WO2012023626A1 - Composition liante pour utilisation dans des électrodes - Google Patents

Composition liante pour utilisation dans des électrodes Download PDF

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Publication number
WO2012023626A1
WO2012023626A1 PCT/JP2011/068818 JP2011068818W WO2012023626A1 WO 2012023626 A1 WO2012023626 A1 WO 2012023626A1 JP 2011068818 W JP2011068818 W JP 2011068818W WO 2012023626 A1 WO2012023626 A1 WO 2012023626A1
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WIPO (PCT)
Prior art keywords
electrode
structural unit
binder composition
mass
active material
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PCT/JP2011/068818
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English (en)
Japanese (ja)
Inventor
武志 茂木
博紀 北口
幸志 樫下
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Jsr株式会社
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Priority to JP2012529638A priority Critical patent/JPWO2012023626A1/ja
Publication of WO2012023626A1 publication Critical patent/WO2012023626A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to an electrode binder composition.
  • Electrochemical devices such as secondary batteries such as lithium ion secondary batteries and nickel metal hydride secondary batteries; capacitors such as lithium ion capacitors and electric double layer capacitors, a laminate in which an electrode active material layer is formed on a current collector
  • the electrode active material layer in this electrode is formed by applying an electrode slurry onto a current collector to form a coating film, then drying the coating film, and preferably further pressing the dried coating film. .
  • the electrode slurry is prepared by mixing an electrode binder composition and an electrode active material.
  • the binder composition for electrodes is a dispersion in which a binder component such as polyvinylidene fluoride is dispersed in a solution or dispersion medium dissolved in a solvent.
  • characteristics such as capacity, cycle characteristics, and discharge rate characteristics are problematic. These characteristics are greatly influenced by the characteristics of the binder as well as the type and amount of the electrode active material and the electrolyte contained in the electrode. For example, if the binding property of the binder is insufficient, a sufficient amount of electrode active material is not bound on the current collector, or the binding force between the electrode active materials is insufficient. The capacity becomes insufficient. In addition, the binding force of the binder may decrease due to repeated charging and discharging. In this case, when charging and discharging are repeated, the electrode active material gradually falls off from the current collector, and as a result, the capacity of the electrochemical device decreases with time (the cycle characteristics are poor). .
  • the binder used in the electrochemical device collects the electrode active material due to high adhesion between the electrode active material and the current collector, high binding property between the electrode active materials, and repeated charge and discharge. High binding durability that does not fall off the electric body is required.
  • JP 2002-42819 A discloses a binder composition containing a polymer having a structural unit derived from a fluorine-containing (meth) acrylate. Japanese Patent No.
  • 3539448 (JP-A-8-287915) has a structural unit derived from (meth) acrylate, a structural unit derived from acrylonitrile, and a structural unit derived from an unsaturated carboxylic acid at the same time. Binder compositions containing polymers have been proposed and have achieved some success.
  • electrochemical devices have begun to be installed in automobiles. For example, secondary batteries such as lithium ion secondary batteries are used as main power sources for electric vehicles and hybrid cars, and capacitors such as electric double layer capacitors are used as auxiliary power sources for large vehicles such as trucks. Since automobiles have significantly different usage environments (especially usage temperatures) depending on the area of use and seasonal factors, electrochemical devices mounted on automobiles are required to exhibit stable performance over a wide temperature range.
  • An object of the present invention is to provide a binder composition for an electrode that provides an electrochemical device that has high binding properties and is excellent in both discharge rate characteristics in a low temperature environment and electrochemical stability in a high temperature environment. Is to provide.
  • Structural unit (A) derived from a monomer represented by the following general formula (1) and Structural unit derived from ⁇ , ⁇ -unsaturated nitrile monomer (B) Containing a polymer having The content ratio of the structural unit (A) is 5 to 60% by mass, The content of the structural unit (B) is 5 to 40% by mass, and This is achieved by a binder composition for electrodes in which the total content of the structural unit (A) and the structural unit (B) is 10 to 70% by mass.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 Represents a fluorinated hydrocarbon group having 1 to 18 carbon atoms.
  • the binder composition for electrodes of the present invention is a polymer having a structural unit (A) derived from the monomer represented by the general formula (1) and a structural unit (B) derived from an ⁇ , ⁇ -unsaturated nitrile monomer. (Hereinafter referred to as “specific polymer”).
  • This binder composition for electrodes further contains a liquid medium and can optionally contain a thickener.
  • the binder composition for electrodes of the present invention may further contain other components such as an emulsifier, a polymerization initiator or a residue thereof, a surfactant, and a neutralizing agent.
  • the specific polymer contained in the binder composition for an electrode of the present invention has a structural unit (A) and a derived structural unit (B). This specific polymer may have another structural unit in addition to the structural unit (A) and the structural unit (B).
  • Structural unit (A) The specific polymer in this invention has the structural unit (A) derived from the monomer represented by the said General formula (1).
  • R in the general formula (1) 2 Examples thereof include a fluorinated alkyl group having 1 to 18 carbon atoms, a fluorinated aryl group having 6 to 18 carbon atoms, and a fluorinated aralkyl group having 7 to 18 carbon atoms.
  • R 2 Is preferably a fluorinated alkyl group having 1 to 11 carbon atoms, and particularly preferably a group represented by the following general formula (2).
  • R 3 Represents a hydrogen atom or a fluorinated hydrocarbon group having 1 to 10 carbon atoms
  • R 4 Represents a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • R in the general formula (2) 3 And R 4 The fluorinated hydrocarbon group having 1 to 10 carbon atoms is preferably a fluorinated alkyl group having 1 to 10 carbon atoms.
