WO2011099344A1 - 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 - Google Patents
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 Download PDFInfo
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- 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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- monomer
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- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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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Abstract
Description
(b)エチレン性不飽和カルボン酸単量体由来の繰り返し単位
を含み、
-80~100℃の範囲に少なくとも1点のガラス移転点を有し、且つ、
貯蔵弾性率の対数の温度微分係数が-0.09以上-0.02以下である温度領域の幅が20℃以上である
重合体(以下、「(A)重合体」ともいう。)と、
(B)液状媒体と
を含む電極バインダー用組成物。
(a)脂肪族共役ジエン系単量体由来の繰り返し単位20~60重量部、および
(b)エチレン性不飽和カルボン酸単量体由来の繰り返し単位0.5~7重量部
を含む前記[1]に記載の電極バインダー用組成物。
(c)アルキル(メタ)アクリレート化合物由来の繰り返し単位
をさらに含む前記[1]または[2]に記載の電極バインダー用組成物。
(d)シアン化ビニル化合物由来の繰り返し単位
をさらに含む前記[1]~[3]のいずれかに記載の電極バインダー用組成物。
(C)電極活物質と
を含む電気化学デバイス電極用スラリー。
前記集電体の少なくとも一方の面に前記[7]に記載の電気化学デバイス電極用スラリーから得られる電極層と
を有する電気化学デバイス用電極。
本発明の電極バインダー用組成物は、(A)(a)脂肪族共役ジエン系単量体由来の繰り返し単位および(b)エチレン性不飽和カルボン酸単量体由来の繰り返し単位を含み、-80~100℃の範囲に少なくとも1点のガラス移転点(Tg)を有し、且つ、貯蔵弾性率の対数の温度微分係数が-0.09以上-0.02以下である温度領域の幅が20℃以上である重合体(以下、「(A)重合体」ともいう。)と、(B)液状媒体(以下。「(B)成分」ともいう。)とを含む。各成分に関して以下に詳述する。
本発明において、(A)重合体は、後述する(B)液状媒体とともに本発明の電極バインダー用組成物に含まれる構成成分である。集電体に対する密着性が高くてプレス加工時に剥離が生じることがなく、高い柔軟性を有する電極層を実現する上で、この(A)重合体は、本発明の電極バインダー用組成物において本来的な役割を果たす。本発明の電極バインダー用組成物において、(A)重合体は(a)脂肪族共役ジエン系単量体由来の繰り返し単位および(b)エチレン性不飽和カルボン酸単量体由来の繰り返し単位を含み、-80~100℃の範囲に少なくとも1点のガラス移転点を有し、且つ、貯蔵弾性率の対数の温度微分係数が-0.09以上-0.02以下の範囲である温度領域(以下、「特定温度領域」ともいう。)の幅が20℃以上であることを特徴とする。
本発明の電極バインダー用組成物が含有する(A)重合体は、-80~100℃の範囲に少なくとも1点のガラス移転点(以下、「Tg」ともいう。)を有する。このような重合体を用いると、本発明の電極バインダー用組成物を含有する電極層と集電体との密着性を維持しつつ、電極に柔軟性を付与することが出来る。
ガラス移転点(Tg)は、以下のように測定することができる。
本発明の電極バインダー用組成物が含有する(A)重合体は、貯蔵弾性率の対数の温度微分係数が-0.09以上-0.02以下の範囲である温度領域の幅が20℃以上である。この温度領域は、重合体において、ガラス状領域とゴム状領域との間に存在する転移領域に相当する。
