monomers such as vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; vinyl ethers such as methyl vinyl ether
  • a (meth) acrylic acid ester monomer is used for the preparation of a conjugated diene polymer such as a copolymer containing an aromatic vinyl monomer unit and an aliphatic conjugated diene monomer unit, )
  • the content of the acrylate monomer is less than 50% by mass based on 100% by mass of all monomers capable of constituting the conjugated diene polymer.
  • the acrylic polymer is a polymer containing a (meth) acrylic acid ester monomer unit.
  • the acrylic polymer is an optional combination of a (meth) acrylic acid ester monomer capable of forming a (meth) acrylic acid ester monomer unit, and a carboxyl group-containing monomer and / or a hydroxyl group-containing monomer. It can obtain by superposing
  • the acrylic polymer may optionally further contain other monomers in addition to the carboxyl group-containing monomer and / or hydroxyl group-containing monomer.
  • the acrylic polymer usually contains 50% by mass or more of a (meth) acrylic acid ester monomer per 100% by mass of all monomers that can constitute the acrylic polymer, and the conjugated diene polymer described above Is different.
  • -(Meth) acrylate monomer- (Meth) acrylate monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, 2-ethylhexyl Acrylic acid alkyl esters such as octyl acrylate such as acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate Octyl methacrylate, etc., methacrylic acid al
  • carboxyl group-containing monomer used for the preparation of the acrylic polymer, a monomer similar to the above-mentioned “ethylenically unsaturated carboxylic acid monomer capable of forming an ethylenically unsaturated carboxylic acid monomer unit” Can be mentioned. These may be used alone or in combination of two or more. Among these, methacrylic acid is preferable as the carboxyl group-containing monomer.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-methylol acrylamide and the like. These may be used alone or in combination of two or more. Of these, N-methylolacrylamide is preferred as the hydroxyl group-containing monomer.
  • -Other monomers examples include monomers copolymerizable with the above-described monomers.
  • other monomers include ⁇ , ⁇ -unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; sulfate group-containing monomers such as acrylamide-2-methylpropanesulfonic acid; acrylamide Amide group-containing monomers such as methacrylamide; crosslinkable monomers (crosslinkable monomers) such as allyl glycidyl ether, allyl (meth) acrylate, N-methylolacrylamide; styrene, chlorostyrene, vinyltoluene, Styrene monomers such as t-butylstyrene, methyl vinylbenzoate, vinylnaphthalene, chloromethylstyrene, ⁇ -methylstyrene, divinylbenzene; olefins such as ethylene
  • the unsaturated carboxylic acid polymer is a polymer containing an unsaturated carboxylic acid monomer unit.
  • unsaturated carboxylic acid monomer capable of forming the unsaturated carboxylic acid monomer unit acrylic acid, methacrylic acid, itaconic acid and the like can be used.
  • the polymerization method of the particulate polymer is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method may be used.
  • As the polymerization reaction addition polymerization such as ionic polymerization, radical polymerization, and living radical polymerization can be used.
  • the polymerization solvent, emulsifier, dispersant, polymerization initiator, chain transfer agent, etc. that can be used for the polymerization can be general ones, and the amount used can also be the amount generally used. it can.
  • the binder composition for non-aqueous secondary battery electrodes of the present invention contains any other component such as a reinforcing material, a leveling agent, a viscosity modifier, an electrolytic solution additive, in addition to the above-described components. Also good. These are not particularly limited as long as they do not affect the battery reaction, and known components such as those described in International Publication No. 2012/115096 can be used. Moreover, these components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the binder composition for non-aqueous secondary battery electrodes of this invention can be prepared by mixing the water-soluble polymer mentioned above and arbitrary particulate polymers, a solvent, and another component by a known method. It can. Specifically, the binder composition is obtained by mixing the above components using a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a fill mix, etc. Product can be prepared.
  • a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a fill mix, etc.
  • the water-soluble polymer and any particulate polymer are prepared by polymerization in an aqueous solvent, they are mixed as they are in the form of an aqueous solution or water dispersion to prepare a binder composition containing water as a solvent. can do. Also, for example, after mixing the water-soluble polymer and the electrode active material, the preparation of the binder composition and the preparation of the slurry composition described later may be performed simultaneously, such as adding an arbitrary particulate polymer. Good.
  • content of a water-soluble polymer and a particulate polymer is as follows. That is, the content of the entire water-soluble polymer is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and 50 parts by mass or more with respect to 100 parts by mass of the particulate polymer. More preferably, it is more preferably 80 parts by mass or more, preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 120 parts by mass or less. If the content of the water-soluble polymer and the particulate polymer in the binder composition is within the above range, the slurry composition and the electrode obtained using the slurry composition tend to be excellent in productivity. .
