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WO2016159198A1 - Liant pour électrode d'élément accumulateur au lithium-ion - Google Patents

Liant pour électrode d'élément accumulateur au lithium-ion Download PDF

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Publication number
WO2016159198A1
WO2016159198A1 PCT/JP2016/060586 JP2016060586W WO2016159198A1 WO 2016159198 A1 WO2016159198 A1 WO 2016159198A1 JP 2016060586 W JP2016060586 W JP 2016060586W WO 2016159198 A1 WO2016159198 A1 WO 2016159198A1
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WIPO (PCT)
Prior art keywords
mass
ion secondary
electrode
lithium ion
acrylate
Prior art date
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Ceased
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PCT/JP2016/060586
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English (en)
Japanese (ja)
Inventor
泰之 三好
三佐和　裕二
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to JP2017510163A priority Critical patent/JP6450453B2/ja
Publication of WO2016159198A1 publication Critical patent/WO2016159198A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a binder for an electrode of a lithium ion secondary battery. More specifically, the present invention is a binder for an electrode of a lithium ion secondary battery that is excellent in binding properties between active materials and between an active material and a current collector, and has excellent flexibility, and a method for producing the same, An aqueous electrode composition for a lithium ion secondary battery containing a binder for an electrode of the lithium ion secondary battery, an electrode of a lithium ion secondary battery formed using the aqueous electrode composition for the lithium ion secondary battery, and The present invention relates to a lithium ion secondary battery containing the electrode.
  • a binder for an aqueous electrode composition containing a water-soluble polymer compound containing a structural unit derived from an ethylenically unsaturated carboxylate monomer and a structural unit derived from an ethylenically unsaturated carboxylic acid ester monomer is In addition to being excellent in the dispersibility of the active material and the conductive auxiliary agent, it is attracting attention because of its excellent binding property between the active materials and between the active material and the current collector (see, for example, Patent Document 1).
  • the binder for electrode compositions is excellent in the dispersibility of the active material and the conductive auxiliary agent and is excellent in the binding property between the active materials and between the active material and the current collector.
  • the development of a binder for an electrode of a lithium ion secondary battery that forms a positive electrode with excellent binding properties between an active material and a current collector and excellent flexibility is awaited.
  • the present invention has been made in view of the prior art, and is an electrode of a lithium ion secondary battery that forms an electrode having excellent binding properties between active materials and between an active material and a current collector, and excellent flexibility. Binder and manufacturing method thereof, lithium ion secondary battery aqueous electrode composition containing the lithium ion secondary battery electrode binder, and lithium ion formed using the lithium ion secondary battery aqueous electrode composition It is an object of the present invention to provide an electrode of a secondary battery and a lithium ion secondary battery containing the electrode.
  • the present invention (1) A binder used in a lithium ion secondary battery, which is an acrylate-based polymer obtained by polymerizing a monomer component containing a polyfunctional monomer and an alkyl acrylate having an alkyl group with 1 to 3 carbon atoms.
  • a binder for an electrode of a lithium ion secondary battery comprising resin particles containing a coalescence
  • a lithium ion which is a binder used in a lithium ion secondary battery, containing resin particles and water, wherein the resin particles are the resin particles according to (1) or (2).
  • Binder for electrodes for secondary batteries (4) The aqueous electrode composition for lithium ion secondary batteries according to any one of (1) to (3), further comprising an electrode active material, (5) An electrode including a current collector and an electrode mixture layer, wherein the electrode mixture layer is formed on the current collector, and the electrode mixture layer is the lithium ion secondary battery according to (4).
  • An electrode of a lithium ion secondary battery formed from an aqueous electrode composition (6) A method for producing a lithium ion secondary battery comprising the lithium ion secondary battery electrode according to (5), and (7) a binder used in the lithium ion secondary battery, wherein Lithium ion secondary battery characterized in that a resin component containing an acrylate polymer is produced by emulsion polymerization of a monomer component containing a monomer and an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms
  • the present invention relates to a method for producing an electrode binder.
  • (meth) acrylate means “acrylate” or “methacrylate”
  • (meth) acryl means “acryl” or “methacryl”.
  • the binder for an electrode of the lithium ion secondary battery of the present invention is excellent in the binding property between the active materials and between the active material and the current collector, and forms an electrode with excellent flexibility. It can be suitably used for an electrode. Since the water-based electrode composition for a lithium ion secondary battery, the electrode of a lithium ion secondary battery, and the lithium ion secondary battery of the present invention use the binder for an electrode of the lithium ion secondary battery, the active materials and Excellent binding properties between the active material and the current collector, and the electrode has excellent flexibility.
  • the binder for an electrode of the lithium ion secondary battery of the present invention is obtained by polymerizing a monomer component containing a polyfunctional monomer and an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms. Resin particles containing an acrylate polymer are contained.
  • the binder for an electrode of the lithium ion secondary battery of the present invention includes, for example, an acrylate polymer by emulsion polymerization of a polyfunctional monomer and a monomer component containing an alkyl acrylate having an alkyl group with 1 to 3 carbon atoms. It can be obtained by producing resin particles containing coalescence.
  • the binder for an electrode of the lithium ion secondary battery of the present invention uses a polyfunctional monomer and an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms in combination, so An electrode having excellent binding properties with an electric body and excellent flexibility is formed.
  • the binder for an electrode of the lithium ion secondary battery of the present invention is a combination of a polyfunctional monomer and an alkyl acrylate containing an alkyl acrylate having an alkyl group with 1 to 3 carbon atoms.
  • an ethylenically unsaturated group for example, an ethylenically unsaturated group, preferably a monomer having one or more (meth) acryloyl groups and having a crosslinkable group, an ethylenically unsaturated group, preferably (meth) And monomers having two or more acryloyl groups.