(A)重合体と(B)成分を含有する電極バインダー用組成物を固形分40%に希釈し、14cm×10cmの大きさの枠に30g流し、40℃で60時間乾燥を行う。作製したフィルムを取り出し、32mm×5mmに切り出すことで測定サンプルを作製する。この乾燥フィルムをTA Instruments製動的粘弾性測定装置(DMA) RSA-IIを用いて、-80℃~100℃の温度領域の貯蔵弾性率を測定する(測定周波数1Hz、昇温スピード3℃/分)。
上記(2-1)貯蔵弾性率の測定によって得られたデータから、0から36までの各整数mに対してT(m)およびE’(m)を抽出する。T(m)は測定データ中、下記式で表される温度との差が最も小さい温度を示す。
なお、1つのmに対してT(m)の候補が2点存在する場合には低い温度の方をT(m)とする。E’(m)は温度T(m)における貯蔵弾性率の値である。
(2-3)特定温度領域の決定
上記(2-2)で求めたa(n)が-0.09以上-0.02以下の範囲に最初に入ったときのnをn1とし、上記範囲から最初に出たときのnをn2とする(ただしn1>n2)。T(n1)からT(n2)の間を特定温度領域とし、下記式で定義されるΔTを特定温度領域の幅とする。
n2より大きいnに対して再度-0.09≦a(n)≦-0.02となるnが存在する場合にはその都度n1、n2を特定し、特定温度領域の幅を計算する。
本発明の電極バインダー用組成物が含有する(A)重合体は、組成物中で粒子として存在し、その平均粒子径は好ましくは80~250nm、より好ましくは83~230nm、さらに好ましくは85~200nmである。粒子径が前記範囲であると、電極バインダー用組成物と活物質を混合して電極スラリーを調整する際の分散安定性が良好となり、塗工性の良好なスラリー性状を得ることができる。さらに、粒子径が前記範囲であると、集電体と電極層の密着性が向上する傾向にある。
本発明の電極バインダー用組成物が含有する(A)重合体は、例えば、乳化重合で得ることができる。乳化重合としては、たとえば、シード粒子を用いたシード重合等を例示することができる。
乳化重合工程は、水性媒体中において、乳化剤、重合開始剤および分子量調節剤の存在下に単量体成分を重合することによって行われる。
本発明では、(A)重合体を構成する必須の単量体成分として、(a)脂肪族共役ジエン系単量体と(b)エチレン性不飽和カルボン酸単量体とが挙げられる。また、これらの単量体成分のほか、所要により(A)重合体を構成しうる単量体成分として、(c)アルキル(メタ)アクリレート化合物、(d)シアン化ビニル化合物等が挙げられる。
本発明の電極バインダー用組成物に含有される(A)重合体の製造に使用される(a)脂肪族共役ジエン系単量体として、1,3-ブタジエン、イソプレン、2-クロロ-1,3-ブタジエン、クロロプレンなどが挙げられるが、好ましくは1,3-ブタジエンである。これらの(a)脂肪族共役ジエン系単量体は、1種単独で、あるいは2種以上を併用することができる。
(A)重合体の製造に使用される(b)エチレン性不飽和カルボン酸単量体として、例えばイタコン酸、アクリル酸、メタクリル酸、フマル酸、マレイン酸などが挙げられ、特にイタコン酸、アクリル酸、メタクリル酸、フマル酸が好ましい。これらの(b)エチレン性不飽和カルボン酸単量体は、1種単独で、あるいは2種以上を併用することもできる。
本発明では、(c)アルキル(メタ)アクリレート化合物もまた、(A)重合体の製造に好適に使用される単量体成分となりうる。ここで、「(メタ)アクリレート」とは、「アクリレート」および対応する「メタクリレート」を包含する概念である。このような(c)アルキル(メタ)アクリレート化合物として、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、ベンジル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソボルニル(メタ)アクリレート、2-シアノエチル(メタ)アクリレートなどが挙げられ、特にメチルメタクリレートが好ましい。
