WO2023210558A1 - Composition pour la formation d'un film mince destiné à une électrode de dispositif de stockage d'énergie - Google Patents

Composition pour la formation d'un film mince destiné à une électrode de dispositif de stockage d'énergie Download PDF

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WO2023210558A1
WO2023210558A1 PCT/JP2023/016043 JP2023016043W WO2023210558A1 WO 2023210558 A1 WO2023210558 A1 WO 2023210558A1 JP 2023016043 W JP2023016043 W JP 2023016043W WO 2023210558 A1 WO2023210558 A1 WO 2023210558A1
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energy storage
group
storage device
electrode
thin film
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PCT/JP2023/016043
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English (en)
Japanese (ja)
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宅磨 長▲濱▼
博史 太田
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日産化学株式会社
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    • 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
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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 thin film forming composition for energy storage device electrodes.
  • a lithium ion secondary battery houses a positive electrode and a negative electrode that can absorb and release lithium, and a separator interposed between them in a container, and contains an electrolyte (in the case of a lithium ion polymer secondary battery, a liquid). It has a structure filled with gel-like electrolyte (instead of electrolyte).
  • the positive and negative electrodes are generally made by coating a composition containing an active material that can absorb and release lithium, a conductive material mainly made of carbon material, and a polymer binder on a current collecting substrate such as copper foil or aluminum foil. It is manufactured by This binder is used to bond active materials and conductive materials, as well as these and metal foils, and is made of fluorine-based resins soluble in N-methylpyrrolidone (NMP) such as polyvinylidene fluoride (PVdF), and olefin-based polymers. Aqueous dispersions of the combination are commercially available.
  • NMP N-methylpyrrolidone
  • PVdF polyvinylidene fluoride
  • Aqueous dispersions of the combination are commercially available.
  • the adhesive strength of the above-mentioned binder to the current collector substrate is not sufficient, and some of the active material and conductive material may peel off or fall off from the current collector substrate during manufacturing processes such as cutting and winding the electrode. , causing micro short circuits and variations in battery capacity.
  • the contact resistance between the electrode mixture and the current collecting substrate increases due to volume changes in the electrode mixture due to swelling of the binder due to the electrolyte and changes in volume due to lithium absorption and release from the active material.
  • Patent Document 1 discloses a technique in which a conductive layer containing carbon as a conductive filler is disposed as an undercoat layer between a current collector substrate and an electrode mixture layer.
  • a composite current collector with an undercoat layer it is possible to reduce the contact resistance between the current collecting substrate and the electrode composite layer, and also suppress capacity loss during high-speed discharge, which also prevents battery deterioration. It has been shown that it can be suppressed.
  • Patent Document 4 and Patent Document 5 disclose an undercoat layer using carbon nanotubes as a conductive filler.
  • the undercoat layer disclosed in each of these patent documents is a wet method in which a slurry-like composition for forming an electrode composite layer is applied onto the undercoat layer and dried to form an electrode composite layer.
  • the composition for forming an electrode composite layer is once formed into a sheet shape, and this is laminated on an undercoat layer by heat compression bonding, etc., or on the electrode composite layer formed on a base material.
  • Dry methods such as methods that involve transferring an electrode composite layer by forming an undercoat layer on the surface, laminating a current collector substrate on top of the current collector substrate, and then peeling off the base material, may lack adhesion or make transfer difficult. There are problems such as.
  • the present invention has been made in view of the above circumstances, and it is possible to transfer the electrode composite material layer, and the present invention provides an energy source that provides a primer layer that has both practical adhesion and excellent adhesion retention after transfer.
  • An object of the present invention is to provide a thin film forming composition for storage device electrodes.
  • a conductive carbon material a polymer having an oxazoline group in the side chain, a hydroxyl group-containing polymer having a weight average molecular weight within a specific range, and a solvent. It has been discovered that a composition containing the above is capable of transferring an electrode mixture layer and provides a thin film (primer layer) that has both practical adhesion and excellent adhesion retention after transfer, and has achieved the present invention. completed.
  • the present invention provides an energy storage device electrode.
  • a thin film forming composition for an energy storage device electrode comprising a conductive carbon material, a polymer having an oxazoline group in a side chain, a hydroxyl group-containing polymer having a weight average molecular weight of 50,000 to 5,000,000, and a solvent.
  • 2. 1. The thin film forming composition for an energy storage device electrode according to 1, wherein the mass proportion of hydroxyl groups in the molecule of the hydroxyl group-containing polymer is 1 ⁇ 10 ⁇ 5 to 100 ⁇ 10 ⁇ 5 . 3.