  • the crosslinkable group is a functional group that causes a crosslinking reaction under conditions such as heating, acidic or basic conditions.
  • Examples of the monomer having one or more ethylenically unsaturated groups, preferably (meth) acryloyl groups and having a crosslinkable group include N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, Amide group-containing polyfunctional monomers such as Nn-butoxymethyl (meth) acrylamide; Epoxy group-containing polyfunctional monomers such as epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; ⁇ - (meta ) Alkoxysilyl group-containing (meth) acrylates such as acryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropylmethyldiethoxysilane, ⁇ -methacryloxypropyltriethoxysilane; vinyltrichlorosilane; Vinyl tris ( ⁇ -methoxyethoxy Examples include silicon atom-
  • Examples of monomers having two or more ethylenically unsaturated groups, preferably (meth) acryloyl groups, include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, and tripropylene.
  • Monomers having two or more (meth) acryloyl groups such as glycol diacrylate, tripropylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate;
  • the present invention is not limited to such examples.
  • These polyfunctional monomers may be used alone or in combination of two or more.
  • amide group-containing polyfunctional monomers are preferable from the viewpoint of improving the binding between the active materials and between the active material and the current collector, and N-methylol (meth) acrylamide is more preferable. preferable.
  • the content of the polyfunctional monomer in the monomer component is preferably 0.5 from the viewpoint of improving the strength of the resin particles and improving the binding between the active materials and between the active material and the current collector.
  • % By mass or more preferably 1% by mass or more, more preferably 1.5% by mass or more, and preferably 5% by mass from the viewpoint of improving the binding between the active materials and the active material and the current collector.
  • it is more preferably 4% by mass or less, and further preferably 3% by mass or less.
  • one of the features of the present invention is that an alkyl acrylate having 1 to 3 carbon atoms is used.
  • the alkyl acrylate having 1 to 3 carbon atoms is used as described above, the binding property between the active materials and the binding property between the active material and the current collector are improved. be able to.
  • an alkyl methacrylate having 1 to 3 carbon atoms similar to the alkyl acrylate is used instead of the alkyl acrylate having 1 to 3 carbon atoms, the active materials and the active material and the current collector are collected. The binding property with the body cannot be improved sufficiently.
  • alkyl acrylate having 1 to 3 carbon atoms examples include methyl acrylate, ethyl acrylate and propyl acrylate. These alkyl acrylates may be used alone or in combination of two or more. Among these alkyl acrylates, methyl acrylate and ethyl acrylate are preferable, and methyl acrylate is more preferable from the viewpoint of improving the binding properties between the active materials and between the active material and the current collector.
  • the content of the alkyl acrylate having 1 to 3 carbon atoms in the monomer component is preferably 25 from the viewpoint of enhancing cohesion and improving the binding between the active materials and between the active material and the current collector.
  • the monomer component includes a polyfunctional monomer and an alkyl group having 1 to 3 carbon atoms so that the total amount of monomers used in the monomer component is 100% by mass.
  • a monofunctional monomer other than the alkyl acrylate having 1 to 3 carbon atoms in the alkyl group (hereinafter referred to as another monomer) can be used for the remainder of the alkyl acrylate. .
  • Examples of other monomers include alkyl methacrylates having an alkyl group with 1 to 3 carbon atoms, alkyl (meth) acrylates with an alkyl group having 4 to 18 carbon atoms, carboxyl group-containing monomers, and nitrile groups. Containing monomer, nitrogen atom-containing monomer other than nitrile group-containing monomer, monomer having alicyclic structure, hydroxyl group-containing (meth) acrylate, carbonyl group-containing monomer, aromatic monomer, Although a fluorine atom containing monomer etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.
  • Monomers and nitrile group-containing monomers are preferred.
  • alkyl methacrylate having 1 to 3 carbon atoms in the alkyl group examples include methyl methacrylate, ethyl methacrylate, and propyl methacrylate. These alkyl methacrylates may be used alone or in combination of two or more. Among these alkyl methacrylates, methyl methacrylate and ethyl methacrylate are preferable, and methyl methacrylate is more preferable from the viewpoint of improving binding properties between the active materials and between the active material and the current collector.
  • the content of the alkyl methacrylate having 1 to 3 carbon atoms of the alkyl group in the monomer component is 0% by mass or more, but the cohesive force of the resin particles is increased, and the active materials and the active materials and the current collector From the viewpoint of improving the binding properties of the monomer component, it is preferably 40% by mass or less, more preferably 35% by mass or less, and no alkyl methacrylate having 1 to 3 carbon atoms in the alkyl group in the monomer component is contained. More preferably.
  • alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms examples include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and sec-butyl (meth) acrylate.
  • alkyl (meth) acrylates may be used alone or in combination of two or more.
  • (Meth) acrylate is preferred, and n-butyl (meth) acrylate, tert-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferred.
  • the content of the alkyl (meth) acrylate having 4 to 18 carbon atoms in the monomer component increases the flexibility of the resin particles, and improves the binding between the active materials and between the active material and the current collector. From the viewpoint of improving, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and still more preferably 20% by mass or more. From the viewpoint of improving the binding property, it is preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less.
  • carboxyl group-containing monomer examples include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and the like, but the present invention is not limited to such examples. These carboxyl group-containing monomers may be used alone or in combination of two or more. Among the carboxyl group-containing monomers, (meth) acrylic acid is preferable from the viewpoint of improving the binding between the active materials and the active material and the current collector.