本発明では、(d)シアン化ビニル化合物もまた、(A)重合体の製造に好適に使用される単量体成分となりうる。このような(d)シアン化ビニル化合物として、アクリロニトリル、メタクリロニトリルなどが挙げられ、特にアクリロニトリルが好ましい。
また、本発明では、(A)重合体の製造に使用することができる(e)その他の単量体成分として、上記単量体(a)~(d)と共重合可能な他のビニル系単量体が挙げられる。このような『(e)その他のビニル系単量体』として、芳香族ビニル化合物、酢酸ビニル、アクリルアミド系化合物などが挙げられる。
(a)脂肪族共役系ジエン単量体
本発明の電極バインダー用組成物に含有される(A)重合体の製造に使用される(a)脂肪族共役ジエン系単量体は、(A)重合体を構成する全ての単量体成分(以下、「全単量体成分」と称す。)の総量を100重量部としたときに20~60重量部、好ましくは25~55重量部含まれることが望ましい。すなわち、全単量体成分の総量を100重量部としたときに、(a)脂肪族共役ジエン系単量体由来の繰り返し単位の含量は、20~60重量部、好ましくは25~55重量部である。
本発明の電極バインダー用組成物に含有される(A)重合体の製造に使用される(b)エチレン性不飽和カルボン酸単量体は、全単量体成分の総量を100重量部としたときに0.3~10重量部、好ましくは0.5~8重量部、より好ましくは0.5~7重量部含まれることが望ましい。すなわち、全単量体成分の総量を100重量部としたときに、(b)エチレン性不飽和カルボン酸単量体由来の繰り返し単位の含量は、0.3~10重量部、好ましくは0.5~8重量部、より好ましくは0.5~7重量部である。
本発明の電極バインダー用組成物に含有される(A)重合体は、所要により、(c)アルキル(メタ)アクリレート化合物由来の繰り返し単位を含んでいてもよい。この場合、全単量体成分の総量を100重量部としたときにアルキル(メタ)アクリレート化合物は5~25重量部、好ましくは7~20重量部含まれることが望ましい。すなわち、全単量体成分の総量を100重量部としたときに、(c)アルキル(メタ)アクリレート化合物由来の繰り返し単位の望ましい含量は、5~25重量部、好ましくは7~20重量部である。
本発明の電極バインダー用組成物に含有される(A)重合体は、(d)シアン化ビニル化合物由来の繰り返し単位を含んでいてもよい。この場合、全単量体成分の総量を100重量部としたときに1~20重量部、好ましくは2~17重量部含まれることが望ましい。すなわち、全単量体成分の総量を100重量部としたときに、(d)シアン化ビニル化合物由来の繰り返し単位の望ましい含量は、1~20重量部、好ましくは2~17重量部である。
本発明の電極バインダー用組成物に含有される(A)重合体は、(e)その他の単量体成分由来の繰り返し単位を含んでいてもよい。この場合、全単量体成分の総量を100重量部としたときに0.5~40重量部、好ましくは1~35重量部含まれることが望ましい。すなわち、全単量体成分の総量を100重量部としたときに、(e)その他の単量体成分由来の繰り返し単位の望ましい含量は、0.5~40重量部、好ましくは1~35重量部である。
乳化剤としては、アニオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤などを単独でまたは2種以上組み合わせて用いることができる。アニオン性界面活性剤としては、高級アルコールの硫酸エステル、アルキルベンゼンスルホン酸塩、脂肪族スルホン酸塩、ポリエチレングリコールアルキルエーテルの硫酸エステルなどを用いることができる。ノニオン性界面活性剤としては、ポリエチレングリコールのアルキルエステル型のもの、アルキルエーテル型のもの、アルキルフェニルエーテル型のものなどを用いることができる。両性界面活性剤の具体例としては、アニオン部分が、カルボン酸塩、硫酸エステル塩、スルホン酸塩、リン酸エステル塩で、カチオン部分が、アミン塩、第4級アンモニウム塩であるものを用いることができ、具体的には、ラウリルベタイン、ステアリルベタインなどのベンタイン類、ラウリル-β-アラニン、ウラリルジ(アミノエチル)グリシン、オクチルジ(アミノエチル)グリシンなどのアミノ酸タイプのものを例示することができる。乳化剤の使用量は、用いられる全単量体成分の総量100重量部に対して0.5~5重量部であることが好ましい。
