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WO2011099344A1 - Composition pour liant d'électrode, composition pour électrode, électrode et dispositif électrochimique - Google Patents

Composition pour liant d'électrode, composition pour électrode, électrode et dispositif électrochimique Download PDF

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Publication number
WO2011099344A1
WO2011099344A1 PCT/JP2011/051043 JP2011051043W WO2011099344A1 WO 2011099344 A1 WO2011099344 A1 WO 2011099344A1 JP 2011051043 W JP2011051043 W JP 2011051043W WO 2011099344 A1 WO2011099344 A1 WO 2011099344A1
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electrode
composition
polymer
electrochemical device
monomer
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English (en)
Japanese (ja)
Inventor
武志 茂木
達朗 本多
真坂　房澄
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JSR Corp
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JSR Corp
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Priority to JP2011553784A priority Critical patent/JPWO2011099344A1/ja
Priority to KR1020127021311A priority patent/KR20130006597A/ko
Priority to CN2011800095538A priority patent/CN102763252A/zh
Publication of WO2011099344A1 publication Critical patent/WO2011099344A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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 an electrochemical device electrode binder composition for obtaining an electrode of an electrochemical device such as a secondary battery, an electric double layer capacitor, or a lithium ion capacitor, an electrochemical device electrode composition, and the electrochemical device electrode
  • the present invention relates to an electrochemical device electrode obtained from a composition, and an electrochemical device comprising the electrochemical device electrode.
  • a liquid composition containing a binder and an electrode active material is applied to the surface of a current collector. Then, a method of forming an electrode layer on the current collector by drying is known.
  • an electrode binder composition for obtaining such an electrochemical device electrode a composition in which a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride is dissolved in an organic solvent is known.
  • a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride is dissolved in an organic solvent.
  • the fluororesin is not sufficiently high in adhesion to the metal constituting the current collector and is not sufficiently high in flexibility, it can be obtained particularly when a wound battery is manufactured. There is a problem that a crack occurs in the obtained electrode layer, or peeling between the obtained electrode layer and the current collector occurs.
  • Patent Document 1 As a composition for an electrode binder capable of forming a highly flexible electrode layer having high adhesion to the metal constituting the current collector, a composition comprising a styrene-butadiene latex (Patent Document 1) It has been known.
  • the present invention has been made on the basis of the circumstances as described above, and an object of the present invention is to provide a highly flexible electrode that has high adhesion to a current collector and does not cause peeling during press working. It is providing the composition for electrode binders which can form a layer, the composition for electrodes, the electrode obtained from this composition for electrodes, and the electrochemical device provided with this electrode.
  • the object of the present invention is achieved by the following means [1] to [9].
  • (A) (a) a repeating unit derived from an aliphatic conjugated diene monomer, and (b) a repeating unit derived from an ethylenically unsaturated carboxylic acid monomer, Has at least one glass transition point in the range of -80 to 100 ° C., and A polymer having a temperature differential coefficient of logarithm of storage elastic modulus of ⁇ 0.09 or more and ⁇ 0.02 or less and a width of a temperature region of 20 ° C. or more (hereinafter also referred to as “(A) polymer”); (B) The composition for electrode binders containing a liquid medium.
  • the polymer (A) is (C) The composition for electrode binders according to [1] or [2], further comprising a repeating unit derived from an alkyl (meth) acrylate compound.
  • the polymer (A) is (D) The composition for an electrode binder according to any one of [1] to [3], further comprising a repeating unit derived from a vinyl cyanide compound.
  • composition for an electrode binder according to any one of [1] to [4], wherein the (A) polymer has a number average particle diameter of 80 to 250 nm.
  • composition for an electrode binder according to any one of [1] to [5], wherein the polymer (A) is obtained by emulsion polymerization in multiple stages, and the polymerization temperature is less than 70 ° C. throughout the entire polymerization process. object.
  • the electrode for electrochemical devices which has an electrode layer obtained from the slurry for electrochemical device electrodes as described in said [7] in the at least one surface of the said electrical power collector.
  • an electrode layer that has high adhesion to the current collector, does not cause peeling during press processing, and has high flexibility.
  • composition for electrode binder of the present invention comprises (A) (a) a repeating unit derived from an aliphatic conjugated diene monomer and (b) a repeating unit derived from an ethylenically unsaturated carboxylic acid monomer. At least one glass transition point (Tg) in the range of ⁇ 80 to 100 ° C., and the logarithmic temperature differential coefficient of the storage modulus is ⁇ 0.09 or more and ⁇ 0.02 or less.