  • the content of the carboxyl group-containing monomer in the monomer component is preferably from the viewpoint of enhancing the dispersion stability of the resin particles and improving the binding properties between the active materials and between the active material and the current collector. 3% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, and preferably 15% by mass from the viewpoint of improving the binding between the active materials and the active material and the current collector. % Or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • nitrile group-containing monomer examples include (meth) acrylonitrile, but the present invention is not limited to such examples. These nitrile group-containing monomers may be used alone or in combination of two or more. Among the nitrile group-containing monomers, acrylonitrile is preferable from the viewpoint of improving the binding between the active materials and the active material and the current collector.
  • the content of the nitrile group-containing monomer in the monomer component is 0% by mass or more, it increases the cohesive strength of the resin particles and improves the binding between the active materials and between the active material and the current collector. From the viewpoint, it is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more, and improves the binding property between the active materials and between the active material and the current collector. From the viewpoint, it is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • nitrogen atom-containing monomers other than nitrile group-containing monomers include (meth) acrylamide compounds such as (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and dimethylaminoethyl (meth) acrylate. And nitrogen atom-containing (meth) acrylates such as diethylaminoethyl (meth) acrylate, and the like, but the present invention is not limited to such examples. These nitrogen atom-containing monomers may be used alone or in combination of two or more.
  • (meth) acrylamide compounds and nitrogen atom-containing (meth) acrylates are preferred, (meth) acrylamide compounds are more preferred, More preferred is (meth) acrylamide.
  • the content of the nitrogen atom-containing monomer other than the nitrile group-containing monomer in the monomer component is 0% by mass or more, but the cohesive strength and elasticity of the resin particles are increased, and the binding property to the current collector is improved. From the viewpoint of improving, it is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. From the viewpoint of improving the binding property to the current collector, preferably 20% by mass. It is not more than mass%, more preferably not more than 15 mass%, still more preferably not more than 10 mass%.
  • the alicyclic structure is preferably a cycloalkyl group having 4 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 10 carbon atoms.
  • Examples of the monomer having an alicyclic structure include cycloalkyl (meth) acrylate and cycloalkylalkyl (meth) acrylate, and these monomers may be used alone or in combination of two or more. May be used in combination. Moreover, these monomers may have a substituent.
  • substituents examples include alkyl groups such as a methyl group and a tert-butyl group, nitro groups, nitrile groups, alkoxy groups, acyl groups, sulfone groups, hydroxyl groups, halogen atoms, and the like. It is not limited to illustration only.
  • cycloalkyl (meth) acrylate for example, a cycloalkyl group such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., preferably has 4 to 20 carbon atoms, more preferably 4 to 10 cycloalkyl (meth) acrylates.
  • the present invention is not limited to such examples.
  • These cycloalkyl (meth) acrylates may be used alone or in combination of two or more.
  • Examples of the cycloalkylalkyl (meth) acrylate include carbon numbers of cycloalkyl groups such as cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, and 4-methylcyclohexylmethyl (meth) acrylate. Is preferably 4 to 20, more preferably 4 to 10, and examples thereof include cycloalkylalkyl (meth) acrylates having an alkyl group having 1 to 4 carbon atoms, and these cycloalkylalkyl (meth) acrylates include Each may be used alone or in combination of two or more.
  • cycloalkyl (meth) acrylate having a cycloalkyl group having 4 to 20 carbon atoms is preferable, and cycloalkyl (meth) having a cycloalkyl group having 4 to 10 carbon atoms.
  • Acrylates are more preferred, and isobornyl (meth) acrylate and cyclohexyl (meth) acrylate are more preferred.
  • hydroxyl group-containing (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxy Examples thereof include hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in the ester group such as butyl (meth) acrylate and glycerin mono (meth) acrylate, but the present invention is not limited to such examples. . These monomers may be used alone or in combination of two or more.
  • hydroxyl group-containing (meth) acrylates 2-hydroxyethyl (meth) acrylate and glycerin mono (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.
  • Examples of the carbonyl group-containing monomer include acrolein, methacrolein, humylstyrene, vinyl ethyl ketone, acryloxyalkyl propenal, methacryloxyalkyl propenal, acetonyl acrylate, acetonyl methacrylate, diacetone acrylate, diacetone.
  • These carbonyl group-containing monomers may be used alone or in combination of two or more.
  • aromatic monomer examples include styrene, ⁇ -methyl styrene, p-methyl styrene, tert-methyl styrene, chlorostyrene, aralkyl (meth) acrylate, vinyltoluene, and the like. It is not limited to illustration only.
  • aralkyl (meth) acrylate examples include aralkyl having 7 to 18 carbon atoms such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, naphthylmethyl (meth) acrylate, and the like. Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These aromatic monomers may be used alone or in combination of two or more.
  • fluorine atom-containing monomer examples include alkyls in which hydrogen atoms of alkyl groups such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate are substituted with fluorine atoms ( Examples thereof include, but are not limited to such examples. These monomers may be used alone or in combination of two or more.
  • Lithium that forms alkyl (meth) acrylates other than polyfunctional monomers used in the monomer component is excellent in binding properties between active materials and between active materials and current collectors and has excellent flexibility From the viewpoint of obtaining a binder for an electrode of an ion secondary battery, it preferably has an acryloyl group.
  • a binder for an electrode of a lithium ion secondary battery that is excellent in binding properties between active materials and between an active material and a current collector and forms an electrode having excellent flexibility.
  • an amide group-containing polyfunctional monomer such as N-methylol (meth) acrylamide or 0.5 to 5% by mass of glycidyl (meth) acrylate is contained.
  • a monomer component containing is preferred.
  • an aqueous medium containing a water-soluble organic solvent such as methanol and a lower alcohol, and water an emulsifier is dissolved in a medium such as water, and a single amount is obtained under heating and stirring.
  • emulsifier examples include an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, a polymer emulsifier, and a reactive emulsifier. These emulsifiers may be used alone or in combination of two or more. May be.
  • anionic emulsifier examples include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Examples include polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearate. It is not limited to illustration only.
  • Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Although the condensate with an amine etc. are mentioned, this invention is not limited only to this illustration.
  • Examples of the cationic emulsifier include alkylammonium salts such as dodecyl ammonium chloride, but the present invention is not limited to such examples.
  • amphoteric emulsifiers examples include betaine ester type emulsifiers, but the present invention is not limited to such examples.
  • polymer emulsifier examples include poly (meth) acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinyl pyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl acrylate; single polymers constituting these polymers.
  • poly (meth) acrylates such as sodium polyacrylate
  • polyvinyl alcohol such as polyvinyl alcohol
  • polyvinyl pyrrolidone polyhydroxyalkyl (meth) acrylates
  • polyhydroxyethyl acrylate such as polyhydroxyethyl acrylate
  • single polymers constituting these polymers single polymers constituting these polymers.
  • reactive emulsifiers include propenyl-alkylsulfosuccinic acid ester salts, (meth) acrylic acid polyoxyethylene sulfonate salts, (meth) acrylic acid polyoxyethylene phosphonate salts [for example, manufactured by Sanyo Chemical Industries, Ltd.
  • the amount of the emulsifier per 100 parts by mass of the monomer component is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more from the viewpoint of improving the monopolymerization stability. From the viewpoint of improving the binding property with the current collector, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less.
  • polymerization initiator examples include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as ammonium persulfate and potassium persulfate;
  • peroxide examples include peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.
  • these polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator per 100 parts by mass of the monomer component is preferably 0.05 parts by mass or more, more preferably 0 from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component. From the viewpoint of improving the binding properties between the active materials and the active material and the current collector, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.
  • the method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dripping. From the viewpoint of advancing the completion time of the polymerization reaction, a part of the polymerization initiator may be added to the flask before or after the monomer component is added to the reaction system.
  • an appropriate amount of a reducing agent such as sodium disulfite or sodium hydrogen sulfite, or a decomposition agent of a polymerization initiator such as transition metal salt such as ferrous sulfate in the reaction system. May be added.
  • additives such as a chain transfer agent such as a compound having a thiol group such as tert-dodecyl mercaptan, a pH buffering agent, a chelating agent, and a film-forming aid are added to the reaction system. May be.
  • the amount of the additive per 100 parts by mass of the monomer component varies depending on the type and cannot be determined unconditionally, but is usually preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts. Part by mass.
  • the atmosphere for emulsion polymerization of the monomer component is not particularly limited, but is preferably an inert gas such as nitrogen gas from the viewpoint of increasing the efficiency of the polymerization initiator.
  • the polymerization temperature when the monomer component is subjected to emulsion polymerization is not particularly limited, but is usually preferably 50 to 100 ° C, more preferably 60 to 95 ° C.
  • the polymerization temperature may be constant or may be changed during the polymerization reaction.
  • the polymerization time for emulsion polymerization of the monomer component is not particularly limited, and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours.
  • resin particles (emulsion particles) containing an acrylate polymer can be obtained.
  • the acrylate polymer constituting the resin particles may have a crosslinked structure.
  • the weight average molecular weight of the acrylate polymer is preferably 100,000 or more, more preferably 300,000 or more, further preferably 550,000 or more, from the viewpoint of improving the binding properties between the active materials and the active material and the current collector. Even more preferably, it is 600,000 or more.
  • the upper limit of the weight average molecular weight of the acrylate polymer is not particularly limited when it has a crosslinked structure, and it is difficult to measure the weight average molecular weight, but when it does not have a crosslinked structure, it is 5 million or less. Preferably there is.
  • the weight average molecular weight of the acrylate polymer is gel permeation chromatography [manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L in series.
  • the glass transition temperature of the acrylate polymer is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 45 ° C. or higher, further preferably ⁇ 40 ° C. or higher, from the viewpoint of improving the charge / discharge characteristics of the battery. From the viewpoint of improving the binding property between the active material and the current collector, it is preferably 30 ° C. or lower, more preferably 20 ° C. or lower, still more preferably 10 ° C. or lower, and even more preferably 0 ° C. or lower.
  • the glass transition temperature of the acrylate polymer can be easily adjusted by adjusting the composition of the monomer used for the monomer component.
  • the glass transition temperature of the homopolymer is, for example, -56 ° C. for n-butyl acrylate homopolymer, 9 ° C. for methyl acrylate homopolymer, 95 ° C. for acrylic acid homopolymer, and methyl methacrylate homopolymer. Is 105 ° C., ethyl acrylate homopolymer is ⁇ 22 ° C., and acrylonitrile homopolymer is 96 ° C.
  • the glass transition temperature of the acrylate polymer means the glass transition temperature determined based on the Fox formula.
  • the measured value of the glass transition temperature of the acrylate polymer is preferably the same as the value obtained based on the Fox equation.
  • the actual measured value of the glass transition temperature of the acrylate polymer can be measured by, for example, DSC (Differential Scanning Calorimeter), DTA (Differential Thermal Analyzer), TMA (Thermomechanical Measuring Device) and the like.
  • the average particle diameter of the resin particles is preferably 50 nm or more, more preferably 100 nm or more, from the viewpoint of improving the mechanical stability of the resin particles themselves, and the binding properties between the active materials and between the active material and the current collector. From the viewpoint of improving the thickness, it is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 200 nm or less.
  • the average particle size of the resin particles is measured using a particle size distribution measuring instrument (Particle Sizing Systems, trade name: NICOMP Model 380) by a dynamic light scattering method. It means the volume average particle diameter.
  • the nonvolatile content in the resin emulsion is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of improving productivity, and preferably 70% by mass or less, more preferably from the viewpoint of improving handleability. 60% by mass or less.
  • the non-volatile content in the resin emulsion was determined by weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 150 ° C. for 30 minutes.