  • the content of the polymer X is 100 masses of the particulate polymer. It is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, still more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, based on 200 parts by mass. It is preferably no greater than part by mass, more preferably no greater than 150 parts by mass, and even more preferably no greater than 120 parts by mass.
  • a binder composition is prepared using a water-soluble polymer and a particulate polymer so that the content of the polymer X is not less than the above lower limit, the viscosity stability of the slurry composition containing the binder composition is further improved. Because it does. Moreover, it is because the adhesiveness with the electrical power collector of the electrode compound-material layer formed using the said slurry composition improves more.
  • a binder composition is prepared using a water-soluble polymer and a particulate polymer so that the content of the polymer X is not more than the above upper limit, while maintaining the high viscosity stability of the slurry composition, This is because it is possible to further improve the adhesion of the electrode mixture layer formed using the slurry composition to the current collector.
  • the slurry composition for non-aqueous secondary battery electrodes of this invention is characterized by including an electrode active material and the binder composition for non-aqueous secondary battery electrodes mentioned above. Moreover, the slurry composition for non-aqueous secondary battery electrodes of the present invention may further contain a conductive material and other components in addition to the electrode active material and the binder composition. If the slurry composition does not contain a binder composition containing a water-soluble polymer containing the polymer X described above, the slurry composition is provided with good viscosity stability, and an electrode assembly formed using the slurry composition. The material layer cannot be satisfactorily adhered to the current collector.
  • the electrode mixture layer is formed using the slurry composition for a non-aqueous secondary battery electrode of the present invention, the adhesion between the current collector and the electrode mixture layer is excellent (having high peel strength). ) An electrode can be obtained.
  • the slurry composition for non-aqueous secondary battery electrodes of this invention is a slurry composition for lithium ion secondary battery negative electrodes is explained in full detail, this invention is not limited to the following example.
  • Electrode active material (negative electrode active material)>
  • a material that can occlude and release lithium is usually used as the negative electrode active material of the lithium ion secondary battery.
  • the material that can occlude and release lithium include a carbon-based negative electrode active material, a non-carbon-based negative electrode active material, and an active material that combines these materials.
  • the carbon-based negative electrode active material refers to an active material having carbon as a main skeleton into which lithium can be inserted (also referred to as “dope”).
  • examples of the carbon-based negative electrode active material include a carbonaceous material and graphite. Quality materials.
  • the carbonaceous material is a material having a low degree of graphitization (ie, low crystallinity) obtained by carbonizing a carbon precursor by heat treatment at 2000 ° C. or lower.
  • the minimum of the heat processing temperature at the time of carbonizing is not specifically limited, For example, it can be 500 degreeC or more.
  • the carbonaceous material include graphitizable carbon that easily changes the carbon structure depending on the heat treatment temperature, and non-graphitizable carbon having a structure close to an amorphous structure typified by glassy carbon.
  • the graphitizable carbon for example, a carbon material using tar pitch obtained from petroleum or coal as a raw material can be mentioned.
  • examples of the non-graphitizable carbon include a phenol resin fired body, polyacrylonitrile-based carbon fiber, pseudo-isotropic carbon, furfuryl alcohol resin fired body (PFA), and hard carbon.
  • the graphite material is a material having high crystallinity close to that of graphite obtained by heat-treating graphitizable carbon at 2000 ° C. or higher.
  • the upper limit of heat processing temperature is not specifically limited, For example, it can be 5000 degrees C or less.
  • the graphite material include natural graphite and artificial graphite.
  • the artificial graphite for example, artificial graphite obtained by heat-treating carbon containing graphitizable carbon mainly at 2800 ° C. or higher, graphitized MCMB heat-treated at 2000 ° C. or higher, and mesophase pitch-based carbon fiber at 2000 ° C. Examples thereof include graphitized mesophase pitch-based carbon fibers that have been heat-treated.
  • the carbon-based negative electrode active material natural graphite (amorphous coated natural graphite) whose surface is at least partially coated with amorphous carbon may be used.
  • the non-carbon-based negative electrode active material is an active material excluding a carbon-based negative electrode active material made of only a carbonaceous material or a graphite material, and examples of the non-carbon-based negative electrode active material include a metal-based negative electrode active material. .
  • the metal-based negative electrode active material is an active material containing a metal, and usually contains an element capable of inserting lithium in the structure, and the theoretical electric capacity per unit mass when lithium is inserted is 500 mAh / g or more. Is an active material.
  • the metal-based negative electrode active material for example, lithium metal, a single metal capable of forming a lithium alloy (for example, Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn, Ti, etc.) and alloys thereof, and oxides, sulfides, nitrides, silicides, carbides, phosphides, and the like thereof are used.