  • Preferable specific examples of the group represented by the general formula (2) include, for example, 2,2,2-trifluoroethyl group, 1,1,1-trifluoropropan-2-yl group, 2- (perfluoro Octyl) ethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,4,4,4-hexafluorobutyl group, 1H, 1H, 9H-perfluoro-1-nonyl group, 1H , 1H, 11H-perfluoroundecyl group, perfluorooctyl group, etc., among which 2,2,2-trifluoroethyl group and 2,2,2-trifluoroisopropyl group are more preferable, In particular, 2,2,2-trifluoroethyl group is preferable.
  • the monomer represented by the general formula (1) for deriving the structural unit (A) only one of the above may be used alone, or two or more selected from the above may be used in combination. May be.
  • the specific polymer in the present invention has a structural unit (B) derived from an ⁇ , ⁇ -unsaturated nitrile monomer together with the structural unit (A).
  • ⁇ , ⁇ -unsaturated nitrile monomer leading to the structural unit (B) include (meth) acrylonitrile, ⁇ -chloroacrylonitrile, vinylidene cyanide and the like. In these, (meth) acrylonitrile is preferable and acrylonitrile is especially preferable. These ⁇ , ⁇ -unsaturated nitrile monomers can be used singly or in combination of two or more. (Other structural unit types) As described above, the specific polymer in the present invention may have another structural unit in addition to the structural unit (A) and the structural unit (B).
  • a structural unit (C) derived from an unsaturated carboxylic acid monomer Structural unit (D) derived from a monomer represented by the following general formula (3), Structural units (E) derived from at least one monomer selected from the group consisting of conjugated dienes and aromatic vinyl monomers and Structural units derived from other monomers (F)
  • R 5 Represents a hydrogen atom or a methyl group
  • R 6 Represents a hydrocarbon group having 1 to 18 carbon atoms.
  • Examples of the unsaturated carboxylic acid monomer that leads to the structural unit (C) include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, monoalkyl ester of unsaturated dicarboxylic acid, monoamide of unsaturated dicarboxylic acid, and the like.
  • Examples of the monocarboxylic acid include (meth) acrylic acid and crotonic acid;
  • Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, and the like.
  • (meth) acrylic acid and itaconic acid are preferable as the unsaturated carboxylic acid monomer for leading the structural unit (C), and methacrylic acid is particularly preferable.
  • R in the general formula (3) 6 Is preferably an alkyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-amyl group, i- An amyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, i-nonyl group, n-decyl group, etc. can be mentioned.
  • the monomer represented by the general formula (3) for deriving the structural unit (D) can be used alone or in combination of two or more.
  • examples of conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 2- Such as chloro-1,3-butadiene (chloroprene);
  • examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, and divinylbenzene.
  • Monomers that lead to the structural unit (E) can be used singly or in combination of two or more.
  • Examples of other monomers that lead to the structural unit (F) include hydroxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate and hydroxyethyl (meth) acrylate; Polyfunctional (meth) acrylate monomers such as ethylene glycol di (meth) acrylate; Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; Unsaturated dicarboxylic acid anhydrides; Monoamides of unsaturated dicarboxylic acids; Examples thereof include aminoalkylamides of ethylenically unsaturated carboxylic acids such as aminoethylacrylamide, dimethylaminomethylmethacrylamide, and methylaminopropylmethacrylamide, and one or more selected from these are used.
  • the content ratio of the structural unit (A) in the specific polymer is 5 to 60% by mass, preferably 7 to 55% by mass in all the structural units.
  • the content ratio of the structural unit (A) in the specific polymer is 5 to 40% by mass, preferably 5 to 35% by mass, based on all the structural units.
  • the total content of the structural unit (A) and the structural unit (B) is 10 to 70% by mass, preferably 15 to 65% by mass, based on all the structural units. .
  • this ratio is within the above range, the discharge rate characteristics under a low temperature environment and the electrochemical stability under a high temperature environment are further improved, which is preferable.
  • the electrode active material is aggregated when the binder composition of the present invention is mixed with the electrode active material. Therefore, it is possible to produce a slurry for an electrode having good dispersibility of the electrode active material.
  • the specific polymer having too much content of the structural unit (C) is inferior in oxidation resistance, so that the polymer is oxidatively deteriorated by repeated charge and discharge, and the electrode active material layer cannot be retained. As a result, there may be a disadvantage that the charge / discharge characteristics deteriorate with time.
  • the content ratio of the structural unit (C) in the specific polymer is preferably 10% by mass or less, more preferably 1 to 5% by mass in all the structural units.
  • the content ratio of the structural unit (D) in the specific polymer is preferably 90% by mass or less, and more preferably 25 to 80% by mass in all the structural units.
  • a binder composition for an electrode containing a specific polymer having the structural unit (E) together with the structural unit (A) and the structural unit (B) is applied to the negative electrode, a carbon material generally used as a negative electrode active material (for example, there is an advantage of having an appropriate binding property to graphite. Furthermore, the obtained electrode layer has good flexibility and adhesion to the current collector.
  • the specific polymer having too much content of the structural unit (E) is inferior in its ionic conductivity and oxidation resistance, and therefore has the disadvantages of increased electrode resistance and deterioration over time in charge / discharge characteristics.
  • the content ratio of the structural unit (E) in the specific polymer is preferably 75% by mass or less, more preferably 40 to 60% by mass in all the structural units. It is preferable that the content rate of the structural unit (F) in a specific polymer shall be 10 mass% or less in all the structural units. By setting the ratio in this range, it is possible to suppress deterioration of ion conductivity and adhesion due to the introduction of the structural units (C), (D), and (E).
  • the specific polymer contained in the composition includes the structural unit (C) and the structural unit together with the structural unit (A) and the structural unit (B). It has a unit (D) and it is preferable that these content rates are as follows in all the structural units.