  • [Non-volatile content in resin emulsion (mass%)] ([Residue mass] / [resin emulsion 1 g]) ⁇ 100 Means the value obtained based on
  • a resin emulsion containing resin particles can be obtained.
  • the resin emulsion containing the resin particles can be suitably used as an electrode binder as it is.
  • the binder for an electrode of the lithium ion secondary battery of the present invention may be in any form in which the resin particles are dispersed in water or in a state where the resin particles are dried.
  • the binder for electrodes of the lithium ion secondary battery of the present invention may contain a water-soluble organic solvent.
  • the water-soluble organic solvent include a water-soluble alcohol, a water-soluble ketone compound, a water-soluble ether compound, and the like, but the present invention is not limited to such examples.
  • the electrode binder of the present invention may contain other resin components and resin particles as long as the object of the present invention is not impaired.
  • the aqueous electrode composition for a lithium ion secondary battery of the present invention is an aqueous electrode composition for forming an electrode of a lithium ion secondary battery, contains a binder and an electrode active material, and the binder is the electrode binder. It is characterized by being.
  • the aqueous electrode composition for a lithium ion secondary battery of the present invention can be prepared, for example, by mixing the electrode binder, the electrode active material, and, if necessary, other components.
  • aqueous electrode composition for lithium ion secondary batteries examples include an aqueous positive electrode composition for lithium ion secondary batteries and an aqueous negative electrode composition for lithium ion secondary batteries.
  • the binder for electrodes of the present invention can be used for any composition, it can be suitably used for an aqueous positive electrode composition for lithium ion secondary batteries.
  • the aqueous positive electrode composition for a lithium ion secondary battery is an aqueous electrode composition for a lithium ion secondary battery used when forming a positive electrode.
  • As essential components in addition to the binder for an electrode, a positive electrode active material and a conductive assistant. Contains agents.
  • the content of the non-volatile content of the binder for the electrode in the non-volatile content of the aqueous positive electrode composition for a lithium ion secondary battery is preferably 0.2 to 3 mass from the viewpoint of improving the output characteristics and electrical characteristics of the lithium ion secondary battery. %, More preferably 0.3 to 2.5% by mass.
  • the positive electrode active material used in the aqueous positive electrode composition for lithium ion secondary batteries is preferably a positive electrode active material capable of occluding or releasing lithium ions.
  • the compound capable of inserting or extracting lithium ions include lithium-containing metal oxides.
  • the metal oxide containing lithium include lithium cobalt oxide, lithium iron phosphate, lithium manganese phosphate, lithium manganate, lithium nickel manganese cobalt oxide, and lithium nickel cobalt aluminum composite oxide. The invention is not limited to such examples.
  • These positive electrode active materials may be used alone or in combination of two or more.
  • the content of the positive electrode active material in the nonvolatile content of the aqueous positive electrode composition for a lithium ion secondary battery is preferably 70 to 98.8% by mass from the viewpoint of improving the output characteristics and electrical characteristics of the lithium ion secondary battery. Preferably, it is 80 to 98.3% by mass.
  • the conductive auxiliary agent is used to improve the output of the lithium ion secondary battery.
  • conductive carbon is mainly used.
  • the conductive carbon include carbon black, fiber-like carbon, and graphite.
  • the present invention is not limited to such examples.
  • carbon black is preferred.
  • carbon black include ketjen black and acetylene black, but the present invention is not limited to such examples.
  • the content of the conductive assistant in the nonvolatile content of the aqueous positive electrode composition for lithium ion secondary batteries is preferably 1 to 20% by mass, more preferably from the viewpoint of improving the output characteristics and electrical characteristics of the lithium ion secondary battery. 1.5 to 10% by mass.
  • water-based positive electrode composition for a lithium ion secondary battery as other components, for example, (meth) acrylic polymer, nitrile polymer, diene polymer and other non-fluorine polymers, polytetrafluoroethylene, etc.
  • Polymers such as fluorine-based polymers, surfactants such as anionic surfactants, nonionic surfactants and cationic surfactants; dispersants such as polymer dispersants such as styrene-maleic acid copolymers and polyvinylpyrrolidone , Carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, polyacrylic acid (salt), alkali-soluble (meth) acrylic acid- (meth) acrylic acid ester copolymer thickeners, preservatives, etc. Good.
  • the content of other components in the non-volatile content of the aqueous positive electrode composition for lithium ion secondary batteries is preferably 0 to 15% by mass, more preferably 0 to 10% by mass.
  • the viscosity of the water-based positive electrode composition for a lithium ion secondary battery measured using a viscometer (manufactured by Toki Sangyo Co., Ltd., product number: TVB-10) at a temperature of 25 ⁇ 1 ° C. and 30 rpm is From the viewpoint of improving the workability, it is preferably 1 to 20 Pa ⁇ s, more preferably 2 to 15 Pa ⁇ s.
  • the viscosity of the aqueous positive electrode composition for lithium ion secondary batteries can be easily adjusted by adjusting the amount of water and the amount of thickener contained in the aqueous positive electrode composition for lithium ion secondary batteries. Can do.
  • the pH of the aqueous positive electrode composition for lithium ion secondary batteries at 25 ° C. is preferably 6 to 11 from the viewpoint of suppressing corrosion of the current collector.
  • the pH is a value measured using a glass electrode-type hydrogen ion thermometer [manufactured by Horiba, Ltd., product number: F-21].
  • the aqueous positive electrode composition for a lithium ion secondary battery is, for example, mixed with an electrode binder, a positive electrode active material, a conductive auxiliary agent and other components as necessary, and dispersed using a bead mill, a ball mill, a stirring type mixer or the like.
  • a bead mill a ball mill, a stirring type mixer or the like.
  • the binder for an electrode of the present invention and the conductive auxiliary agent can be used.