  • an active material containing silicon silicon-based negative electrode active material
  • silicon-based negative electrode active materials examples include silicon (Si), silicon-containing alloys, SiO, SiO x , and a composite of a Si-containing material obtained by coating or combining a Si-containing material with conductive carbon and conductive carbon. Etc.
  • these silicon type negative electrode active materials may be used individually by 1 type, and may be used in combination of 2 types. From the viewpoint of increasing the capacity of the lithium ion secondary battery, the silicon-based negative electrode active material is preferably an alloy containing silicon and SiO x .
  • the alloy containing silicon examples include an alloy composition containing silicon and at least one element selected from the group consisting of titanium, iron, cobalt, nickel, and copper.
  • the alloy containing silicon examples include an alloy composition containing silicon, aluminum, and a transition metal such as iron, and further containing a rare earth element such as tin and yttrium.
  • the dispersion medium of the lithium ion secondary battery negative electrode slurry composition is not particularly limited, and a known dispersion medium such as water, n-methylpyrrolidone, or the like can be used. Among these, water is preferably used as the dispersion medium. In addition, at least one part of the dispersion medium of a slurry composition can be made into the solvent which the binder composition used for preparation of a slurry composition contained, without being specifically limited.
  • the slurry composition for lithium ion secondary battery negative electrodes may further contain other components in addition to the components described above.
  • other components that can be included in the slurry composition include, for example, a conductive material; components similar to the other components that can be included in the binder composition described above.
  • the slurry composition for a lithium ion secondary battery negative electrode can be prepared by dispersing the above components in a dispersion medium. Specifically, the above components and the dispersion medium are mixed using a mixer such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crushed crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, or a fill mix. Thus, a slurry composition can be prepared.
  • water is usually used as the dispersion medium, but an aqueous solution of an arbitrary compound or a mixed solution of a small amount of an organic medium and water may be used.
  • the ratio of each said component in a slurry composition can be adjusted suitably.
  • the content of the binder composition in the slurry composition is preferably 0.5 parts by mass or more in terms of solid content per 100 parts by mass in terms of solid content in the slurry composition. More preferably, it is 7 parts by mass or more, more preferably 1 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass or less. Is more preferable.
  • the content of the water-soluble polymer in the slurry composition is preferably 0.2 parts by mass or more and 0.4 parts by mass or more per 100 parts by mass of the slurry composition in terms of solid content. More preferably, it is preferably 3 parts by mass or less, and more preferably 2 parts by mass or less. Furthermore, the content of the electrode active material in the slurry composition is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, in terms of solid content, and more preferably 95 parts by mass or more. It is preferably 5 parts by mass or less, and more preferably 99.3 parts by mass or less.
  • the abundance ratio of the electrode active material and the water-soluble polymer in the slurry composition is 90:10 to 99.5: 0.5 in terms of solid content. Preferably, it is 95: 5 to 99: 1.
  • the electrode for a non-aqueous secondary battery of the present invention has a current collector and an electrode mixture layer formed using the above-described slurry composition for a non-aqueous secondary battery electrode of the present invention.
  • the electrode composite material layer has a structure formed on the current collector.
  • the electrode mixture layer includes at least an electrode active material and a water-soluble polymer containing the polymer X having a predetermined composition.
  • Each component such as the electrode active material is contained in the slurry composition for a non-aqueous secondary battery electrode described above, and a suitable abundance ratio of each component is in the binder composition and / or the slurry composition. It is the same as the preferred abundance ratio of each component in the product.
  • the electrode for a non-aqueous secondary battery of the present invention has an electrode mixture layer formed using a slurry composition containing the binder composition for a non-aqueous secondary battery electrode of the present invention.
  • the peel strength between the material layer and the current collector is high, and the adhesion is good. Therefore, when the nonaqueous secondary battery electrode of the present invention is used for the production of a secondary battery, a secondary battery excellent in battery characteristics, particularly in life characteristics such as cycle characteristics, can be obtained.
  • an electrically conductive and electrochemically durable material is used.
  • a current collector made of a metal material such as iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, or platinum can be used.
  • the said material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the electrode mixture layer includes, for example, a step of applying a slurry composition for a non-aqueous secondary battery electrode (application step), a step of drying the applied slurry composition for a non-aqueous secondary battery electrode (drying step), and It is formed through.
  • a method for applying the slurry composition for a non-aqueous secondary battery electrode on, for example, a current collector is not particularly limited, and a known method can be used. Specifically, as a coating method, a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method, or the like can be used. At this time, the slurry composition may be applied to only one side of the current collector or may be applied to both sides. Further, the thickness of the slurry composition film on the current collector after application and before drying can be appropriately set according to the thickness of the electrode mixture layer obtained by drying.