  • the specific polymer contained in the electrode binder composition applied to the positive electrode or the capacitor electrode has a content ratio of the structural unit (E) and the structural unit (F) of 5% by mass or less in each of the structural units. It is preferable to contain neither the structural unit (E) nor the structural unit (F).
  • the specific polymer contained in the composition includes the structural unit (C) and the structural unit (E) together with the structural unit (A) and the structural unit (B). It is preferable that these content ratios are as follows in all structural units.
  • the specific polymer contained in the binder composition for an electrode applied to the negative electrode is preferably such that the content ratio of the structural unit (D) and the structural unit (F) is 5% by mass or less in all the structural units. It is preferable that neither the structural unit (D) nor the structural unit (F) is contained.
  • the specific polymer can be produced by polymerizing a mixture of the monomers described above.
  • the polymerization method of the monomer mixture is not particularly limited, but it is preferable to use an emulsion polymerization method.
  • an emulsifier, a polymerization initiator, a molecular weight regulator and the like can be appropriately used.
  • anionic surfactant, nonionic surfactant, amphoteric surfactant etc. can be used individually by 1 type or in combination of 2 or more types.
  • anionic surfactant examples include, for example, higher alcohol sulfates, alkylbenzene sulfonates, aliphatic sulfonates, and polyethylene glycol alkyl ether sulfates;
  • nonionic surfactant may include, for example, polyethylene glycol alkyl ester, polyethylene glycol alkyl ether, polyethylene glycol alkylphenyl ether, and the like.
  • amphoteric surfactant a salt in which the anion portion is a carboxylate salt, a sulfate ester salt, a sulfonate salt or a phosphate ester salt and the cation portion is an amine salt or a quaternary ammonium salt can be used.
  • amphoteric surfactants include betaines such as lauryl betaine and stearyl betaine; Examples thereof include surfactants of amino acid type such as lauryl- ⁇ -alanine, lauryl di (aminoethyl) glycine, octyldi (aminoethyl) glycine.
  • the use ratio of such an emulsifier is preferably 0.5 to 5 parts by mass with respect to a total of 100 parts by mass of the monomers used.
  • the polymerization initiator include water-soluble polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate; Oil-soluble polymerization initiators such as benzoyl peroxide, lauryl peroxide, 2,2′-azobisisobutyronitrile; Examples thereof include a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite. These polymerization initiators can be used alone or in combination of two or more.
  • the use ratio of the polymerization initiator is preferably 0.3 to 3 parts by mass with respect to 100 parts by mass in total of the monomers used.
  • the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrachloride; mercaptan derivatives such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid; Xanthogen derivatives such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide; Other molecular weight regulators such as terpinolene and ⁇ -methylstyrene dimer can be mentioned.
  • the usage-amount of a molecular weight modifier shall be 5 mass parts or less with respect to 100 mass parts of total of the monomer used.
  • Emulsion polymerization is preferably carried out in a suitable aqueous medium, particularly preferably in water.
  • the total content of the monomers in the aqueous medium can be 10 to 50% by weight, and preferably 20 to 40% by weight.
  • the conditions for emulsion polymerization are not particularly limited.
  • the polymerization temperature can be 40 to 85 ° C. and the polymerization time can be 2 to 16 hours.
  • Particularly preferred emulsion polymerization methods are as follows.
  • emulsion polymerization is started by adding an emulsion of a monomer mixture (hereinafter referred to as “monomer emulsion”), and, if necessary, polymerization is continued after the addition of the monomer emulsion is completed.
  • the temperature of the aqueous medium containing the polymerization initiator is preferably 40 to 85 ° C, and more preferably 60 to 80 ° C.
  • a polymerization initiator is added thereto, and after the polymerization initiator is added. It is preferable to start adding the monomer emulsion before the excessive time has elapsed.
  • the aqueous medium containing a polymerization initiator may further contain optional components such as the molecular weight regulator described above.
  • the monomer emulsified liquid can be prepared by adding a monomer and an emulsifier and other optional components as required to an aqueous medium, and sufficiently stirring them.
  • the monomer content in the emulsion is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
  • the addition of the monomer emulsion into the aqueous medium containing the polymerization initiator is preferably performed slowly so that the polymerization initiator is not unevenly distributed in the reaction solution and a non-uniform polymerization reaction does not occur.
  • the addition time is preferably 0.5 to 6 hours, and more preferably 1 to 4 hours. It is preferable to continue the polymerization after completing the addition of the monomer emulsion.
  • the temperature of the continuous polymerization is preferably 40 to 85 ° C, more preferably 60 to 80 ° C.
  • the continuous polymerization time is preferably 0.5 to 6 hours, more preferably 1 to 4 hours.
  • the total polymerization time from the start of addition of the monomer emulsion is preferably 1 to 12 hours, and more preferably 3 to 8 hours.
  • the specific polymer contained in the electrode binder composition of the present invention preferably has a glass transition temperature (Tg) of ⁇ 45 to 25 ° C.
  • the glass transition temperature (Tg) of the specific polymer can be measured as follows. About 4 g of the latex in which the specific polymer is dispersed is poured into a 5 cm ⁇ 4 cm Teflon (registered trademark) petri dish and dried in a thermostat at 70 ° C. for 24 hours to obtain a film having a thickness of about 100 ⁇ m.
  • the binder composition for electrodes of the present invention contains a liquid medium together with the above specific polymer.
  • the liquid state body can be an aqueous medium or a non-aqueous medium.
  • the electrode binder composition of the present invention is in the form of a slurry or latex in which the specific polymer as described above is dispersed in an aqueous medium, or in the form of a solution in which the specific polymer is dissolved in a non-aqueous medium. Is preferred.
  • the aqueous medium contains water.
  • the aqueous medium can contain a small amount of a non-aqueous medium in addition to water.
  • non-aqueous medium examples include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, sulfone compounds, and the like, and one or more selected from these are used. can do.