  • the aqueous negative electrode composition for a lithium ion secondary battery is an aqueous electrode composition for a lithium ion secondary battery used when forming a negative electrode, and contains a negative electrode active material in addition to the electrode binder as an essential component. .
  • the content of the non-volatile content of the electrode binder in the non-volatile content of the aqueous negative electrode composition for a lithium ion secondary battery is preferably 0.3 to 4 mass from the viewpoint of improving the output characteristics and electrical characteristics of the lithium ion secondary battery. %, More preferably 0.5 to 2.5% by mass.
  • the content of the conductive assistant in the nonvolatile content of the aqueous negative electrode composition for lithium ion secondary batteries is preferably 1 to 20% by mass, more preferably from the viewpoint of improving the output characteristics and electrical characteristics of the lithium ion secondary battery. 1.5 to 10% by mass.
  • Examples of the negative electrode active material used in the aqueous negative electrode composition for lithium ion secondary batteries include carbon materials such as graphite, natural graphite, and artificial graphite, polyacene conductive polymers, composite metal oxides such as lithium titanate, lithium Although an alloy, a silicon-type material, etc. are mentioned, this invention is not limited only to this illustration. These negative electrode active materials may be used alone or in combination of two or more. Among these negative electrode active materials, carbon materials and / or lithium titanate are preferable.
  • the content of the carbon material and / or lithium titanate in the negative electrode active material is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 80 to 100% by mass.
  • the content of the negative electrode active material in the nonvolatile content of the aqueous negative electrode composition for lithium ion secondary batteries is preferably 85 to 99.7% by mass from the viewpoint of improving the output characteristics and electrical characteristics of the lithium ion secondary battery.
  • the content is preferably 90 to 99.5% by mass.
  • the lithium-ion secondary battery aqueous negative electrode composition may contain other components such as a dispersant, a thickener, and a preservative.
  • the content of other components in the non-volatile content of the aqueous negative electrode composition for lithium ion secondary batteries is preferably 0 to 15% by mass, more preferably from the viewpoint of improving the output characteristics and electrical characteristics of the lithium ion secondary battery. 0 to 10% by mass.
  • the aqueous negative electrode composition for a lithium ion secondary battery is, for example, mixed with a binder for an electrode, a negative electrode active material, a conductive additive and other components as necessary, and dispersed using a bead mill, a ball mill, a stirring type mixer, or the like.
  • a binder for an electrode for example, mixed with a binder for an electrode, a negative electrode active material, a conductive additive and other components as necessary, and dispersed using a bead mill, a ball mill, a stirring type mixer, or the like.
  • the electrode for a lithium ion secondary battery includes a current collector and an electrode mixture layer, the electrode mixture layer is formed on the current collector, and the electrode mixture layer is an aqueous system for the lithium ion secondary battery. It is formed from an electrode composition.
  • the lithium ion secondary battery electrode includes a positive electrode for a lithium ion secondary battery and a negative electrode for a lithium ion secondary battery.
  • the positive electrode for a lithium ion secondary battery has a positive electrode mixture layer formed from an aqueous positive electrode composition for a lithium ion secondary battery on a positive electrode current collector.
  • the positive electrode can be produced, for example, by applying an aqueous positive electrode composition for a lithium ion secondary battery to a positive electrode current collector and drying to form an electrode mixture layer.
  • the positive electrode may be subjected to pressure treatment using, for example, a die press, a roll press, or the like, if necessary.
  • Examples of the metal used for the positive electrode current collector include iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, and platinum. Among these, aluminum is preferable.
  • the shape and dimensions of the positive electrode current collector are not particularly limited.
  • the negative electrode for a lithium ion secondary battery has a negative electrode mixture layer formed from an aqueous negative electrode composition for a lithium ion secondary battery on a negative electrode current collector.
  • the negative electrode can be produced, for example, by applying an aqueous negative electrode composition for a lithium ion secondary battery to a negative electrode current collector and drying to form an electrode mixture layer.
  • the negative electrode may be subjected to pressure treatment using a die press, a roll press, or the like, if necessary.
  • the metal used for the negative electrode current collector include iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, and platinum. Among these, copper is preferable.
  • the shape and dimensions of the negative electrode current collector are not particularly limited.
  • a film made of a polyolefin resin such as polyethylene or polypropylene, or a resin such as a fluororesin can be used.
  • an electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent can be used.
  • a lithium salt is used as the supporting electrolyte.
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (FSO 2 ) 2 NLi, (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) 2 NLi, and the like, but the present invention is not limited to such examples.
  • organic solvent examples include carbonates such as dimethyl carbonate, ethylene carbonate, diethyl carbonate, propylene carbonate, butylene carbonate, and methyl ethyl carbonate, esters such as ⁇ -butyrolactone and methyl formate, 1,2-dimethoxyethane, and tetrahydrofuran. Although ether etc. are mentioned, this invention is not limited only to this illustration.
  • a lithium ion secondary battery is easily manufactured by, for example, stacking a positive electrode and a negative electrode through a separator, putting the obtained laminate into a battery container, injecting an electrolyte into the battery container, and sealing the battery container.
  • the battery container may contain an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like to prevent an increase in pressure inside the battery or overcharge / discharge.
  • the shape of the battery include a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, and a flat shape. However, the present invention is not limited to such examples.
  • the electric capacity maintenance rate after 50 cycles of charging / discharging the secondary battery 50 times is preferably 85% or more, more preferably 95% or more.
  • a single solution comprising 366.3 parts by mass of an aqueous 2.7% polyoxyethylene polycyclic phenyl ether sulfate salt salt, 705 parts by mass of methyl acrylate, 250 parts by mass of butyl acrylate, 20 parts by mass of acrylic acid and 25 parts by mass of N-methylol acrylamide.