  • the thin film forming composition for an energy storage device electrode according to 2 wherein the mass proportion of hydroxyl groups in the molecule of the hydroxyl group-containing polymer is 1 ⁇ 10 ⁇ 5 to 50 ⁇ 10 ⁇ 5 . 4.
  • the polymer having an oxazoline group in the side chain comprises an oxazoline monomer represented by formula (1) having a polymerizable carbon-carbon double bond-containing group at the 2-position, and a (meth)acrylic monomer having a hydrophilic functional group.
  • the thin film forming composition for an electrode of an energy storage device according to any one of 1 to 3, which is a polymer obtained by radically polymerizing.
  • X represents a chain hydrocarbon group containing a polymerizable carbon-carbon double bond; represents an alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, which may have the following structure.
  • the conductive carbon material is one or more selected from acetylene black, carbon black, Ketjen black, furnace black, channel black, and lamp black. Composition. 10.
  • R a and R b are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon atom which may have a substituent
  • X a is N or CH.
  • Thin film forming composition for an energy storage device electrode wherein the substituent is at least one selected from the group consisting of a carboxy group, a hydroxy group, a thiol group, an amino group, a sulfonic acid group, and an epoxy group. 12. 10. A thin film forming composition for an energy storage device electrode, wherein the heterocyclic compound is represented by the following formula (n2). (In the formula, Y a represents a hydrogen atom, a carboxy group, a hydroxy group, a thiol group, an amino group, a sulfonic acid group, or an epoxy group. X a is the same as above.) 13.
  • compositions for energy storage device electrodes wherein the heterocyclic compound is represented by the following formula (n3).
  • a primer layer consisting of a thin film obtained from the composition for forming a thin film for an electrode of an energy storage device according to any one of 1 to 3.
  • a composite current collector for an electrode of an energy storage device comprising a current collecting substrate and fourteen primer layers formed on the current collecting substrate. 16.
  • a composite current collector for an electrode of an energy storage device wherein the current collecting substrate is a copper foil or an aluminum foil.
  • An electrode for an energy storage device comprising a composite current collector for an electrode of an energy storage device of 16. 18.
  • An energy storage device comprising 17 energy storage device electrodes. 20.
  • the composition for forming a thin film for an electrode of an energy storage device of the present invention allows transfer of an electrode mixture layer and provides a primer layer having both practical adhesion and excellent adhesion retention. Therefore, by using the composition for forming a thin film for energy storage device electrodes of the present invention, it becomes possible to apply a dry process for transferring the electrode composite layer composition or electrode composite layer sheet adhered to the base material. In addition, an electrode including an electrode composite material layer with excellent thickness accuracy can be produced.
  • composition for energy storage device electrodes of the present invention
  • composition comprises a conductive carbon material, a polymer having an oxazoline group in its side chain, a hydroxyl group-containing polymer, and a solvent. It is characterized by including.
  • Conductive carbon material Specific examples of the conductive carbon material used in the composition of the present invention include acetylene black, carbon black, Ketjen black, furnace black, channel black, lamp black, carbon nanotubes, carbon whiskers, It is possible to appropriately select and use known conductive carbon materials such as carbon fiber, natural graphite, and artificial graphite, but from the viewpoint of conductivity, dispersibility, adhesion, transferability, etc., acetylene black, carbon black, etc. , Ketjen black, furnace black, channel black, and lamp black are preferred, acetylene black, carbon black, and Ketjen black are more preferred, and acetylene black is even more preferred.
  • the said electroconductive carbon material may be used individually, or may use 2 or more types together.
  • Commercially available conductive carbon materials can be used, and specific examples include Denka Black (Li-100, Li-250, Li-400, Li-435, etc.), which is acetylene black manufactured by Denka Corporation. , NH Carbon manufactured by Nippon Chemi-Con Co., Ltd., and the like.
  • polymer having an oxazoline group in its side chain acts as a dispersant and a binder polymer for the conductive carbon material. It is.
  • This polymer is not particularly limited as long as it is a polymer in which an oxazoline group is bonded directly to the repeating unit constituting the main chain or via a spacer group such as an alkylene group.
  • X represents a polymerizable carbon-carbon double bond-containing group
  • R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, or a branched structure having 1 to 5 carbon atoms.
  • the polymerizable carbon-carbon double bond-containing group possessed by the oxazoline monomer is not particularly limited as long as it contains a polymerizable carbon-carbon double bond;
  • a hydrocarbon group such as a vinyl group, an allyl group, an isopropenyl group, or an alkenyl group having 2 to 8 carbon atoms is preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • alkyl group which may have a branched structure having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group. group, n-pentyl group, etc.