  • Tg glass transition point
  • a polymer having a region width of 20 ° C. or more hereinafter also referred to as “(A) polymer”
  • component (B)”) are included. Each component is described in detail below.
  • the (A) polymer is a constituent component contained in the composition for an electrode binder of the present invention together with the liquid medium (B) described later.
  • this (A) polymer is inherent in the electrode binder composition of the present invention. Play a role.
  • the polymer (A) includes (a) a repeating unit derived from an aliphatic conjugated diene monomer and (b) a repeating unit derived from an ethylenically unsaturated carboxylic acid monomer.
  • a temperature region having a glass transition point in the range of ⁇ 80 to 100 ° C. and a logarithmic temperature differential coefficient of storage modulus of ⁇ 0.09 to ⁇ 0.02 (hereinafter referred to as “temperature range”) , “Specific temperature region”) is 20 ° C. or more.
  • the polymer (A) contained in the electrode binder composition of the present invention has at least one glass transition point (hereinafter also referred to as “Tg”) in the range of ⁇ 80 to 100 ° C. When such a polymer is used, flexibility can be imparted to the electrode while maintaining the adhesion between the electrode layer containing the composition for electrode binder of the present invention and the current collector.
  • Tg glass transition point
  • Tg glass transition point
  • the composition for an electrode binder containing the polymer (A) and the component (B) is poured into a 5 ⁇ 4 cm frame and dried in a constant temperature bath at 70 ° C. ⁇ 24 hours to form a film having a thickness of about 100 ⁇ m. Make it. About 10 mg is cut out from the produced film, collected in an aluminum container and sealed. Using a differential scanning calorimeter (DSC204F1, manufactured by NETZSCH) in an air atmosphere, a DSC chart is created for a temperature range of ⁇ 80 ° C. to 100 ° C. at a temperature rising rate of 20 ° C./min, and Tg is calculated. In addition, the reading method of Tg from a DSC chart follows the method of calculating
  • the (A) polymer contained in the electrode binder composition of the present invention has a temperature range where the logarithmic temperature differential coefficient of the storage elastic modulus is in the range of ⁇ 0.09 to ⁇ 0.02.
  • the width is 20 ° C. or more. This temperature region corresponds to a transition region existing between the glassy region and the rubbery region in the polymer.
  • a polymer having a specific temperature region as described above indicates that the high storage elastic modulus polymer and the low storage elastic modulus polymer exist while changing the composition stepwise, unlike the state where the heterogeneous structure is formed. ing. By using such a polymer, it is possible to impart appropriate flexibility to the electrode layer while maintaining the characteristics of the highly elastic polymer required when the electrode is press-molded.
  • the width of the temperature region is less than 20 ° C., it may be difficult to achieve compatibility between current collector plate adhesion, press suitability, and winding performance.
  • the specific temperature range is determined according to the following procedure.
  • the width of the specific temperature region of the polymer can be determined according to the following procedure.
  • T (m) represents a temperature having the smallest difference from the temperature represented by the following formula in the measurement data.
  • T (m) ⁇ 80 + 5 m [° C.]
  • T (m) ⁇ 80 + 5 m [° C.]
  • E ′ (m) is a value of the storage elastic modulus at the temperature T (m).
  • a (n) is calculated according to the following definition for each integer n from 0 to 35, and the storage elastic modulus at the temperature T (n) of the polymer is calculated.
  • a (n) (Log (E ′ (n + 1)) ⁇ Log (E ′ (n))) / (T (n + 1) ⁇ T (n)) (2-3) Determination of specific temperature range
  • n is n1
  • n2 is set (where n1> n2).
  • a range between T (n1) and T (n2) is a specific temperature region, and ⁇ T defined by the following equation is a width of the specific temperature region.
  • ⁇ T T (n2) ⁇ T (n1) [° C.]
  • the (A) polymer contained in the electrode binder composition of the present invention is present as particles in the composition, and the average particle size is preferably 80 to 250 nm, more preferably 83 to 230 nm, More preferably, it is 85 to 200 nm.
  • the particle diameter is in the above range, the dispersion stability when adjusting the electrode slurry by mixing the electrode binder composition and the active material is improved, and a slurry property having good coatability can be obtained.
  • the particle size is in the above range, the adhesion between the current collector and the electrode layer tends to be improved.
  • the average particle diameter (hydrodynamic diameter) is determined by, for example, using the laser particle size analysis system LPA-3000s / 3100 manufactured by Otsuka Electronics Co., Ltd., by the dynamic light scattering method. It can be calculated by measuring.