  • a pre-emulsion was prepared by mixing the monomer components so as to have a uniform composition.
  • Resin emulsion A was obtained.
  • the pH of the resin emulsion at 25 ° C. was measured using a glass electrode type hydrogen ion thermometer [manufactured by Horiba, Ltd., product number: F-21].
  • the viscosity of Resin Emulsion A was 2310 mPa ⁇ s when measured using a viscometer (manufactured by Toki Sangyo Co., Ltd., product number: TVB-10) at a temperature of 25 ⁇ 1 ° C. and 30 rpm. .
  • the glass transition temperature of the acrylic polymer constituting the resin particles (emulsion particles) contained in the obtained resin emulsion A was ⁇ 10 ° C.
  • % Resin emulsion B was obtained.
  • the pH of the resin emulsion at 25 ° C. was measured using a glass electrode type hydrogen ion thermometer [manufactured by Horiba, Ltd., product number: F-21].
  • the glass transition temperature of the acrylic polymer polymer which comprises the resin particle (emulsion particle) contained in the obtained resin emulsion B was 15 degreeC.
  • Resin emulsion C was obtained.
  • the pH of the resin emulsion at 25 ° C. was measured using a glass electrode type hydrogen ion thermometer [manufactured by Horiba, Ltd., product number: F-21].
  • the glass transition temperature of the acrylic polymer constituting the resin particles (emulsion particles) contained in the obtained resin emulsion C was ⁇ 35 ° C.
  • a single amount comprising 366.3 parts by mass of an aqueous 2.7% polyoxyethylene polycyclic phenyl ether sulfate salt salt, 855 parts by mass of ethyl acrylate, 100 parts by mass of acrylonitrile, 20 parts by mass of acrylic acid and 25 parts by mass of N-methylolacrylamide.
  • a pre-emulsion was prepared by mixing the body components with a uniform composition.
  • % Resin emulsion D was obtained.
  • the pH of the resin emulsion at 25 ° C. was measured using a glass electrode type hydrogen ion thermometer [manufactured by Horiba, Ltd., product number: F-21].
  • the glass transition temperature of the acrylic polymer constituting the resin particles (emulsion particles) contained in the obtained resin emulsion D was ⁇ 12 ° C.
  • % Resin emulsion E was obtained.
  • the pH of the resin emulsion at 25 ° C. was measured using a glass electrode type hydrogen ion thermometer [manufactured by Horiba, Ltd., product number: F-21].
  • the glass transition temperature of the acrylic polymer constituting the resin particles (emulsion particles) contained in the obtained resin emulsion E was ⁇ 10 ° C.
  • a monomer comprising 366.3 parts by mass of an aqueous 2.7% polyoxyethylene polycyclic phenyl ether sulfate salt salt, 250 parts by mass of butyl acrylate, 705 parts by mass of methyl acrylate, 20 parts by mass of acrylic acid and 25 parts by mass of glycidyl methacrylate.
  • a pre-emulsion was prepared by mixing the components so as to have a uniform composition.
  • Resin emulsion F was obtained.
  • the pH of the resin emulsion at 25 ° C. was measured using a glass electrode type hydrogen ion thermometer [manufactured by Horiba, Ltd., product number: F-21]. Further, the glass transition temperature of the acrylic polymer constituting the resin particles (emulsion particles) contained in the obtained resin emulsion F was ⁇ 10 ° C.
  • Comparative production example 1 A resin emulsion G having a nonvolatile content of 40% by mass was obtained in the same manner as in Production Example 1 except that N-methylolacrylamide was not used in Production Example 1.
  • the glass transition temperature of the acrylic polymer constituting the resin particles (emulsion particles) contained in the obtained resin emulsion G was ⁇ 10 ° C.
  • Comparative production example 2 In a four-necked separable flask equipped with a stirrer, a thermometer, a cooler, a nitrogen gas inlet tube and a dropping funnel, 494.5 parts by mass of ion-exchanged water was charged. While maintaining the internal temperature of the flask at 75 ° C., nitrogen gas was gently allowed to flow into the flask under stirring to completely replace the inside of the flask with nitrogen gas.
  • Resin emulsion H was obtained.
  • the pH of the resin emulsion at 25 ° C. was measured using a glass electrode type hydrogen ion thermometer [manufactured by Horiba, Ltd., product number: F-21].
  • the glass transition temperature of the acrylic polymer constituting the resin particles (emulsion particles) contained in the obtained resin emulsion H was ⁇ 10 ° C.
  • the nonvolatile content in the resin emulsion was measured based on the following method.
  • Example 1 A uniform composition of 75 parts by mass of an aqueous solution of 2% by mass carboxymethylcellulose [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Serogen BSH-6] and 7 parts by mass of acetylene black powder [manufactured by Denki Kagaku Kogyo Co., Ltd.] The mixture was obtained by mixing.
  • the peel strength of the sample was measured based on the following method using the aqueous positive electrode composition for a lithium ion secondary battery obtained above, the peel strength was 42 N / m.
  • An aqueous positive electrode composition for a lithium ion secondary battery is applied to an aluminum foil as a current collector with an applicator, dried at 80 ° C. for 10 minutes, and then pressed with a roll press machine at a linear pressure of 5 kN. Was made.
  • the positive electrode obtained above was dried under reduced pressure in an atmosphere at 80 ° C. to obtain a sample having a density of 15 mg / cm 2 .
  • the sample obtained above was cut into a width of 25 mm and a length of 100 mm, attached to an aluminum plate, and peeled in a peeling direction of 90 ° using a tensile tester (manufactured by Tester Sangyo Co., Ltd.) in an atmosphere of 23 ° C. The peel strength at a speed of 20 mm / min was measured.