  • the content ratio of such a non-aqueous medium is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the whole of the aqueous medium. It is most preferable that it consists only of.
  • the specific polymer is preferably particulate in an aqueous medium.
  • the number average particle diameter of the specific polymer in the aqueous medium is preferably 50 to 190 nm, and more preferably 70 to 185 nm.
  • the number average particle diameter of the specific polymer is a number from the hydrodynamic diameter measured by a dynamic light scattering method using water as a dispersion medium using a laser particle size analysis system “LPA-3000s / 3100” manufactured by Otsuka Electronics Co., Ltd. It can be calculated as an average value.
  • the non-aqueous medium can be suitably used as long as it can dissolve the specific polymer.
  • the non-aqueous medium include aliphatic hydrocarbons such as n-octane, isooctane, nonane, decane, decalin, pinene, and chlorododecane; Cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, methylcyclopentane; Aromatic hydrocarbons such as chlorobenzene, chlorotoluene, ethylbenzene, diisopropylbenzene, cumene; Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, benzyl alcohol, glycerin; Ketones such as acetone, methyl ethyl ketone, cyclopentanone, isophorone; Ethers such as methyl
  • the content ratio of the specific polymer in the electrode binder composition of the present invention is preferably 20 to 60% by mass, and more preferably 25 to 50% by mass.
  • Thickener The above thickener can be contained in the electrode binder composition of the present invention in order to further improve the applicability, charge / discharge characteristics and the like of the electrode binder composition.
  • thickeners examples include cellulose derivatives such as carboxymethylcellulose, methylcellulose, and hydroxypropylcellulose; In addition to polyacrylates such as sodium polyacrylate, Polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, (meth) acrylic acid-vinyl alcohol copolymer, maleic acid-vinyl alcohol copolymer, modified polyvinyl alcohol, polyethylene glycol, ethylene-vinyl alcohol copolymer, polyvinyl acetate partial ken And the like.
  • the content of the thickener in the electrode binder composition of the present invention is 20% by weight or less based on the total solid content of the electrode binder composition (total mass of components other than the liquid medium in the composition).
  • the binder composition for electrodes of the present invention is preferably in the form of a latex in which the specific polymer is in the form of particles and dispersed in an aqueous medium.
  • the electrode binder composition of the present invention the polymerization reaction mixture after synthesizing (polymerizing) the specific polymer as described above in an aqueous medium is used as it is after adjusting the liquidity as necessary. It is particularly preferred. Therefore, the electrode binder composition of the present invention can contain other components such as an emulsifier, a polymerization initiator or a residue thereof, a surfactant, and a neutralizer in addition to the polymer particles and the aqueous medium.
  • the content ratio of these other components is preferably 3% by weight or less, more preferably 2% by weight or less as a ratio of the total weight of the other components to the solid content of the composition.
  • the solid content concentration of the electrode binder composition (the ratio of the total mass of components other than the liquid medium in the composition to the total mass of the composition) is preferably 20 to 60% by weight, 25 More preferably, it is ⁇ 50% by weight.
  • the liquid property of the binder composition for electrodes is preferably near neutral, more preferably pH 6.0 to 8.5, and particularly preferably pH 7.0 to 8.0. For adjusting the liquidity of the composition, a known water-soluble acid or base can be used.
  • the binder composition for electrodes of the present invention contains a polymer having a structural unit (A) and a structural unit (B). Therefore, as will be apparent from the examples described later, high binding properties are obtained, and the electrochemical device is excellent in both discharge rate characteristics in a low temperature environment and electrochemical stability in a high temperature environment. Can be given.
  • the slurry for an electrode of the present invention is Electrode active material and The electrode binder composition of the present invention as described above Containing.
  • the electrode slurry of the present invention may contain other components as required in addition to the electrode active material and the electrode binder composition of the present invention.
  • the electrode active material is appropriately selected according to the type of the target electrochemical device.
  • examples of the electrode active material (positive electrode active material) include lithium cobalt oxide. Lithium nickelate, lithium manganate, lithium iron phosphate, ternary nickel cobalt lithium manganate and the like can be suitably used.
  • examples of the electrode active material include carbon materials, Carbon or the like can be suitably used.
  • examples of the carbon material include carbon materials obtained by firing organic polymer compounds, coke, pitch, and the like.
  • examples of the organic polymer compounds that are precursors of the carbon materials include phenol resins and polyacrylonitrile. And cellulose.
  • Examples of the carbon include artificial graphite and natural graphite.
  • the electrode binder composition of the present invention When the electrode binder composition of the present invention is applied to an electrode slurry for forming an electrode for an electric double layer capacitor, examples of the electrode active material include graphite, non-graphitizable carbon, and hard carbon; Carbon material obtained by firing coke, pitch, etc .; A polyacene organic semiconductor (PAS) or the like can be used. (Other ingredients)
  • the electrode slurry of the present invention may further contain a thickener, a dispersant, a surfactant, an antifoaming agent, and the like as necessary.
  • the binder composition for electrodes of this invention can contain arbitrarily;
  • the dispersant include sodium hexametaphosphate, sodium tripolyphosphate, and sodium polyacrylate;
  • the surfactant include a nonionic surfactant or an anionic surfactant as a latex stabilizer.
  • the content ratio of these other components is preferably 10% by weight or less based on the total solid content of the slurry for electrodes of the present invention (total mass of components other than the liquid medium in the composition). It is more preferable that it is ⁇ 5% by weight.
  • the electrode slurry preferably contains 0.1 to 10 parts by mass, and 0.3 to 4 parts by mass of the electrode binder composition in terms of solid content with respect to 100 parts by mass of the electrode active material. More preferably.