  • the method for drying the slurry composition coated on the current collector is not particularly limited, and a known method can be used. For example, a drying method using hot air, hot air, low-humidity air, a vacuum drying method, infrared rays or electronic The drying method by irradiation of a line etc. is mentioned.
  • a drying method using hot air, hot air, low-humidity air, a vacuum drying method, infrared rays or electronic The drying method by irradiation of a line etc. is mentioned.
  • an electrode mixture layer can be formed on the current collector, and an electrode having a current collector and an electrode mixture layer can be obtained.
  • the electrode mixture layer may be subjected to pressure treatment using a die press or a roll press. The adhesion between the electrode mixture layer and the current collector can be improved by the pressure treatment.
  • the electrode mixture layer is formed using the slurry composition for a non-aqueous secondary battery electrode of the present invention, it is difficult to generate a springback even after being subjected to pressure treatment. Therefore, a high-density electrode can be manufactured.
  • an electrode compound-material layer contains a curable polymer, it is preferable to harden the said polymer after formation of an electrode compound-material layer.
  • the non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolytic solution, and at least one of the positive electrode and the negative electrode is the above-described electrode for a non-aqueous secondary battery of the present invention. That is, the non-aqueous secondary battery of the present invention may have a positive electrode that is a non-aqueous secondary battery electrode of the present invention and a negative electrode that is a known negative electrode, and the negative electrode is a non-aqueous secondary battery electrode of the present invention.
  • the positive electrode may be a known positive electrode
  • both the positive electrode and the negative electrode may be the nonaqueous secondary battery electrode of the present invention.
  • the non-aqueous secondary battery of this invention is equipped with the electrode for non-aqueous secondary batteries of this invention, it can have lifetime characteristics, such as the outstanding cycling characteristics.
  • the non-aqueous secondary battery is a lithium ion secondary battery
  • the present invention is not limited to the following example.
  • the positive electrode is not particularly limited, and can be the electrode for a non-aqueous secondary battery of the present invention described above. That is, the positive electrode can have a positive electrode mixture layer and a current collector formed using the slurry composition for a non-aqueous secondary battery electrode of the present invention.
  • the positive electrode is formed on a known positive electrode, for example, a positive electrode made of a thin metal plate, or on a current collector and a current collector.
  • a positive electrode having a positive electrode composite material layer can be used.
  • the positive electrode mixture layer usually contains a positive electrode active material, a conductive material, and a binder, and can optionally further contain other components such as a thickener.
  • a thin film made of a metal material such as aluminum can be used.
  • a method for forming the positive electrode active material, the conductive material, the binder, and the positive electrode mixture layer on the current collector for example, a method described in JP2013-145663A can be used.
  • the negative electrode is not particularly limited and can be the electrode for a non-aqueous secondary battery according to the present invention described above. That is, the negative electrode can have a negative electrode mixture layer formed using the slurry composition for a non-aqueous secondary battery electrode of the present invention and the above-described current collector, for example.
  • the negative electrode may be a known negative electrode. As the known negative electrode, for example, the negative electrode described in JP2013-145663A can be used.
  • the separator is not particularly limited.
  • a microporous film using a polyolefin-based resin polyethylene, polypropylene, polybutene, polyvinyl chloride), polyethylene terephthalate, polycycloolefin, polyether sulfone, polyamide, polyimide
  • microporous membranes using resins such as polyimide amide, polyaramid, polycycloolefin, nylon, and polytetrafluoroethylene, woven or non-woven fabrics using polyolefin fibers, and aggregates of particles made of insulating materials.
  • a microporous film using a polyolefin resin (polyethylene, polypropylene, polybutene, polyvinyl chloride) is preferred.
  • a microporous film made of polypropylene resin is more preferable.
  • an electrolytic solution in which an electrolyte is dissolved in a solvent can be used.
  • the solvent an organic solvent capable of dissolving the electrolyte can be used.
  • carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), ethyl methyl carbonate (EMC);
  • DMC dimethyl carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • EMC ethyl methyl carbonate
  • esters such as ⁇ -butyrolactone and methyl formate
  • ethers such as 1,2-dimethoxyethane and tetrahydrofuran
  • sulfur-containing compounds such as sulfolane and dimethyl sulfoxide
  • a lithium salt can be used as the electrolyte.
  • the lithium salt for example, compounds described in JP 2012-204303 A can be used.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable as the electrolyte because they are easily dissolved in an organic solvent and exhibit a high degree of dissociation.
  • electrolyte may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. Usually, the lithium ion conductivity tends to increase as the supporting electrolyte having a higher degree of dissociation is used, and therefore the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
  • the non-aqueous secondary battery of this invention can be manufactured using a known assembly method, without being restrict
  • the non-aqueous secondary battery of the present invention includes, for example, a negative electrode obtained as described above, a positive electrode, and a separator as necessary in a battery shape, folded into a battery container, and put into a battery container. It can manufacture by inject
  • an overcurrent prevention element such as a fuse or PTC element, an expanded metal, a lead plate, etc. are provided as necessary. May be.