  • Example 2 In Example 1, a sample was prepared in the same manner as in Example 1 except that the resin emulsion B was used instead of the resin emulsion A, and the peel strength was examined. As a result, the peel strength of the sample obtained above was 31 N / m.
  • the positive electrode obtained as described above was examined based on the test method for flexibility, the positive electrode was slightly cracked to the extent that there was no problem in use.
  • Example 3 In Example 1, a sample was prepared in the same manner as in Example 1 except that the resin emulsion C was used instead of the resin emulsion A, and the peel strength was examined. As a result, the peel strength of the sample obtained above was 30 N / m.
  • Example 4 In Example 1, a sample was prepared in the same manner as in Example 1 except that the resin emulsion D was used instead of the resin emulsion A, and the peel strength was examined. As a result, the peel strength of the sample obtained above was 33 N / m.
  • Example 5 In Example 1, a sample was prepared in the same manner as in Example 1 except that the resin emulsion E was used instead of the resin emulsion A, and the peel strength was examined. As a result, the peel strength of the sample obtained above was 39 N / m.
  • Example 6 In Example 1, a sample was prepared in the same manner as in Example 1 except that the resin emulsion F was used instead of the resin emulsion A, and the peel strength was examined. As a result, the peel strength of the sample obtained above was 34 N / m.
  • Example 1 a sample was prepared in the same manner as in Example 1 except that the resin emulsion G was used instead of the resin emulsion A, and the peel strength was examined. As a result, the peel strength of the sample obtained above was 22 N / m, and the peel strength was low.
  • Example 2 a sample was prepared in the same manner as in Example 1 except that the resin emulsion H was used instead of the resin emulsion A, and the peel strength was examined. As a result, the peel strength of the sample obtained above was 22 N / m, and the peel strength was low.
  • the active materials are excellent in binding property between active materials and the active material and current collector, and suitable for an electrode of a lithium ion secondary battery. It turns out that the binder for electrodes of the lithium ion secondary battery which can be used is obtained. It can also be seen that the electrode binders obtained in each Example, especially the electrode binders obtained in Example 1 and Examples 3 to 6, form an electrode having excellent flexibility.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un liant pour électrode d'élément accumulateur au lithium-ion, le liant contenant des particules de résine qui renferment un polymère d'acrylate obtenu par polymérisation d'un monomère polyfonctionnel et d'un composant monomère contenant un acrylate d'alkyle doté de groupes alkyle en C1 à C3 ; une composition aqueuse pour électrode d'élément accumulateur au lithium-ion, la composition contenant le liant ; une électrode pour élément accumulateur au lithium-ion, l'électrode étant formée à partir de la composition aqueuse pour électrode d'élément accumulateur au lithium-ion ; et un élément accumulateur au lithium-ion contenant l'électrode.
PCT/JP2016/060586 2015-03-31 2016-03-30 Liant pour électrode d'élément accumulateur au lithium-ion Ceased WO2016159198A1 (fr)

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KR20180109740A (ko) 2017-03-28 2018-10-08 아라까와 가가꾸 고교 가부시끼가이샤 열가교형 리튬이온 전지용 슬러리 및 그 제조방법, 리튬이온 전지용 전극, 리튬이온 전지용 세퍼레이터, 리튬이온 전지용 세퍼레이터/전극적층체, 및 리튬이온 전지
JP2018181487A (ja) * 2017-04-06 2018-11-15 東洋インキＳｃホールディングス株式会社 水系電極用塗工液およびその利用
CN116864691A (zh) * 2023-08-12 2023-10-10 福建蓝海黑石新材料科技有限公司 一种二次电池的水性粘合剂及其制备方法
WO2025074556A1 (fr) * 2023-10-05 2025-04-10 株式会社レゾナック Liant pour électrode de batterie secondaire non aqueuse, composition de liant pour électrode de batterie secondaire non aqueuse, suspension pour électrode de batterie secondaire non aqueuse, électrode de batterie secondaire non aqueuse et batterie secondaire non aqueuse

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JP2015018776A (ja) * 2013-07-12 2015-01-29 株式会社日本触媒 電池用水系電極組成物用バインダー

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JP2002260665A (ja) * 2001-02-28 2002-09-13 Asahi Kasei Corp 非水電解液二次電池
JP2006278303A (ja) * 2005-03-25 2006-10-12 Nippon Zeon Co Ltd 非水電解質二次電池電極用バインダー、バインダー組成物、電極用組成物、ならびに電極
WO2008120786A1 (fr) * 2007-03-30 2008-10-09 Zeon Corporation Liant pour une électrode de batterie secondaire, électrode de batterie secondaire, et batterie secondaire
JP2015018776A (ja) * 2013-07-12 2015-01-29 株式会社日本触媒 電池用水系電極組成物用バインダー

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180109740A (ko) 2017-03-28 2018-10-08 아라까와 가가꾸 고교 가부시끼가이샤 열가교형 리튬이온 전지용 슬러리 및 그 제조방법, 리튬이온 전지용 전극, 리튬이온 전지용 세퍼레이터, 리튬이온 전지용 세퍼레이터/전극적층체, 및 리튬이온 전지
JP2018181487A (ja) * 2017-04-06 2018-11-15 東洋インキＳｃホールディングス株式会社 水系電極用塗工液およびその利用
CN116864691A (zh) * 2023-08-12 2023-10-10 福建蓝海黑石新材料科技有限公司 一种二次电池的水性粘合剂及其制备方法
WO2025074556A1 (fr) * 2023-10-05 2025-04-10 株式会社レゾナック Liant pour électrode de batterie secondaire non aqueuse, composition de liant pour électrode de batterie secondaire non aqueuse, suspension pour électrode de batterie secondaire non aqueuse, électrode de batterie secondaire non aqueuse et batterie secondaire non aqueuse

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