  • the (A) polymer contained in the electrode binder composition of the present invention can be obtained, for example, by emulsion polymerization.
  • examples of the emulsion polymerization include seed polymerization using seed particles.
  • the emulsion polymerization step is carried out by polymerizing monomer components in the presence of an emulsifier, a polymerization initiator and a molecular weight regulator in an aqueous medium.
  • (A) an aliphatic conjugated diene monomer and (b) an ethylenically unsaturated monomer are used as essential monomer components constituting the polymer (A). And carboxylic acid monomers.
  • (c) alkyl (meth) acrylate compounds, (d) vinyl cyanide compounds, etc. may be mentioned as monomer components that can constitute the polymer (A) if necessary.
  • (a) Aliphatic conjugated diene monomer (a) (a) Aliphatic conjugated diene used in the production of the polymer (A) contained in the composition for electrode binders of the present invention
  • the monomer include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, chloroprene, and the like, with 1,3-butadiene being preferred.
  • These (a) aliphatic conjugated diene monomers can be used alone or in combination of two or more.
  • (b) Ethylenically unsaturated carboxylic acid monomer (A) Examples of (b) ethylenically unsaturated carboxylic acid monomer used in the production of the polymer include itaconic acid, Acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like can be mentioned, and itaconic acid, acrylic acid, methacrylic acid and fumaric acid are particularly preferable. These (b) ethylenically unsaturated carboxylic acid monomers may be used alone or in combination of two or more.
  • alkyl (meth) acrylate compound is also a monomer preferably used for the production of (A) polymer.
  • (meth) acrylate” is a concept including “acrylate” and corresponding “methacrylate”.
  • alkyl (meth) acrylate compounds methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) Examples include acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, and methyl methacrylate is particularly preferable.
  • (d) Vinyl cyanide compound in the present invention, can also be a monomer component suitably used in the production of (A) polymer.
  • Examples of such (d) vinyl cyanide compound include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred.
  • (A) other monomer components that can be used for the production of the polymer (A) examples include other vinyl monomers copolymerizable with the monomers (a) to (d).
  • Examples of such “(e) other vinyl monomers” include aromatic vinyl compounds, vinyl acetate, acrylamide compounds, and the like.
  • examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, and the like, and styrene is particularly preferable.
  • acrylamide compounds include acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropyl (meth) acrylamide and the like.
  • each repeating unit (a) Aliphatic conjugated diene monomer (A) used in the production of the polymer (A) contained in the electrode binder composition of the present invention (a)
  • the aliphatic conjugated diene monomer is 20 to 20 parts by weight when the total amount of all monomer components (hereinafter referred to as “total monomer components”) constituting the polymer (A) is 100 parts by weight. It is desirable to include 60 parts by weight, preferably 25 to 55 parts by weight. That is, when the total amount of all monomer components is 100 parts by weight, the content of (a) the repeating unit derived from the aliphatic conjugated diene monomer is 20 to 60 parts by weight, preferably 25 to 55 parts by weight. It is.
  • the ethylenically unsaturated carboxylic acid monomer used in the production of the polymer (A) contained in the composition for an electrode binder of the present invention is all When the total amount of monomer components is 100 parts by weight, 0.3 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 0.5 to 7 parts by weight is desirable. That is, when the total amount of all the monomer components is 100 parts by weight, the content of the repeating unit derived from (b) the ethylenically unsaturated carboxylic acid monomer is 0.3 to 10 parts by weight, preferably 0.00. 5 to 8 parts by weight, more preferably 0.5 to 7 parts by weight.
  • the (A) polymer contained in the composition for an electrode binder of the present invention may optionally contain a repeating unit derived from (c) an alkyl (meth) acrylate compound. .
  • the alkyl (meth) acrylate compound is desirably contained in an amount of 5 to 25 parts by weight, preferably 7 to 20 parts by weight. That is, when the total amount of all monomer components is 100 parts by weight, the desirable content of the repeating unit derived from the (c) alkyl (meth) acrylate compound is 5 to 25 parts by weight, preferably 7 to 20 parts by weight. is there.
  • the ratio of the alkyl (meth) acrylate compound When the ratio of the alkyl (meth) acrylate compound is too small, it becomes a polymer having poor affinity with the electrolyte used, and tends to adversely affect battery characteristics. On the other hand, when the proportion of the alkyl (meth) acrylate compound is excessive, the affinity with the electrolyte solution to be used becomes too large, so that the polymer tends to swell and tends to adversely affect the battery characteristics. .