  • the shape of the secondary battery may be any of a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, and the like.
  • battery members such as a positive electrode, a negative electrode, and a separator included in the secondary battery are usually arranged so that the positive electrode is in contact with one side of the separator and the negative electrode is in contact with the other side of the separator. More specifically, the positive electrode mixture layer is disposed on one side of the separator, and the negative electrode mixture layer is disposed on the other side of the separator so as to be in contact with the separator.
  • ⁇ Glass transition temperature> The aqueous solution containing the polymer X was dried for 3 days in an environment with a relative humidity of 50% and a temperature of 23 ° C. to 26 ° C. to form a film having a thickness of 1 ⁇ 0.3 mm.
  • the formed film was dried with a vacuum dryer at a temperature of 60 ° C. for 10 hours.
  • a differential scanning calorimeter product name, manufactured by Nanotechnology Co., Ltd.
  • the glass transition temperature (° C.) was measured using “DSC6220SII”).
  • ⁇ Electrolytic solution swelling> The aqueous solution containing the polymer X was dried in an environment with a relative humidity of 50% and a temperature of 23 ° C. to 25 ° C. to form a film having a thickness of 1 ⁇ 0.3 mm.
  • the film formed was dried with a vacuum dryer at a temperature of 60 ° C. for 10 hours, then cut into film pieces, and the mass W0 of the obtained film pieces was precisely weighed.
  • solvent ethylene carbonate
  • EMC ethyl methyl carbonate
  • solubility in water was measured and evaluated by filtration as follows. Specifically, 10 ⁇ 0.5 g of polymer X in terms of solid content is added to 100 g of ion-exchanged water and mixed in a disper (rotation speed: 2,000 rpm) for 2 hours in an environment of temperature 20 ° C. and pH 7. did. The resulting mixture was then filtered through a 400 mesh screen. Then, the residue remaining on the screen without passing through the screen is weighed and subtracted from the mass of the added polymer X, whereby the mass (g) of the polymer X dissolved in the ion-exchanged water is obtained at a temperature of 20 ° C.
  • the solubility of polymer X in water was calculated.
  • the solubility of polymer X in water at a temperature of 20 ° C. is 1 g / 100 g-H 2 O or more, the solubility is sufficient (corresponding to “ ⁇ ” in the table) and less than 1 g / 100 g-H 2 O When it was, it was evaluated that the solubility was insufficient (corresponding to “x” in the table).
  • DELTA viscosity maintenance factor
  • Viscosity maintenance factor ⁇ is 90% or more and 110% or less
  • B Viscosity maintenance factor ⁇ is 80% or more and less than 90%
  • C Viscosity maintenance factor ⁇ is 70% or more and less than 80%
  • D Viscosity maintenance factor ⁇ is less than 70%, Or over 110%
  • the springback of the negative electrode mixture layer was evaluated based on the electrode density. Specifically, first, the negative electrode composite material layer side of the produced negative electrode raw material was roll-pressed under the condition of a linear pressure of 11 t (tons) in an environment of a temperature of 25 ⁇ 3 ° C., and the electrode composite material layer density was 1.70 g. / Cm 3 was adjusted. Thereafter, the negative electrode was left for one week in an environment of a temperature of 25 ⁇ 3 ° C. and a relative humidity of 50 ⁇ 5%. And the electrode mixture layer density (g / cm ⁇ 3 >) of the negative electrode after standing was measured, and the following references
  • ⁇ Negative electrode adhesion> The prepared negative electrode for a lithium ion secondary battery was cut into a rectangle having a length of 100 mm and a width of 10 mm to obtain a test piece. Next, a cellophane tape (as defined in JIS Z1522) is applied to the surface of the negative electrode mixture layer with the surface having the negative electrode mixture layer facing down, and one end of the current collector is pulled vertically at a pulling speed of 50 mm / min. The peel strength (N / m) when the film was pulled and peeled was measured (note that the cellophane tape is fixed to the test bench). The same measurement as above was performed three times, the average value was obtained, and evaluated according to the following criteria.
  • ⁇ Bulge of negative electrode> The manufactured lithium ion secondary battery was allowed to stand for 5 hours in an environment at a temperature of 25 ° C. with the electrode immersed in the electrolyte. Next, the stationary secondary battery was charged to a cell voltage of 3.65 V by a constant current method at a rate of 0.2 C in an environment at a temperature of 25 ° C. Then, the aging process was performed with respect to the charged secondary battery for 12 hours in the environment of a temperature of 60 degreeC. Subsequently, the secondary battery subjected to the aging treatment was discharged to a cell voltage of 3.00 V by a constant current method at a rate of 0.2 C in an environment at a temperature of 25 ° C.