  • the content ratio of the electrode binder composition is 0.1 to 10 parts by mass in terms of solid content, the specific polymer becomes difficult to dissolve in the electrolyte solution used in the electrochemical device. An adverse effect on device characteristics due to the rise can be suppressed.
  • the electrode slurry is prepared by mixing the electrode binder composition of the present invention, the electrode active material as described above, and other components used as necessary.
  • a known mixing device such as a stirrer, a defoamer, a bead mill, a high-pressure homogenizer, or the like can be used.
  • the preparation of the electrode slurry is preferably performed under reduced pressure, thereby preventing bubbles from being generated in the obtained electrode active material layer.
  • the electrode slurry as described above contains the electrode binder composition of the present invention to form an electrode active material layer having high adhesion between the electrode active materials and between the electrode active material and the current collector.
  • the electrode in the present invention is A current collector, An electrode active material layer formed through a process of applying and drying the electrode slurry described above on the surface of the current collector; Is provided. After the coating film is dried, press working is preferably performed.
  • a current collector for example, a metal foil, an etching metal foil, an expanded metal, or the like can be used. Specific examples of these materials include metals such as aluminum, copper, nickel, tantalum, stainless steel, titanium, and the like, which can be appropriately selected and used according to the type of the target electrochemical device. For example, when forming the positive electrode of a lithium ion secondary battery, it is preferable to use aluminum among the above as a collector.
  • the thickness of the current collector is preferably 5 to 30 ⁇ m, and more preferably 8 to 25 ⁇ m.
  • the thickness of the current collector is preferably 5 to 30 ⁇ m, and more preferably 8 to 25 ⁇ m.
  • the thickness of the current collector is preferably 5 to 30 ⁇ m, and more preferably 8 to 25 ⁇ m.
  • the thickness of the current collector is preferably 5 to 100 ⁇ m, more preferably 10 to 70 ⁇ m, and particularly preferably 15 to 30 ⁇ m.
  • the electrode active material layer in the electrode is formed by applying and drying the electrode slurry on the surface of the current collector as described above.
  • a method for applying the electrode slurry onto the current collector for example, an appropriate method such as a doctor blade method, a reverse roll method, a comma bar method, a gravure method, or an air knife method can be applied.
  • the coating film is preferably dried in a temperature range of 20 to 250 ° C., more preferably 50 to 150 ° C., preferably for 1 to 120 minutes, more preferably 5 to 60 minutes.
  • the dried coating film is preferably subjected to press working.
  • Examples of means for performing the pressing include a roll press machine, a high-pressure super press machine, a soft calendar, and a 1-ton press machine.
  • the press working conditions are appropriately set according to the type of processing machine used and the desired thickness and density of the electrode active material layer.
  • the electrode active material layer has a thickness of 40 to 100 ⁇ m and a density of 1.3 to 2.0 g / cm. 3 It is preferable that (Characteristics of electrode)
  • the electrode formed as described above is Since the electrode active material layer is formed using the electrode slurry containing the binder composition of the present invention, the electrode active material layer has high adhesion between the electrode active materials and between the electrode active material and the current collector. Is.
  • the electrode of the present invention can be suitably used as an electrode of an electrochemical device such as a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor.
  • an electrochemical device such as a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor.
  • the electrode formed using the binder composition of the present invention exhibits a performance superior to that of the prior art, both as a positive electrode and a negative electrode.
  • the electrochemical device in the present invention includes the electrode as described above.
  • the electrochemical device according to the present invention has a structure in which the electrode as described above is opposed to the counter electrode via the electrolytic solution, and is preferably isolated by the presence of the separator.
  • a manufacturing method thereof for example, two electrodes (two of a positive electrode and a negative electrode or two of a capacitor electrode) are overlapped via a separator, and this is wound or folded in accordance with the battery shape. And injecting the electrolyte into the battery container and sealing it.
  • the shape of the battery can be an appropriate shape such as a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, or a flat shape.
  • the electrolytic solution is appropriately selected and used according to the type of target electrochemical device.
  • the electrolytic solution a solution in which an appropriate electrolyte is dissolved in a solvent is used.
  • a lithium compound is used as an 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 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 N etc. can be mentioned.
  • the electrolyte concentration in this case is preferably 0.5 to 3.0 mol / L, more preferably 0.7 to 2.0 mol / L.
  • an electric double layer capacitor for example, tetraethylammonium tetrafluoroborate, triethylmethylammonium tetrafluoroborate, tetraethylammonium hexafluorophosphate or the like is used as an electrolyte.
  • the electrolyte concentration in this case is preferably 0.5 to 3.0 mol / L, more preferably 0.7 to 2.0 mol / L.
  • the type and concentration of the electrolyte in manufacturing the lithium ion capacitor are the same as in the case of the lithium ion secondary battery.
  • examples of the solvent used in the electrolyte include carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactones such as ⁇ -butyrolactone; Ethers such as trimethoxysilane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran; Sulfoxides such as dimethyl sulfoxide; Oxolane derivatives such as 1,3-dioxolane, 4-methyl-1,3-dioxolane; Nitrogen-containing compounds such as acetonitrile and nitromethane; Esters such as methyl formate, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, phosphate triester; Glyme compounds such as diglyme, triglyme and
  • Such an electrochemical device has high adhesion between the electrode active materials and between the electrode active material and the current collector in the electrode active material layer, and also has a discharge rate characteristic in a low temperature environment and electrochemical in a high temperature environment. Excellent in both stability and stability. Therefore, this electrochemical device is suitable as a secondary battery or a capacitor mounted on an automobile such as an electric vehicle, a hybrid car, and a truck, as well as a secondary battery used for AV equipment, OA equipment, communication equipment, It is also suitable as a capacitor.