  • the (A) polymer contained in the composition for electrode binders of the present invention may contain (d) a repeating unit derived from a vinyl cyanide compound.
  • a repeating unit derived from a vinyl cyanide compound when the total amount of all the monomer components is 100 parts by weight, 1 to 20 parts by weight, preferably 2 to 17 parts by weight is desirable. That is, when the total amount of all monomer components is 100 parts by weight, the desirable content of the repeating unit derived from (d) vinyl cyanide compound is 1 to 20 parts by weight, preferably 2 to 17 parts by weight.
  • the ratio of the vinyl cyanide compound When the ratio of the vinyl cyanide compound is too small, the polymer becomes poor in affinity with the electrolyte used, and tends to adversely affect battery characteristics. On the other hand, when the proportion of the vinyl cyanide compound is excessive, the affinity for the electrolyte solution to be used becomes too high, so that the polymer tends to swell and tends to adversely affect battery characteristics.
  • the (A) polymer contained in the composition for electrode binders of the present invention may contain (e) a repeating unit derived from another monomer component.
  • 0.5 to 40 parts by weight, preferably 1 to 35 parts by weight is desirable when the total amount of all monomer components is 100 parts by weight. That is, when the total amount of all the monomer components is 100 parts by weight, (e) the desirable content of repeating units derived from other monomer components is 0.5 to 40 parts by weight, preferably 1 to 35 parts by weight. Part.
  • Emulsifier As the emulsifier, anionic surfactants, nonionic surfactants, amphoteric surfactants and the like can be used alone or in combination of two or more.
  • anionic surfactant sulfates of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, sulfates of polyethylene glycol alkyl ethers, and the like can be used.
  • nonionic surfactant an alkyl ester type of polyethylene glycol, an alkyl ether type, an alkylphenyl ether type, or the like can be used.
  • amphoteric surfactants include those in which the anion moiety is a carboxylate salt, sulfate ester salt, sulfonate salt, or phosphate ester salt, and the cation moiety is an amine salt or a quaternary ammonium salt.
  • amino acid types such as bentines such as lauryl betaine and stearyl betaine, lauryl- ⁇ -alanine, lauryl di (aminoethyl) glycine, octyldi (aminoethyl) glycine and the like can be exemplified.
  • the amount of the emulsifier used is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the total amount of all monomer components used.
  • polymerization initiator As the polymerization initiator, water-soluble polymerization initiators such as sodium persulfate, potassium persulfate and ammonium persulfate, benzoyl peroxide, lauryl peroxide, 2,2′-azobisiso Oil-soluble polymerization initiators such as butyronitrile and redox polymerization initiators in combination with a reducing agent such as sodium bisulfite can be used alone or in combination of two or more.
  • water-soluble polymerization initiators such as sodium persulfate, potassium persulfate and ammonium persulfate, benzoyl peroxide, lauryl peroxide, 2,2′-azobisiso
  • Oil-soluble polymerization initiators such as butyronitrile and redox polymerization initiators in combination with a reducing agent such as sodium bisulfite can be used alone or in combination of two or more.
  • the amount of the polymerization initiator used is preferably 0.3 to 3 parts by weight based on 100 parts by weight of the total amount of all monomer components.
  • molecular weight regulator examples include halogenated hydrocarbons such as chloroform and carbon tetrachloride, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dotezyl mercaptan, Those used in usual emulsion polymerization such as mercaptans such as thioglycolic acid, xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide, terpinolene and ⁇ -methylstyrene dimer can be used.
  • halogenated hydrocarbons such as chloroform and carbon tetrachloride
  • n-hexyl mercaptan such as chloroform and carbon tetrachloride
  • n-octyl mercaptan n-dodecyl mercaptan
  • the amount of the molecular weight regulator used is usually 5 parts by weight or less with respect to 100 parts by weight of the total amount of all monomer components.
  • the polymerization process for obtaining the polymer (A) contained in the composition for electrode binder of the present invention is a method in which the monomer is charged in several stages. Is preferred. For example, a method in which a part of the monomer is polymerized and then the remaining monomer is divided into several stages and continuously added is preferable, and it is particularly preferable to add in 3 to 4 stages.
  • the polymerization temperature is preferably adjusted to a range of 40 to 70 ° C. Moreover, it is preferable to raise the polymerization temperature in each polymerization stage as the polymerization reaction proceeds.
  • the polymerization conversion rate is preferably 50% to 95%, more preferably 60% to 90%.
  • the monomer composition ratio in each stage particularly (a) the content of the aliphatic conjugated diene monomer is changed. It is desirable to do.