  • the lithium ion secondary battery which performed the discharge process was disassembled, and the value remove
  • the lithium ion secondary battery is assembled again, and the assembled secondary battery is charged and discharged under the conditions of a cell voltage of 4.20 V to 3.00 V and a charge / discharge rate of 1 C in an environment at a temperature of 25 ° C. 50 cycles were performed. Finally, the secondary battery after 50 cycles was charged at a rate of 1C in an environment at a temperature of 25 ° C.
  • the charged secondary battery was disassembled, the negative electrode was taken out, and a value obtained by removing the thickness of the current collector from the thickness of the entire negative electrode was measured as the thickness (d1) of the negative electrode after cycling.
  • the smaller the swelling of the negative electrode after the cycle the more the negative electrode mixture layer maintains the structure even when the charge / discharge cycle is repeated, indicating that the secondary battery has a longer life.
  • Example 1 Preparation of aqueous solution containing polymer X> 720 parts of ion exchange water was charged into a 1 L flask with a septum, heated to a temperature of 40 ° C., and the inside of the flask was replaced with nitrogen gas at a flow rate of 100 mL / min. Next, 10 parts of ion-exchanged water, 25 parts of acrylic acid as an ethylenically unsaturated carboxylic acid monomer, 35 parts of acrylamide as a (meth) acrylamide monomer, and as a hydroxyl group-containing vinyl monomer 40 parts of 2-hydroxyethyl acrylate was mixed and injected into the flask with a syringe.
  • the polymerization reaction was stopped by opening the flask in the air, and the product was deodorized at a temperature of 80 ° C. to remove residual monomers. Thereafter, by adjusting the pH of the product to 8 using a 10% aqueous solution of lithium hydroxide, an ethylenically unsaturated carboxylic acid monomer unit, a (meth) acrylamide monomer unit, and a hydroxyl group-containing vinyl monomer An aqueous solution containing a polymer X containing body units at a ratio within a predetermined range was obtained.
  • the composition of each monomer unit contained in the obtained polymer X was the same as the ratio (preparation ratio) of each monomer in all monomers used for polymerization of the polymer X.
  • the obtained polymer X was water-soluble according to the definition 1 of this specification. And using the aqueous solution containing the obtained polymer X, according to the above-mentioned method, the glass transition temperature of the polymer X, electrolyte solution swelling degree, and the solubility with respect to water were measured and evaluated. The results are shown in Table 1.
  • ⁇ Preparation of aqueous dispersion containing particulate polymer> In a 5 MPa pressure vessel equipped with a stirrer, 65 parts of styrene as an aromatic vinyl monomer, 35 parts of 1,3-butadiene as an aliphatic conjugated diene monomer, 2 parts of itaconic acid as a carboxyl group-containing monomer, 1 part of 2-hydroxyethyl acrylate as a hydroxyl group-containing monomer, 0.3 part of t-dodecyl mercaptan as a molecular weight modifier, 5 parts of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water as a solvent, And 1 part of potassium persulfate as a polymerization initiator was added, and after stirring sufficiently, the temperature was raised to 55 ° C.
  • a slurry composition containing a binder composition containing a water-soluble polymer and a particulate polymer was prepared as follows without preparing the binder composition in advance prior to the preparation of the slurry composition. . That is, the binder composition and the slurry composition were prepared in the same process. In other words, in a planetary mixer, 98 parts of artificial graphite (theoretical capacity: 360 mAh / g) as a negative electrode active material and an aqueous solution (solid content concentration: 4.5%) containing the water-soluble polymer obtained above were solidified. 1 part was added in minutes.
  • the slurry composition for a negative electrode of a lithium ion secondary battery is applied to the surface of a copper foil having a thickness of 15 ⁇ m, which is a current collector, with a comma coater so that the coating amount is 13.8 to 14.2 mg / cm 2. Applied. Thereafter, the copper foil coated with the lithium ion secondary battery negative electrode slurry composition is transported at a rate of 400 mm / min in an oven at a temperature of 80 ° C. for 2 minutes and further in an oven at a temperature of 110 ° C. for 2 minutes.
  • the slurry composition on copper foil was dried, and the negative electrode original fabric by which the negative electrode compound-material layer was formed on the electrical power collector was obtained. And using the obtained negative electrode raw material, according to the above-mentioned method, the springback of the negative mix layer was measured and evaluated. The results are shown in Table 1.
  • the obtained negative electrode original fabric was roll-pressed so that the electrode mixture layer density was adjusted to 1.68 to 1.72 g / cm 3 .