  • aryl group having 6 to 20 carbon atoms include phenyl group, xylyl group, tolyl group, biphenyl group, and naphthyl group.
  • aralkyl group having 7 to 20 carbon atoms include benzyl group, phenylethyl group, phenylcyclohexyl group, and the like.
  • oxazoline monomer having a polymerizable carbon-carbon double bond-containing group at the 2-position represented by formula (1) include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-4-propyl-2-oxazoline, 2-vinyl-4-butyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2- Vinyl-5-ethyl-2-oxazoline, 2-vinyl-5-propyl-2-oxazoline, 2-vinyl-5-butyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4- Methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-4-propyl-2-oxazoline, 2-isopropenyl-4-butyl
  • the oxazoline polymer is water-soluble.
  • a water-soluble oxazoline polymer may be a homopolymer of the oxazoline monomer represented by the above formula (1), but in order to further increase the solubility in water, it may be a homopolymer of the oxazoline monomer and the above oxazoline monomer having a hydrophilic functional group (meth). ) It is preferably obtained by radical polymerizing at least two types of monomers with an acrylic acid ester monomer.
  • (meth)acrylic monomers having hydrophilic functional groups include (meth)acrylic acid, 2-hydroxyethyl acrylate, methoxypolyethylene glycol acrylate, monoesters of acrylic acid and polyethylene glycol, and acrylic acid.
  • oxazoline monomer and (meth)acrylic monomer having a hydrophilic functional group are used in combination within a range that does not adversely affect the conductive carbon material dispersion ability of the obtained oxazoline polymer. be able to.
  • specific examples of other monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, and (meth)acrylate.
  • (meth)acrylic acid ester monomers such as perfluoroethyl acid and phenyl (meth)acrylate; ⁇ -olefin monomers such as ethylene, propylene, butene, and pentene; haloolefins such as vinyl chloride, vinylidene chloride, and vinyl fluoride Monomers: Styrenic monomers such as styrene and ⁇ -methylstyrene; Carboxylic acid vinyl ester monomers such as vinyl acetate and vinyl propionate; Vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether; each of these may be used alone. However, two or more types may be used in combination.
  • the content of the polymer having an oxazoline group in the side chain in the composition of the present invention is not particularly limited as long as it can disperse the conductive carbon material, but it can sufficiently disperse the conductive carbon material and function as a binder. In consideration of exhibiting this, the content is preferably 20 to 60 parts by weight, more preferably 30 to 60 parts by weight, and even more preferably 40 to 60 parts by weight, based on 100 parts by weight of the conductive carbon material.
  • the hydroxyl group-containing polymer has a mass proportion of hydroxyl groups in the molecule of the hydroxyl group-containing polymer of 1 ⁇ 10 ⁇ 5 to 100 ⁇ 10 -5 is preferable, and 1 ⁇ 10 ⁇ 5 to 50 ⁇ 10 ⁇ 5 is more preferable.
  • the weight average molecular weight of the hydroxyl group-containing polymer is 50,000 to 5,000,000, preferably 50,000 to 2,500,000, and more preferably 100,000 to 1,000,000.
  • Polyalkylene glycols and/or polyvinyl alcohols are used. Note that polyalkylene glycol in the present invention also includes polyalkylene oxide.
  • the weight average molecular weight is a polystyrene equivalent value determined by gel permeation chromatography.
  • the lower limit of the melting point of the hydroxyl group-containing polymer is preferably 25°C or higher, and the upper limit is preferably 100°C or lower, more preferably 70°C or lower.
  • polyalkylene glycol examples include polyethylene glycol (polyethylene oxide), polypropylene glycol (polypropylene oxide), polytetramethylene ether glycol, and the like.
  • the hydroxyl group-containing polymer may be a copolymer containing multiple types of repeating units, such as a copolymer of alkylene oxide and allyl glycidyl ether.
  • copolymers include copolymers of ethylene oxide and allyl glycidyl ether, copolymers of propylene oxide and allyl glycidyl ether, copolymers of ethylene oxide, propylene oxide, and allyl glycidyl ether, and the like.
  • the above copolymer may be a random copolymer, a block copolymer, or a graft copolymer, but a random copolymer is preferable.