  • a tape having a width of 18 mm (JIS Z1522-compliant product, trade name “Cerotape (registered trademark)”, manufactured by Nichiban Co., Ltd.) was attached to the current collector side surface of the test piece on the aluminum plate. While maintaining the angle with the aluminum plate at 90 °, the peel strength (mN / 2 cm) when this tape was pulled upward at a speed of 50 mm / min and peeled at a peel angle of 90 ° was measured 6 times. The average value was calculated as the peel strength (mN / 2 cm) of the electrode active material layer. “MN / 2 cm” is a unit indicating the peel strength per 2 cm width.
  • the low temperature rate characteristic (3.0 C / 0.2 C) (%) of the lithium ion secondary battery was calculated by the following formula.
  • Low-temperature rate characteristic (%) ⁇ (C 3.0 ) ⁇ (C 0.2 ) ⁇ ⁇ 100 It can be determined that the larger the value of the low temperature rate characteristic is, the smaller the change in the characteristic of the electrode is in the low temperature environment. In particular, this value is good when it is 80% or more.
  • “1C” indicates a current value at which discharge is completed in one hour after constant current discharge of a cell having a certain electric capacity.
  • “0.1 C” is a current value at which discharge is completed over 10 hours
  • 10 C is a current value at which discharge is completed over 0.1 hours.
  • the battery was charged at a normal temperature (25 ° C.) by a constant current (0.2 C) / constant voltage (3.8 V) method, left at 85 ° C. for 3 days, and then allowed to cool to normal temperature (25 ° C.).
  • the discharge capacity (C after ) when discharged by the constant current (0.2 C) method was measured.
  • Cycle characteristics A cycle in which a lithium ion secondary battery was charged by a constant current (0.2 C) / constant voltage (3.8 V) system and discharged by a constant current (0.2 C) system was repeated 50 times.
  • the third cycle discharge capacity (C 3Cycles) and 50th cycle discharge capacity (C 50Cycles) was measured to calculate the cycle characteristics (%) by the following equation.
  • Cycle characteristics (%) ⁇ (C 50 Cycles ) / (C 3 Cycles ) ⁇ ⁇ 100 It can be determined that the deterioration of the battery characteristics due to the oxidative decomposition of the binder due to charging and discharging is suppressed as the value of the cycle characteristics is closer to 100%.
  • Self-discharge rate (%) [ ⁇ (V before ) ⁇ (V after ) ⁇ ⁇ (V before )] ⁇ 100 It can be determined that the smaller the value of the self-discharge rate, the more the self-discharge is suppressed in a high temperature environment. In particular, this value is good when it is less than 30%.
  • Cycle characteristics The cycle in which the electric double layer capacitor was charged by the constant current (1C) / constant voltage (3.5 V) method and discharged by the constant current (1C) method was repeated 100 times. In this case, the third cycle discharge capacity (C 3Cycles) and 100 th cycle discharge capacity (C 100Cycles) was measured to calculate the cycle characteristics (%) by the following equation.
  • Cycle characteristics (%) ⁇ (C 100 Cycles ) / (C 3 Cycles ) ⁇ ⁇ 100 It can be determined that the deterioration of the battery characteristics due to the oxidative decomposition of the binder due to charging and discharging is suppressed as the value of the cycle characteristics is closer to 100%. In particular, this value is good when it is 80% or more.
  • ether sulfate type emulsifier (trade name “ADEKA rear soap SR1025”, manufactured by ADEKA Co., Ltd.) as an emulsifier, 0.8 parts in terms of solid content, and 2,2,2 as monomers -A monomer emulsion containing 25 parts of trifluoroethyl methacrylate, 25 parts of acrylonitrile, 10 parts of methyl methacrylate, 40 parts of 2-ethylhexyl acrylate and 5 parts of methacrylic acid and containing a mixture of the above monomers was stirred well.
  • ether sulfate type emulsifier trade name “ADEKA rear soap SR1025”, manufactured by ADEKA Co., Ltd.
  • the temperature inside the separable flask was started, and when the temperature inside the separable flask reached 60 ° C., 0.5 part of ammonium persulfate was added as a polymerization initiator. Then, when the temperature inside the separable flask reaches 70 ° C., the addition of the monomer emulsion prepared above is started, and the monomer emulsion is added while maintaining the temperature inside the separable flask at 70 ° C. Slowly added over time. Thereafter, the temperature inside the separable flask was raised to 85 ° C., and this temperature was maintained for 3 hours to carry out the polymerization reaction.
  • an electrode binder composition (s1).
  • the solid content concentration of the obtained binder composition for electrodes (s1) was 30% by mass.
  • the polymer in the electrode binder composition (s1) was in the form of particles having a glass transition temperature of ⁇ 10 ° C. and a number average particle diameter of 100 nm.
  • Examples 2 to 6 and Comparative Examples 1 to 5 and 7 The electrode binder compositions (s2) to (s6) and (r1) to (r5) and (r7) were carried out in the same manner as in Example 1 except that the monomers were used in accordance with the formulation shown in Table 1 below. ) Were prepared respectively.
  • Example 7 In a 7-liter separable flask, 150 parts of water and 0.2 part of sodium dodecylbenzenesulfonate were charged, and the inside of the separable flask was sufficiently purged with nitrogen.
  • ether sulfate type emulsifier (trade name “ADEKA rear soap SR1025”, manufactured by ADEKA Co., Ltd.) as an emulsifier, 0.8 parts in terms of solid content, and 2,2,2 as monomers -A monomer emulsion containing 25 parts of trifluoroethyl methacrylate, 25 parts of acrylonitrile, 10 parts of methyl methacrylate, 40 parts of 2-ethylhexyl acrylate and 5 parts of methacrylic acid and containing a mixture of the above monomers was stirred well.
  • ether sulfate type emulsifier trade name “ADEKA rear soap SR1025”, manufactured by ADEKA Co., Ltd.