  • the negative electrode for lithium ion secondary batteries was obtained by placing it in an environment of 105 ° C. under vacuum conditions for 4 hours. And using the obtained negative electrode, according to the above-mentioned method, the adhesiveness of the negative electrode was measured and evaluated. The results are shown in Table 1.
  • the obtained slurry composition for a lithium ion secondary battery positive electrode was applied onto an aluminum foil having a thickness of 20 ⁇ m as a current collector with a comma coater in an amount of 26.0 to 27.0 mg / cm 2. It applied so that it might become.
  • the aluminum foil coated with the slurry composition for a positive electrode of a lithium ion secondary battery was dried by conveying it in an oven at a temperature of 60 ° C. at a rate of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a positive electrode raw material.
  • the obtained positive electrode raw material was pressed with a roll press machine so that the electrode mixture layer density was 3.40 to 3.50 g / cm 3, and for the purpose of removing the dispersion medium, The positive electrode was obtained by placing in an environment at a temperature of 120 ° C. for 3 hours.
  • Example 2 In the preparation of the aqueous solution containing the polymer X, the amount of acrylic acid was changed to 10 parts, the amount of acrylamide was changed to 25 parts, and the amount of 2-hydroxyethyl acrylate was changed to 65 parts. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 3 In the preparation of the aqueous solution containing the polymer X, the amount of acrylic acid was changed to 15 parts, the amount of acrylamide was changed to 10 parts, and the amount of 2-hydroxyethyl acrylate was changed to 75 parts. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 4 In the preparation of the aqueous solution containing the polymer X, the amount of acrylic acid was changed to 30 parts, the amount of acrylamide was changed to 45 parts, and the amount of 2-hydroxyethyl acrylate was changed to 25 parts. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 5 In the preparation of the aqueous solution containing the polymer X, the amount of acrylic acid was changed to 15 parts, the amount of acrylamide was changed to 55 parts, and the amount of 2-hydroxyethyl acrylate was changed to 30 parts. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 6 In the preparation of the aqueous solution containing the polymer X, the amount of acrylic acid was changed to 35 parts and the amount of 2-hydroxyethyl acrylate was changed to 30 parts. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 7 In the preparation of the aqueous solution containing the polymer X, the amount of acrylic acid was changed to 8 parts, the amount of acrylamide was changed to 37 parts, and the amount of 2-hydroxyethyl acrylate was changed to 55 parts. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 8 In the preparation of the aqueous solution containing the polymer X, the amount of 2-hydroxyethyl acrylate was changed to 25 parts, and 15 parts of 2-hydroxyethyl methacrylate was added. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 9 In the preparation of the aqueous solution containing the polymer X, the amount of acrylic acid was changed to 24.5 parts, and a polyfunctional ethylenically unsaturated carboxylic acid ester unit capable of forming a polyfunctional ethylenically unsaturated carboxylic acid ester monomer unit was used. 0.5 parts of ethoxylated pentaerythritol tetraacrylate (product name: “ATM-35E” manufactured by Shin-Nakamura Chemical Co., Ltd.) as a tetrameric ethylenically unsaturated carboxylic acid ester monomer as a monomer was added.
  • ethoxylated pentaerythritol tetraacrylate product name: “ATM-35E” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1.
  • the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 10 In the preparation of the aqueous solution containing the polymer X, the amount of acrylamide was changed to 20 parts, and 15 parts of methyl acrylate as another monomer was added. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 11 In the preparation of the aqueous solution containing the polymer X, 2-hydroxyethyl acrylate was not used, but 40 parts of N-hydroxyethyl acrylamide was used. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 12 In the preparation of the aqueous solution containing the water-soluble polymer, 0.5 part of the aqueous solution containing the obtained polymer X was equivalent to the solid content, and 0.5 parts of the carboxymethyl cellulose as the other water-soluble polymer was equivalent to the solid content.
  • An aqueous solution containing a water-soluble polymer (polymer X and carboxymethyl cellulose) was obtained by mixing the parts. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1.
  • the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • Example 13 In the preparation of the binder composition and the slurry composition, an aqueous dispersion containing a particulate polymer prepared by the following method was used as an aqueous dispersion containing a particulate polymer. Except for the above, a polymer X, a water-soluble polymer, a particulate polymer, a binder composition, a slurry composition, a negative electrode, a positive electrode, and a secondary battery were produced in the same manner as in Example 1. In addition, the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • ⁇ Preparation of aqueous dispersion containing particulate polymer> In a 5 MPa pressure vessel with a stirrer, 82 parts of n-butyl acrylate as a (meth) acrylic acid ester monomer, 2 parts of methacrylic acid as a carboxyl group-containing monomer, N-methylol as a hydroxyl group-containing monomer 1 part of acrylamide, 2 parts of acrylonitrile as another monomer, 1 part of allyl glycidyl ether, 4 parts of sodium lauryl sulfate as an emulsifier, 150 parts of ion-exchanged water as a solvent, and ammonium persulfate as a polymerization initiator After 5 parts were added and sufficiently stirred, the temperature was raised to 80 ° C.