  • (A) By having polymerization steps with different aliphatic conjugated diene monomer content, it becomes easy to obtain a polymer having the temperature dependence of the storage elastic modulus characteristic of the present invention.
  • Seed polymerization As a polymerization method for obtaining the polymer (A) contained in the composition for electrode binder of the present invention, seed polymerization using seed particles can be applied.
  • seed particles that can be used to obtain the (A) polymer contained in the composition for electrode binder of the present invention are particularly limited as long as the object of the present invention can be achieved.
  • a typical example is seed latex, which is a seed particle made of latex.
  • the monomer composition of the seed latex that can be used in the present invention is not particularly limited. For example, a conjugated diene copolymer represented by butadiene, an aromatic vinyl monomer represented by styrene, and butyl acrylate.
  • an ethylenically unsaturated carboxylic acid it is preferable to use 1 to 20 parts by weight of ethylenically unsaturated carboxylic acid with respect to all monomers forming the seed latex.
  • the seed latex used is desirably a certain size or more from the viewpoint of controllability, From the viewpoint of electrode plate adhesion, it is desirable to keep it below a certain level.
  • the seed latex used preferably has an average particle size of 0.01 to 0.2 ⁇ m. When the particle diameter is in the above range, the adjustment of the particle diameter of the polymer (A) becomes easy.
  • Monomer components, emulsifiers, polymerization initiators, and molecular weight regulators used for seed polymerization are the same components as the conventional emulsion polymerization described in the section (4-1) Emulsion polymerization. Can be used.
  • the polymer (A) contained in the composition for an electrode binder of the present invention comprises, in an aqueous medium, the above (a) aliphatic conjugated diene monomer and (b) Ethylenically unsaturated carboxylic acid monomer and other monomer used as necessary, that is, (c) alkyl (meth) acrylate compound, (d) vinyl cyanide compound and (e) other monomer
  • the components can be produced by the method described in the item (4-1) Emulsion polymerization except that the components are subjected to emulsion polymerization in the presence of the seed latex.
  • the amount of seed particles used is usually 3 to 20 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the total amount of the monomers (a) to (e).
  • the amount of seed particles is usually 3 to 20 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the total amount of the monomers (a) to (e).
  • the binder particle diameter is excessively enlarged and the adhesion tends to be lowered.
  • the amount of seed particles used is excessive, it is difficult to obtain a polymer having a predetermined storage modulus, and the adhesion, press suitability, and winding property tend to be inferior.
  • (B) Liquid medium in the composition for electrode binders of the present invention, in addition to the (A) polymer, the liquid medium as the component (B) is contained as an essential component.
  • the liquid medium which is the component (B) contained in the composition for electrode binders of the present invention serves as a dispersion medium for dispersing the polymer (A).
  • the “liquid medium” is also referred to as “dispersion medium” in the following description of the present specification.
  • a liquid medium that is, a dispersion medium
  • water can be used as such a liquid medium.
  • the water dispersion medium used at the time of polymerization can be used as it is, or this can be used. Can be used after being concentrated.
  • the dispersion medium of the electrode binder composition of the present invention can be used by replacing it with an organic dispersion medium suitable for the active material, if necessary.
  • the organic dispersion medium is not particularly limited, and aromatic hydrocarbon compounds, non-aromatic hydrocarbon compounds, chlorine-containing hydrocarbon compounds, nitrogen-containing hydrocarbon compounds, sulfur-containing hydrocarbon compounds, and the like can be used. Specific examples thereof include toluene, N-methylpyrrolidone (NMP), methyl isobutyl ketone (MIBK), cyclohexanone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and the like. These organic dispersion media can be used singly or in combination of two or more.
  • the method for substitution with the organic dispersion medium is not particularly limited.
  • a method in which an organic dispersion medium is added to a latex obtained by emulsion polymerization and water is volatilized by distillation under reduced pressure For example, a method of redispersing the solid content in an organic dispersion medium can be used.
  • the concentration of the component (A) in the composition for an electrode binder of the present invention can be set as appropriate depending on the type of the component (B) used so that the viscosity range is easy to handle.
  • the solid content concentration in the electrode binder composition of the present invention is preferably 15 to 53% by mass, more preferably 20 to 50% by mass. When this solid content concentration exceeds 53% by mass, the viscosity of the electrode binder composition is increased, which may make it difficult to handle in a blending process such as weighing. On the other hand, when the solid content concentration is less than 15% by mass, in the preparation of the composition for an electrochemical device electrode described later, the composition for the electrode binder in a specified amount in terms of solid content with respect to the active material, conductive carbon, etc. If an object is added, the solid content of the obtained composition for an electrochemical device electrode is lowered, and it may be difficult to produce an electrode having a desired thickness.