重合開始剤としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの水溶性重合開始剤、過酸化ベンゾイル、ラウリルパーオキサイド、2,2’-アゾビスイソブチロニトリル等の油溶性重合開始剤、重亜硫酸ナトリウム等の還元剤との組み合わせによるレドックス系重合開始剤などを、単独でまたは2種以上を組み合わせて用いることができる。
分子量調節剤としては、クロロホルム、四塩化炭素などのハロゲン化炭化水素類、n-ヘキシルメルカプタン、n-オクチルメルカプタン、n-ドデシルメルカプタン、t-ドテジルメルカプタン、チオグリコール酸などのメルカプタン類、ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイドなどのキサントゲン類、ターピノーレン、α-メチルスチレンダイマーなどの通常の乳化重合に使用されるものを用いることができる。
本発明の電極バインダー用組成物に含有される(A)重合体を得るための重合工程としては単量体の投入を数段階に分けて重合する方法が好ましい。例えば、単量体の一部を重合した後、残りの単量体を数段階に分け、連続的に添加する方法が好ましく、特に3~4段階に分けて投入することが好ましい。重合温度としては40~70℃の範囲に調整することが好ましい。また、各重合段階における重合温度は重合反応の進行に伴い上昇させることが好ましい。
本発明の電極バインダー用組成物に含有される(A)重合体を得る重合方法として、シード粒子を用いたシード重合を適用することもできる。
本発明の電極バインダー用組成物に含有される(A)重合体を得るために用いることのできるシード粒子は、本発明の目的が達成できる限り特に限られるものではないが、その典型例として、ラテックスからなるシード粒子であるシードラテックスが挙げられる。本発明で用いることのできるシードラテックスの単量体組成は特に限定されるものではなく、例えばブタジエンに代表される共役ジエン共重合体、スチレンに代表される芳香族ビニル単量体、アクリル酸ブチル、アクリル酸2-エチルヘキシル、アクリル酸2-ヒドロキシエチル、メタアクリル酸メチルに代表されるメタアクリル酸、アクリル酸のアルキルエステル類、アクリロニトリルに代表されるシアン化ビニル単量体、アクリルアミドに代表されるアミド基含有エチレン系単量体、イタコン酸、フマル酸、アクリル酸、メタアクリル酸に代表される不飽和カルボン酸系単量体などを使用することが出来る。
シード重合に用いられる単量体成分、乳化剤、重合開始剤、分子量調節剤は上記(4-1)乳化重合の項で示した従来の乳化重合と同様の成分を使用することが出来る。
本発明の電極バインダー用組成物に含有される(A)重合体は、水性媒体中において、前記(a)脂肪族共役ジエン系単量体と、(b)エチレン性不飽和カルボン酸単量体と、必要により用いられるそれ以外の単量体、すなわち、(c)アルキル(メタ)アクリレート化合物、(d)シアン化ビニル化合物および(e)その他の単量体成分とを、前記したシードラテックス存在下で乳化重合させる点を除けば、上記(4-1)乳化重合の項に記載した方法によって製造することができる。
本発明の電極バインダー用組成物においては、上記の(A)重合体に加えて、(B)成分である液状媒体が必須の成分として含有されている。
また、本発明の電極バインダー用組成物においては、上記の(A)成分および(B)成分に加えて、必要に応じて他の成分が含有されていてもよい。
本発明の電気化学デバイス電極用スラリー(以下、「電極用組成物」ともいう。)は、電極活物質と、上記の電極バインダー用組成物とを含有してなるスラリー状の組成物である。
電極活物質は、特に限定されるものではないが、リチウムイオン二次電池電極に用いる場合には、負極用として、カーボン、例えばフェノール樹脂、ポリアクリロニトリル、セルロース等の有機高分子化合物を焼成することにより得られる炭素材料、コークスやピッチを焼成することにより得られる炭素材料、人造グラファイト、天然グラファイトなどを用いることができ、また、電気二重層キャパシタ電極に用いる場合には、活性炭、活性炭繊維、シリカ、アルミナなどを用いることができ、また、リチウムイオンキャパシタ電極に用いる場合には、黒鉛、難黒鉛化炭素、ハードカーボン、コークスなとの炭素材料や、ポリアセン系有機半導体(PAS)などを用いることができる。