  • Example 14 In the preparation of the aqueous solution containing the water-soluble polymer, the aqueous solution containing the obtained polymer X was 0.5 parts in terms of solids, and sodium alginate as another water-soluble polymer was 0.5 parts in terms of solids.
  • the obtained polymer X and water-soluble polymer were water-soluble according to the definition 1 of this specification. And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.
  • AA indicates an acrylic acid unit
  • MAA indicates a methacrylic acid unit
  • AAm indicates an acrylamide unit
  • MAAm indicates a methacrylamide unit
  • 2-HEA refers to 2-hydroxyethyl acrylate units
  • 2-HEMA refers to 2-hydroxyethyl methacrylate units
  • HEAAm indicates N-hydroxyethylacrylamide unit
  • EPETA refers to an ethoxylated pentaerythritol tetraacrylate unit
  • MA represents a methyl acrylate unit
  • CMC refers to the sodium salt of carboxymethylcellulose
  • SBR indicates a styrene-butadiene copolymer
  • ACR indicates an acrylic polymer
  • A-Na refers to sodium alginate.
  • Tables 1 and 2 show that the polymer X contains an ethylenically unsaturated carboxylic acid monomer unit, a (meth) acrylamide monomer unit, and a hydroxyl group-containing vinyl monomer unit within a predetermined range.
  • the slurry composition is excellent in viscosity stability and the electrode mixture layer is in good contact with the current collector.
  • Comparative Example 1 in which the polymer X does not contain a (meth) acrylamide monomer unit, both excellent viscosity stability of the slurry composition and excellent adhesion between the electrode mixture layer and the current collector are compatible. It cannot be seen that the viscosity stability of the slurry composition is particularly poor. Further, in Comparative Examples 2 to 4 in which the content ratio of the (meth) acrylamide monomer unit in the polymer X is more than 60% by mass, the excellent viscosity stability of the slurry composition, the electrode mixture layer and the current collector It can be seen that the excellent adhesion between the two is not compatible.
  • a slurry composition capable of forming an electrode mixture layer having excellent viscosity stability and adhesion to a current collector, and a binder composition capable of preparing the slurry composition. be able to.
  • an electrode which has an electrode compound-material layer excellent in adhesiveness with a collector, and a secondary battery provided with the said electrode can be provided.

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Abstract

L'invention concerne une composition de liant, laquelle permet de préparer une composition de suspension épaisse qui possède une excellente stabilité de viscosité et est apte à former une couche de mélange d'électrodes, laquelle présente une excellente adhésion à un collecteur. Selon la présente invention, une composition de liant destinée à des électrodes de batterie secondaire non aqueuse comprend un polymère soluble dans l'eau comprenant un polymère X, lequel comprend de 1 % en masse à 50 % en masse (inclus) d'une unité monomère d'acide carboxylique éthyléniquement insaturé, de 10 % en masse à 60 % en masse (inclus) d'une unité monomère de (meth)acrylamide, et de 5 % en masse à 89 % en masse (inclus) d'une unité monomère vinylique comprenant un groupe hydroxyle.
PCT/JP2017/024192 2016-07-07 2017-06-30 Composition de liant destinée à des électrodes de batterie secondaire non aqueuse, composition de suspension épaisse destinée à des électrodes de batterie secondaire non aqueuse, électrode de batteries secondaires non aqueuses, et batterie secondaire non aqueuse Ceased WO2018008555A1 (fr)

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EP3783699A1 (fr) * 2019-08-22 2021-02-24 Arakawa Chemical Industries, Ltd. Solution aqueuse de liant thermiquement réticulable pour batterie lithium-ion, suspension thermiquement réticulable pour électrode négative de batterie lithium-ion, électrode négative pour batterie lithium-ion et batterie lithium-ion
JP2021044238A (ja) * 2019-09-05 2021-03-18 荒川化学工業株式会社 リチウムイオン電池電極用バインダー水溶液、リチウムイオン電池電極用スラリー、リチウムイオン電池電極及びリチウムイオン電池
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US20230197961A1 (en) * 2021-12-15 2023-06-22 Lg Energy Solution, Ltd. Anode composition, lithium secondary battery anode comprising same, and lithium secondary battery comprising anode
WO2023120533A1 (fr) * 2021-12-21 2023-06-29 富士フイルム株式会社 Composition de liant pour batteries secondaires, feuille d'électrode, batterie secondaire, procédé de production de feuille d'électrode et procédé de production de batterie secondaire
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