  • solid content conversion shows converting in the component remove
  • composition for electrode binders of the present invention in addition to the components (A) and (B), other components may be contained as necessary.
  • thickeners such as sodium polyacrylate, nonionic or anionic surfactants as latex stabilizers, additives such as antifoaming agents, and the like can be used.
  • Electrochemical Device Electrode Slurry The electrochemical device electrode slurry of the present invention (hereinafter also referred to as “electrode composition”) is a slurry containing an electrode active material and the above electrode binder composition. Of the composition.
  • Electrode active material is not particularly limited, but when used for a lithium ion secondary battery electrode, it is suitable for use as a negative electrode, such as carbon, for example, phenolic resin, polyacrylonitrile, cellulose, and other organic high materials. Carbon materials obtained by firing molecular compounds, carbon materials obtained by firing coke and pitch, artificial graphite, natural graphite, etc. can be used, and when used for electric double layer capacitor electrodes, Activated carbon, activated carbon fiber, silica, alumina, etc. can be used. When used for lithium ion capacitor electrodes, carbon materials such as graphite, non-graphitizable carbon, hard carbon, coke, and polyacene organic semiconductors ( PAS) can be used.
  • PAS polyacene organic semiconductors
  • the electrode composition may contain additives such as a thickener, a dispersant, a nonionic or anionic surfactant as a latex stabilizer, and an antifoaming agent.
  • additives such as a thickener, a dispersant, a nonionic or anionic surfactant as a latex stabilizer, and an antifoaming agent.
  • the solid content in the electrode binder composition that is, the remainder obtained by removing the component (B) from the electrode binder composition Is preferably contained in a proportion of 0.1 to 10 parts by weight, more preferably 0.3 to 4 parts by weight.
  • the ratio of the solid content of the composition for electrode binders is too small, good adhesion tends not to be obtained.
  • the ratio of the solid content of the electrode binder composition is excessive, the overvoltage tends to increase and affect the battery characteristics.
  • the electrode composition As a means for mixing the electrode binder composition, the electrode active material, and the additive used as necessary, a stirrer, a defoamer, a bead mill, a high-pressure homogenizer, or the like is used. be able to.
  • the preparation of the electrode composition can be performed under reduced pressure, thereby preventing bubbles from being generated in the obtained electrode layer.
  • Electrode for Electrochemical Device the electrode composition is applied to the surface of the current collector and dried, and the resulting coating film is pressed to form an electrode layer on the surface of the current collector. Thus, an electrode for an electrochemical device is obtained.
  • the current collector As the current collector, one made of metal foil, etching metal foil, expanded metal, or the like can be used. As a material constituting the current collector, aluminum, copper, nickel, tantalum, stainless steel In addition, a metal material such as titanium can be appropriately selected according to the type of the target electrochemical device.
  • the current collector has a thickness of 5 to 30 ⁇ m, preferably 8 to 25 ⁇ m, for example, when forming an electrode for a lithium secondary battery, and for example, when forming an electrode for an electric double layer capacitor. The thickness is 5 to 100 ⁇ m, preferably 10 to 70 ⁇ m, more preferably 15 to 30 ⁇ m.
  • Electrode layer As a means for applying the electrode composition, a doctor blade method, a reverse roll method, a comma bar method, a gravure method, an air knife method, or the like can be used.
  • the treatment temperature is preferably 20 to 250 ° C., for example, and more preferably 50 to 150 ° C.
  • the treatment time is preferably 1 to 120 minutes, for example, and more preferably 5 to 60 minutes.
  • a means for pressing a high pressure super press, a soft calendar, a one-ton press machine, or the like can be used.
  • the press processing conditions are set as appropriate according to the processing machine to be used.
  • the electrode layer thus formed has, for example, a thickness of 40 to 100 ⁇ m and a density of 1.3 to 2.0 g / cm 2 .
  • Electrochemical Device The electrode for an electrochemical device thus obtained can be suitably used as an electrode for an electrochemical device such as a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor.
  • electrolyte LiClO 4, LiBF 4, LiI , LiPF 6, LiCF 3 SO 3, LiAsF 6, LiSbF 6, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) 4, LiCH 3 SO 3,
  • Examples include LiC 4 F 9 SO 3 , Li (C 4 F 9 SO 2 ) 2 N, Li (CO 2 ) 4 B, and the like.