  • the temperature increase was started, and when the temperature inside the separable flask reached 60 ° C., 0.5 parts of ammonium persulfate as a polymerization initiator was used. Was added.
  • the temperature inside the separable flask was raised to 70 ° C., and this temperature was maintained for 3 hours, and then the temperature was raised to 85 ° C. to conduct a polymerization reaction for another 3 hours. Thereafter, the separable flask was cooled to stop the reaction, and then ammonium water was added to adjust the pH to 7.6 to prepare an electrode binder composition (s7).
  • the solid content concentration of the obtained binder composition for electrodes (s7) was 30% by mass.
  • the polymer in the electrode binder composition (s7) was in the form of particles having a glass transition temperature of ⁇ 10 ° C. and a number average particle diameter of 100 nm.
  • Comparative Example 6 An electrode binder composition (r6) was prepared in the same manner as in Example 7 except that the monomer was used in accordance with the formulation shown in Table 1 below.
  • the glass transition temperature of the polymer and the number average particle diameter of the polymer particles in the obtained binder composition for electrodes (r6) are shown in Table 1 below.
  • Example 8 In a temperature-controllable autoclave equipped with a stirrer, 200 parts of water, 0.6 part of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate and 0.5 part of sodium bisulfite and 2,2,2 as monomers -25 parts of trifluoroethyl methacrylate, 25 parts of acrylonitrile, 16 parts of styrene, 35 parts of butadiene and 4 parts of methacrylic acid were charged all at once and a polymerization reaction was carried out at 80 ° C for 6 hours to obtain a polymer dispersion.
  • the glass transition temperature of the polymer and the number average particle diameter of the polymer particles in the obtained binder composition for electrodes (r8) are shown in Table 1 below.
  • an electrode active material layer was formed by pressing using a roll press so that the density of the film was 1.7 g / cm 3 to form a laminate.
  • a disc-shaped positive electrode for a lithium ion secondary battery having a diameter of 15.95 mm was manufactured.
  • the peel strength of the electrode active material layer in each of the obtained positive electrodes for lithium ion secondary batteries is shown in Table 2 below.
  • the slurry for negative electrodes was prepared by stirring and mixing for 1.5 minutes at 1,800 rpm.
  • the negative electrode slurry prepared above is uniformly applied to the surface of a current collector made of copper foil having a thickness of 20 ⁇ m by a doctor blade method so that the film thickness after drying is 150 ⁇ m, and dried at 120 ° C. for 20 minutes.
  • a coating film was obtained.
  • a disc-shaped negative electrode for a lithium ion secondary battery having a diameter of 16.16 mm was produced.
  • Lithium Ion Secondary Battery A negative electrode for a lithium ion secondary battery was placed on a bipolar coin cell (trade name “HS Flat Cell”, manufactured by Hosen Co., Ltd.) in a glove box. Next, a separator (trade name “Celguard # 2400”, manufactured by Celgard Co., Ltd.) made of a disk-shaped polypropylene porous film having a diameter of 18 mm is placed on the negative electrode, and an electrolyte solution is added so that air does not enter. Injected. Next, after placing a positive electrode for a lithium ion secondary battery on this separator, a lithium ion secondary battery was manufactured by tightening and sealing the outer body of the bipolar coin cell with a screw.
  • Table 2 shows the low-temperature rate characteristics, the self-discharge rate under a high-temperature environment, and the cycle characteristics of each obtained lithium ion secondary battery.
  • the electrode binder compositions (s1) to (s7) of the present invention are used, a positive electrode for a lithium ion secondary battery having a high peel strength of the electrode active material layer can be obtained. .
  • binder compositions for electrodes (s1) to (s3) using 2,2,2-trifluoroethyl methacrylate as the specific fluorine-containing (meth) acrylate and acrylonitrile as the ⁇ , ⁇ -unsaturated nitrile compound are as follows:
  • a lithium ion secondary battery positive electrode for a lithium ion secondary battery having a higher peel strength of the electrode active material layer can be obtained, and further excellent in discharge rate characteristics in a low temperature environment and electrochemical stability in a high temperature environment.
  • the electrode active material layer was formed by pressing using a roll press so that the density of the film was 1.8 g / cm 3 to form a laminate.
  • a disc-shaped negative electrode for a lithium ion secondary battery having a diameter of 16.16 mm was produced.
  • the peel strength of the electrode active material layer in each of the obtained negative electrodes for lithium ion secondary batteries is shown in Table 3 below.
  • a slurry for positive electrode was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes below.
  • the positive electrode slurry prepared above was uniformly applied to the surface of a current collector made of an aluminum foil having a thickness of 30 ⁇ m by a doctor blade method so that the film thickness of the coated film after drying was 90 ⁇ m.
  • the coating film was obtained by drying for 20 minutes.
  • a negative electrode is obtained. And it was confirmed that the lithium ion secondary battery provided with such a negative electrode is excellent in both discharge rate characteristics in a low temperature environment and electrochemical stability in a high temperature environment.
  • the difference between the example and the comparative example is about the low temperature rate characteristics and the self-discharge rate under a high temperature environment. Small (see Table 2 above). From this, it was found that the electrode binder composition of the present invention has a greater effect when applied to the positive electrode.
  • Examples 19 and 20 and Comparative Examples 19-21 (1) Manufacture of electrodes for electric double-layer capacitors Activated carbon (trade name “Kuraray Coal YP”) as an electrode active material in a biaxial planetary mixer (trade name “TK Hibismix 2P-03”, manufactured by Primix Co., Ltd.) , Kuraray Chemical Co., Ltd.
  • Activated carbon trade name “Kuraray Coal YP”
  • TK Hibismix 2P-03 manufactured by Primix Co., Ltd.