電極用組成物には、増粘剤、分散剤、ラテックスの安定化剤としてのノニオン性またはアニオン性界面活性剤、消泡剤などの添加剤が含有されていてもよい。
電極用組成物においては、電極活物質100重量部に対して、電極バインダー用組成物における固形分、すなわち電極バインダー用組成物から(B)成分を除いた残りの成分が0.1~10重量部の割合で含有されていることが好ましく、より好ましくは0.3~4重量部である。電極バインダー用組成物の固形分の割合が過小である場合には、良好な密着性が得られなくなる傾向にある。一方、電極バインダー用組成物の固形分の割合が過大である場合には、過電圧が上昇して電池特性に影響を及ぼす傾向にある。
本発明においては、上記の電極用組成物を集電体の表面に塗布して乾燥処理し、得られる塗膜をプレス加工することにより、当該集電体の表面に電極層が形成され、以て、電気化学デバイス用電極が得られる。
集電体としては、金属箔、エッチング金属箔、エキスパンドメタルなどからなるものを用いることができ、集電体を構成する材料としては、アルミニウム、銅、ニッケル、タンタル、ステンレス、チタンなどの金属材料から目的とする電気化学デバイスの種類に応じて適宜選択して用いることができる。また、集電体の厚みは、例えばリチウム二次電池用の電極を構成する場合には、5~30μm、好ましくは8~25μmであり、例えば電気二重層キャパシタ用の電極を構成する場合には、5~100μm、好ましくは10~70μm、より好ましくは15~30μmである。
電極用組成物を塗布する手段としては、ドクターブレード法、リバースロール法、コンマバー法、グラビヤ法、エアーナイフ法などを利用することができる。
このようにして得られる電気化学デバイス用電極は、例えばリチウムイオン二次電池、電気二重層キャパシタ、リチウムイオンキャパシタなどの電気化学デバイスの電極として好適に用いることができる。
(1)第1段階の乳化重合工程:
撹拌機を備えた、温度調節の可能なオートクレーブ中に、水200部、ドデシルベンゼンスルホン酸ナトリウム0.5部、過硫酸カリウム1.0部、重亜硫酸ナトリウム0.5部、並びに表1に示す分子量調節剤および単量体混合物(X)を一括して仕込み、表に記載の温度で6時間乳化重合を行い、重合転化率が70%以上であることを確認した。
上記第1段階の乳化重合工程に続き、下記表1に示す分子量調節剤および単量体混合物(Y)を表に記載の温度で3時間にわたって連続的に添加して乳化重合を行った。
上記第2段階の乳化重合工程に続き、下記表1に示す分子量調節剤および単量体混合物(Z)を60℃で3時間にわたって連続的に添加して乳化重合を行うことにより、ラテックスを得た。最終的な重合添加率は、93~99%であった。
以上のようにして得られたラテックスに対し、水酸化ナトリウム水溶液により、pHを7.2に調整した後、ポリアクリル酸ソーダを1重量部(固形分換算)添加し、減圧処理によって濃縮することにより、固形分濃度が49質量%の電極バインダー用組成物を調製した。
(1)第1段階の乳化重合工程:
撹拌機を備えた、温度調節の可能なオートクレーブ中に、水200部、ドデシルベンゼンスルホン酸ナトリウム0.5部、過硫酸カリウム1.0部、重亜硫酸ナトリウム0.5部、並びに表1に示す分子量調節剤および単量体混合物(X)を一括して仕込み、表に記載の温度で6時間乳化重合を行い、重合転化率が70%以上であることを確認した。
上記第1段階の乳化重合工程に続き、下記表1に示す分子量調節剤および単量体混合物(Y)を表に記載の温度で6時間にわたって連続的に添加して乳化重合を行うことにより、ラテックスを得た。最終的な重合添加率は、99%であった。
(1)第1段階の乳化重合工程:
撹拌機を備えた、温度調節の可能なオートクレーブ中に、水200部、ドデシルベンゼンスルホン酸ナトリウム0.5部、過硫酸カリウム1.0部、重亜硫酸ナトリウム0.5部、並びに表1に示す分子量調節剤および単量体混合物(X)を一括して仕込み、表に記載の温度で12時間乳化重合を行うことにより、ラテックスを得た。最終的な重合添加率は、99%であった。