  • the solvent include carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, lactones such as ⁇ -butyrolactone, trimethoxysilane, 1,2-dimethoxyethane, diethyl Ethers, ethers such as 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, sulfoxides such as dimethyl sulfoxide, oxolanes such as 1,3-dioxolane, 4-methyl-1,3-dioxolane, acetonitrile, nitromethane, etc.
  • carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate
  • lactones such as ⁇ -butyrolactone
  • trimethoxysilane 1,2-dimethoxye
  • Nitrogen-containing compounds methyl formate, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, phosphate triesters, diglyme, triglyme, tetrag Glymes such as Im, ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, sulfones such as sulfolane, oxazolidinones such as 2-methyl-2-oxazolidinone, 1,3-propane sultone, 4-butane sultone, And sultone such as naphtha sultone.
  • ketones such as acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone
  • sulfones such as sulfolane
  • oxazolidinones such as 2-methyl-2-oxazolidinone,
  • the same electrolyte solution as that used in the above lithium ion secondary battery can be used.
  • Second stage emulsion polymerization step Following the emulsion polymerization step in the first stage, emulsion polymerization was carried out by continuously adding the molecular weight regulator and monomer mixture (Y) shown in Table 1 below at the temperatures shown in the table for 3 hours.
  • composition for electrode binder The latex obtained as described above is adjusted to pH 7.2 with an aqueous sodium hydroxide solution, and then 1 part by weight (converted to solid content) of sodium polyacrylate is added and concentrated by decompression treatment. Thus, an electrode binder composition having a solid content concentration of 49% by mass was prepared.
  • Example 3 In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.5 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite, and Table 1 The molecular weight regulator and the monomer mixture (X) were charged all at once, and emulsion polymerization was performed for 6 hours at the temperature shown in the table, and it was confirmed that the polymerization conversion was 70% or more.
  • Second stage emulsion polymerization step Following the emulsion polymerization step in the first stage, the molecular weight regulator and monomer mixture (Y) shown in Table 1 below are added continuously at the temperature shown in the table for 6 hours to carry out emulsion polymerization. Latex was obtained. The final polymerization addition rate was 99%.
  • Example 2 In the same manner as in Example 1, a composition for electrode binder having a solid content concentration of 49% by mass was prepared.
  • ⁇ Comparative example 2> In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.5 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate, 0.5 part of sodium bisulfite, and Table 1 A latex was obtained by charging the molecular weight regulator and the monomer mixture (X) all together and carrying out emulsion polymerization at the temperature shown in the table for 12 hours. The final polymerization addition rate was 99%.
  • Example 2 In the same manner as in Example 1, a composition for electrode binder having a solid content concentration of 49% by mass was prepared.
  • a (n) (Log (E ′ (n + 1)) ⁇ Log (E ′ (n))) / (T (n + 1) ⁇ T (n)) (3) Determination of specific temperature range
  • n n2
  • ⁇ T T (n2)
  • T (n1) is obtained and set as the width of the specific temperature region.
  • the average particle diameter was measured by a dynamic light scattering method in an aqueous medium using a laser particle size analysis system LPA-3000s / 3100 manufactured by Otsuka Electronics Co., Ltd.
  • the electrode binder compositions obtained in the above examples and comparative examples were evaluated according to the following criteria.
  • Adhesion strength On the surface of the current collector made of copper foil having a thickness of 20 ⁇ m, the electrode composition was applied by an applicator so that the mass per unit area was 200 g / m 2, and dried at 70 ° C. for 20 minutes. Furthermore, after drying at 120 degreeC for 20 minutes, the electrode which has an electrode layer with a thickness of 70 micrometers was produced by pressing a coating film at room temperature. About the obtained electrode, the adhesion strength of the electrode layer with respect to an electrical power collector was measured with the 90 degree peeling tester by a tester industry Co., Ltd. product.
  • ⁇ Winding An electrode was produced in the same manner as in (1) above, and the obtained electrode was cut into a size of 2 ⁇ 10 cm. Then, the state of destruction of the electrode layer was visually observed when it was reciprocated three times along the SUS axis having a diameter of 2 ⁇ so that the coated surface was on the outside (opposite side of the SUS axis). “ ⁇ ” indicates that the electrode layer cannot be peeled off, “ ⁇ ” indicates that the microscopic and partial electrode layers are peeled and broken, and “X” indicates that the whole and most of the electrode layer is peeled and broken. did.
  • the electrode obtained from the electrode binder composition using the composition of the present invention was excellent in adhesion strength, press workability and winding property.