  • conductive carbon (trade name “Denka Black”, manufactured by Denki Kagaku Kogyo Co., Ltd.), thickener (trade name “CMC2200”, manufactured by Daicel Chemical Industries, Ltd.) ) 2 parts and 278 parts of water were added and stirred at 60 rpm for 1 hour. Thereafter, 4 parts (in terms of solid content) of each electrode binder composition produced in the above Examples and Comparative Examples were added, and the mixture was further stirred for 1 hour to obtain a paste.
  • conductive carbon trade name “Denka Black”, manufactured by Denki Kagaku Kogyo Co., Ltd.
  • thickener trade name “CMC2200”, manufactured by Daicel Chemical Industries, Ltd.
  • the positive electrode slurry prepared above is uniformly applied to the surface of a current collector made of an aluminum foil having a thickness of 20 ⁇ m by a doctor blade method so that the thickness of the coating film after drying becomes 150 ⁇ m.
  • the coating film was obtained by drying for 20 minutes.
  • an electrode active material layer was formed by pressing using a roll press so that the density of the film was 1.5 g / cm 3 to form a laminate.
  • two types of disc-shaped electrodes for electric double layer capacitors having a diameter of 15.95 mm and 16.16 mm were manufactured.
  • the peel strength of the electrode active material layer in the obtained electric double layer capacitor electrode is shown in Table 4 below.
  • a disk-shaped cellulose separator having a diameter of 18 mm (trade name “TF4535”, manufactured by Nippon Kogyo Paper Industries Co., Ltd.) was placed on the electrode, and an electrolyte was injected so that air did not enter.
  • an electrode for an electric double layer capacitor having a diameter of 15.95 mm was placed on the separator, and then the outer body of the bipolar coin cell was tightened and sealed to manufacture an electric double layer capacitor.
  • the electrolytic solution used here is a propylene carbonate solution containing 1 mol / L triethylmethylammonium tetrafluoroborate. Table 4 below shows the self-discharge rate and cycle characteristics of each electric double layer capacitor obtained under a high temperature environment.

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Abstract

La présente invention concerne une composition liante pour utilisation dans des électrodes, qui contient un polymère qui comprend des motifs structuraux (A) dérivés d'un monomère représenté par la formule générale (1) et des motifs structuraux (B) dérivés d'un monomère de nitrile α,β-insaturé, et qui est caractérisée en ce que : la teneur des motifs structuraux (A) est de 5 à 60 % en masse ; la teneur des motifs structuraux (B) est de 5 à 40 % en masse ; et la teneur totale des motifs structuraux (A) et (B) est de 10 à 70 % en masse. Dans la formule générale (1), R1 est un atome d'hydrogène ou un groupe méthyle, et R2 est un groupe hydrocarboné fluoré en C1-18.
PCT/JP2011/068818 2010-08-20 2011-08-16 Composition liante pour utilisation dans des électrodes WO2012023626A1 (fr)

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CN109997262A (zh) * 2016-11-25 2019-07-09 出光兴产株式会社 电化学元件用粘结剂
CN110828779A (zh) * 2019-12-11 2020-02-21 东莞维科电池有限公司 一种锂离子电池负极片及其制备方法、锂离子电池
CN113613768A (zh) * 2019-03-29 2021-11-05 东洋油墨Sc控股株式会社 分散剂、分散体、树脂组合物、复合材料浆料、电极膜及非水电解质二次电池
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KR20150021018A (ko) * 2012-05-25 2015-02-27 제온 코포레이션 리튬 이온 2 차 전지
JPWO2013176232A1 (ja) * 2012-05-25 2016-01-14 日本ゼオン株式会社 リチウムイオン二次電池
KR101978462B1 (ko) 2012-05-25 2019-05-14 제온 코포레이션 리튬 이온 2 차 전지
JPWO2014024967A1 (ja) * 2012-08-10 2016-07-25 日本ゼオン株式会社 リチウムイオン二次電池負極用スラリー組成物
WO2014024967A1 (fr) * 2012-08-10 2014-02-13 日本ゼオン株式会社 Composition de bouillie pour électrode négative de cellule secondaire lithium-ion
CN108701833A (zh) * 2016-03-10 2018-10-23 日本瑞翁株式会社 非水系二次电池电极用粘结剂、非水系二次电池电极用浆料、非水系二次电池用电极及非水系二次电池
US20190097235A1 (en) * 2016-03-10 2019-03-28 Zeon Corporation Binder for non-aqueous secondary battery electrode, slurry for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery
US10910651B2 (en) * 2016-03-10 2021-02-02 Zeon Corporation Binder for non-aqueous secondary battery electrode, slurry for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery
CN109997262A (zh) * 2016-11-25 2019-07-09 出光兴产株式会社 电化学元件用粘结剂
US20220045360A1 (en) * 2018-12-28 2022-02-10 Zeon Corporation Binder composition for all-solid-state secondary battery
CN113613768A (zh) * 2019-03-29 2021-11-05 东洋油墨Sc控股株式会社 分散剂、分散体、树脂组合物、复合材料浆料、电极膜及非水电解质二次电池
CN110828779A (zh) * 2019-12-11 2020-02-21 东莞维科电池有限公司 一种锂离子电池负极片及其制备方法、锂离子电池
CN110828779B (zh) * 2019-12-11 2022-08-23 东莞维科电池有限公司 一种锂离子电池负极片及其制备方法、锂离子电池
JP2022074127A (ja) * 2020-10-30 2022-05-17 長興材料工業股▲ふん▼有限公司 グラフトコポリマー及びその使用
JP7313412B2 (ja) 2020-10-30 2023-07-24 長興材料工業股▲ふん▼有限公司 グラフトコポリマー及びその使用
US11827730B2 (en) 2020-10-30 2023-11-28 Eternal Materials Co., Ltd. Graft copolymer and use thereof

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