得られた電極バインダー用組成物約4gを5×4cmの枠に流し、恒温槽中で70℃で24時間乾燥させ膜厚約100μmのフィルムを作製した。作製したフィルムから約10mgを切り出し、アルミ容器中に採取して密封した。空気雰囲気下で示差走査熱量測定装置(DSC204F1 NETZSCH社製)を用いて昇温速度20℃/minの条件で-80℃~100℃の温度領域についてDSCチャートを作成し、ガラス移転点(Tg)を測定した。なお、DSCチャートからのガラス移転点(Tg)の読み取り方法はJIS K7121に記載の中間点ガラス転移温度の求め方に従った。
(1)貯蔵弾性率の測定
電極バインダー用組成物を固形分40%に希釈し、14cm×10cmの大きさの枠に30g流し、40℃で60時間乾燥を行した。作製したフィルムを取り出し、32mm×5mmに切り出すことで測定サンプルを作製した。この乾燥フィルムをTA Instruments製動的粘弾性測定装置(DMA) RSA-IIを用いて、-80℃~100℃の温度領域の貯蔵弾性率を測定した(測定周波数1Hz、昇温スピード3℃/分)。
上記(1)貯蔵弾性率の測定によって得られたデータ中、-80℃から100℃までの範囲について温度T(0)~T(36)および貯蔵弾性率E’(0)~E’(36)を決定した。ここで、E’(m)は温度T(m)における貯蔵弾性率の値である(mは0から36までのいずれかの整数である。)。a(0)~a(35)を下記定義に従って算出し、温度T(n)における貯蔵弾性率の対数の温度微分係数とした。例として実施例1の重合体についての数値を表2に、比較例1の重合体についての数値を表3に示した。
(3)特定温度領域の決定
上記(2)で求めたa(n)が-0.09以上-0.02以下の範囲に最初に入ったときのnをn1とし、上記範囲から最初に出たときのnをn2として、ΔT=T(n2)-T(n1)を求め、特定温度領域の幅とした。
大塚電子(株)製レーザー粒径解析システムLPA-3000s/3100を用いて水媒体中で動的光散乱法により測定した。
厚さが20μmの銅箔よりなる集電体の表面に、電極用組成物を単位面積当たりの質量が200g/m2 となるよう、アプリケータによって塗工し、70℃で20分間乾燥し、さらに120℃で20分間乾燥した後、塗膜を室温でプレスすることにより、厚さが70μmの電極層を有する電極を作製した。得られた電極について、テスター産業(株)製の90°剥離試験機により、集電体に対する電極層の密着強度を測定した。
上記(1)と同様にして電極を作製し、得られた電極を、テスター産業(株)の小型プレス機により、500kg/cmの荷重で厚み方向に加圧し、電極層の剥離状態および破壊状態を目視で観察し、電極層の剥離および破壊が認められない場合を「○」、微小および部分的な電極層の剥離および破壊が認められた場合を「△」、全体および大部分の電極層剥離および破壊が認められた場合を「×」として評価した。
上記(1)と同様にして電極を作製し、得られた電極を2×10cmの大きさに切り出した。その後、直径2φのSUS軸に沿って塗工面が外側(SUS軸と反対側)となるように3往復させたときの電極層の破壊状態を目視で観察し、電極層の剥離および破壊が認められない場合を「○」、微小および部分的な電極層の剥離および破壊が認められた場合を「△」、全体および大部分の電極層剥離および破壊が認められた場合を「×」として評価した。
Claims (9)
- (A)
(a)脂肪族共役ジエン系単量体由来の繰り返し単位、および
(b)エチレン性不飽和カルボン酸単量体由来の繰り返し単位
を含み、
-80~100℃の範囲に少なくとも1点のガラス移転点(Tg)を有し、且つ、
貯蔵弾性率の対数の温度微分係数が-0.09以上-0.02以下である温度領域の幅が20℃以上である
重合体と、
(B)液状媒体と
を含む電極バインダー用組成物。 - 前記(A)重合体が、全単量体成分の総量を100重量部としたときに、
(a)脂肪族共役ジエン系単量体由来の繰り返し単位20~60重量部、および
(b)エチレン性不飽和カルボン酸単量体由来の繰り返し単位0.5~7重量部
を含む請求項1に記載の電極バインダー用組成物。 - 前記(A)重合体が、
(c)アルキル(メタ)アクリレート化合物由来の繰り返し単位
をさらに含む請求項1または2に記載の電極バインダー用組成物。 - 前記(A)重合体が、
(d)シアン化ビニル化合物由来の繰り返し単位