  • the polymer used in Comparative Example 2 was obtained by batch polymerization of monomers, and the width of the specific temperature range was narrow, showing a certain degree of winding, but inferior in adhesion and press workability. there were. Even in the case of a polymer obtained by multi-stage polymerization as in Comparative Example 1, a polymer having a narrow specific temperature range is satisfactory in all aspects of adhesion strength, press workability and winding property. could not.

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  • Health & Medical Sciences (AREA)
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Abstract

La présente invention a trait à : une composition pour un liant d'électrode, qui est en mesure de fournir une couche d'électrode qui est dotée d'une adhérence élevée à un collecteur et qui par conséquent ne peut être séparée du collecteur lorsqu'une pression est exercée, tout en étant hautement flexible ; une composition pour une électrode ; une électrode qui est obtenue à partir de la composition pour une électrode ; et un dispositif électrochimique qui comprend l'électrode. Plus particulièrement, la présente invention a trait à une composition pour un liant d'électrode, qui contient (A) un polymère qui comprend (a) un motif répétitif dérivé d'un monomère de diène conjugué aliphatique et (b) un motif répétitif dérivé d'un monomère d'acide carboxylique à insaturation éthylénique, tout en ayant au moins un point de transition vitreuse compris dans la plage allant de -80 °C à 100 °C et une largeur de plage de température de 20 °C ou plus, le coefficient différentiel de température du logarithme du module de conservation étant de -0,09 à -0,02, et (B) un milieu liquide.
PCT/JP2011/051043 2010-02-15 2011-01-21 Composition pour liant d'électrode, composition pour électrode, électrode et dispositif électrochimique Ceased WO2011099344A1 (fr)

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JP2011553784A JPWO2011099344A1 (ja) 2010-02-15 2011-01-21 電極バインダー用組成物、電極用組成物、電極および電気化学デバイス
KR1020127021311A KR20130006597A (ko) 2010-02-15 2011-01-21 전극 결합제용 조성물, 전극용 조성물, 전극 및 전기 화학 디바이스
CN2011800095538A CN102763252A (zh) 2010-02-15 2011-01-21 电极粘合剂用组合物、电极用组合物、电极以及电化学设备

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103956459A (zh) * 2014-03-13 2014-07-30 清华大学 一种环境友好的锂电池负极片制作方法
KR20160037949A (ko) 2013-07-24 2016-04-06 니폰 에이 엔 엘 가부시키가이샤 전극용 바인더, 전극용 조성물 및 전극 시트
JP2016106354A (ja) * 2013-03-27 2016-06-16 Jsr株式会社 蓄電デバイス用バインダー組成物
WO2025187712A1 (fr) * 2024-03-08 2025-09-12 株式会社カネカ Liant pour électrode d'accumulateur lithium-ion

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3480876B1 (fr) * 2016-06-29 2024-02-07 Zeon Corporation Composition de liant pour électrode de batterie secondaire non aqueuse, composition de suspension epaisse pour électrode de batterie secondaire non aqueuse, électrode pour batterie secondaire non aqueuse et batterie secondaire non aqueuse

Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH0987571A (ja) * 1995-09-25 1997-03-31 Nippon Zeon Co Ltd 有機溶媒系バインダー組成物、電極、および電池
JPH1125989A (ja) * 1997-07-04 1999-01-29 Jsr Corp 電池電極用バインダー
JP2002234903A (ja) * 2001-02-08 2002-08-23 Asahi Kasei Corp 共重合体ラテックス

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH0987571A (ja) * 1995-09-25 1997-03-31 Nippon Zeon Co Ltd 有機溶媒系バインダー組成物、電極、および電池
JPH1125989A (ja) * 1997-07-04 1999-01-29 Jsr Corp 電池電極用バインダー
JP2002234903A (ja) * 2001-02-08 2002-08-23 Asahi Kasei Corp 共重合体ラテックス

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016106354A (ja) * 2013-03-27 2016-06-16 Jsr株式会社 蓄電デバイス用バインダー組成物
KR20160037949A (ko) 2013-07-24 2016-04-06 니폰 에이 엔 엘 가부시키가이샤 전극용 바인더, 전극용 조성물 및 전극 시트
CN103956459A (zh) * 2014-03-13 2014-07-30 清华大学 一种环境友好的锂电池负极片制作方法
WO2025187712A1 (fr) * 2024-03-08 2025-09-12 株式会社カネカ Liant pour électrode d'accumulateur lithium-ion

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CN102763252A (zh) 2012-10-31

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