をさらに含む請求項1~3のいずれか一項に記載の電極バインダー用組成物。 - 前記(A)重合体の数平均粒子径が80~250nmである請求項1~4のいずれか1項に記載の電極バインダー用組成物。
- 前記(A)重合体が多段階での乳化重合によって得られ、全重合工程を通して重合温度が70℃未満である請求項1~5のいずれか1項に記載の電極バインダー用組成物。
- 請求項1~6のいずれか1項に記載の電気化学デバイス電極バインダー用組成物と、
(C)電極活物質と
を含む電気化学デバイス電極用スラリー。 - 集電体と、
前記集電体の少なくとも一方の面に請求項7に記載の電気化学デバイス電極用スラリーから得られる電極層と
を有する電気化学デバイス用電極。 - 請求項8に記載の電気化学デバイス用電極を有する電気化学デバイス。
Priority Applications (3)
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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 |
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 |
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JP (1) | JPWO2011099344A1 (ja) |
KR (1) | KR20130006597A (ja) |
CN (1) | CN102763252A (ja) |
TW (1) | TW201138195A (ja) |
WO (1) | WO2011099344A1 (ja) |
Cited By (3)
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 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3480876B1 (en) * | 2016-06-29 | 2024-02-07 | Zeon Corporation | Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery |
Citations (3)
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 |
-
2011
- 2011-01-21 JP JP2011553784A patent/JPWO2011099344A1/ja active Pending
- 2011-01-21 KR KR1020127021311A patent/KR20130006597A/ko not_active Application Discontinuation
- 2011-01-21 WO PCT/JP2011/051043 patent/WO2011099344A1/ja active Application Filing
- 2011-01-21 CN CN2011800095538A patent/CN102763252A/zh active Pending
- 2011-02-11 TW TW100104560A patent/TW201138195A/zh unknown
Patent Citations (3)
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 (3)
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 |
Also Published As
Publication number | Publication date |
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KR20130006597A (ko) | 2013-01-17 |
TW201138195A (en) | 2011-11-01 |
JPWO2011099344A1 (ja) | 2013-06-13 |
CN102763252A (zh) | 2012-10-31 |
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