  • hydroxyl group-containing polymer such as Alcox E-240, E-160, E-100, E-75, E-60, E-45, and E- manufactured by Meisei Chemical Industry Co., Ltd. 30, R-1000, R-400, R-150 (PEG), Alcox CP-A1H, CP-A2H (random copolymer of ethylene oxide, propylene oxide, allyl glycidyl ether), etc.; Fujifilm Wako Pure Chemical ( Polyethylene glycol 2,000, 3,000, 4,000, 6,000, 8,000, 10,000, 12,000, 20,000, 500,000, etc. manufactured by Nippon Ace Vine & Poval Co., Ltd.
  • the content of the hydroxyl group-containing polymer in the composition of the present invention is preferably 10 to 200 parts by mass based on 100 parts by mass of the conductive carbon material, and in consideration of further increasing the adhesion of the primer layer, the content is 30 to 150 parts by mass. Parts by weight are more preferable, and 40 to 120 parts by weight are even more preferable.
  • the present invention in addition to the adhesion between the current collecting substrate and the primer layer, in order to improve the scratch resistance of the primer layer, it is preferable to further include a nitrogen-containing heterocyclic compound containing two or more nitrogen atoms.
  • the nitrogen-containing heterocyclic compound is not particularly limited as long as it contains two or more nitrogen atoms constituting a ring, and can be appropriately selected from conventionally known compounds, but in the present invention , imidazole derivatives, pyrazole derivatives and triazole derivatives are preferred, imidazole derivatives and triazole derivatives are more preferred, and triazole derivatives are even more preferred. Specific examples of these that can be used are listed below.
  • imidazole derivatives include imidazole, benzimidazole, 5-carboxybenzimidazole, 4-carboxybenzimidazole, and the like.
  • pyrazole derivatives include pyrazole, 1,2-benzopyrazole, 4-pyrazolecarboxylic acid, 3-pyrazolecarboxylic acid, adenine, and the like.
  • benzotriazole compounds are preferred, and specific examples thereof include benzotriazole, carboxybenzotriazole, 5-carboxybenzotriazole, 4-carboxybenzotriazole, 5-hydroxybenzotriazole, 5-aminobenzotriazole, and benzotriazole.
  • Triazole-4-sulfonic acid 4-methylbenzotriazole, 5-methyl-1H-benzotriazole, 1-carboxybenzotriazole, 1-hydroxybenzotriazole, 1-aminobenzotriazole, 4-methylbenzotriazole, 5-methyl- 1H-benzotriazole, benzotriazole-1-methylamine, 4-methylbenzotriazole-1-methylamine, 5-methylbenzotriazole-1-methylamine, N-methylbenzotriazole-1-methylamine, N-ethylbenzo Triazole-1-methylamine, N,N-dimethylbenzotriazole-1-methylamine, N,N-diethylbenzotriazole-1-methylamine, N,N-dipropylbenzotriazole-1-methylamine, N,N -dibutylbenzotriazole-1-methylamine, N,N-dihexylbenzotriazole-1-methylamine, N,N-dioctylbenzotriazole-1-methylamine
  • R a and R b each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a carbon number 2 to 6 which may have a substituent.
  • X a is N or CH.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • the alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Straight or branched alkyl groups having 1 to 6 carbon atoms such as isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group Examples include cyclic alkyl groups having 3 to 6 carbon atoms such as groups.
  • alkenyl groups having 2 to 6 carbon atoms include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl -1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl and the like.
  • aryl group having 6 to 12 carbon atoms examples include phenyl, tolyl, 1-naphthyl, 2-naphthyl, and the like.
  • substituents examples include carboxy groups, hydroxy groups, thiol groups, amino groups, sulfonic acid groups, and epoxy groups.
  • Examples of the ring having 4 to 6 carbon atoms formed by bonding R a and R b to each other include a cyclopentane ring, a cyclohexane ring, and a benzene ring.
  • the above X a is preferably N.
  • n2 a compound represented by the following formula (n2) in which R a and R b combine with each other to form a benzene ring.
  • the above Y a represents a hydrogen atom, a carboxyl group, a hydroxy group, a thiol group, an amino group, a sulfonic acid group, or an epoxy group, which ensures the migration suppressing effect and the adhesion between the current collector and the undercoat layer. From the viewpoint of improving performance, carboxy groups, hydroxy groups, thiol groups, amino groups, sulfonic acid groups and epoxy groups are preferred, and carboxy groups are more preferred.
  • the above X a is the same as the above (n1), but N is preferable.
  • heterocyclic compound represented by the above formula (n2) include those represented by the following formula (n3).
  • heterocyclic compound represented by the above formula (n3) include carboxybenzotriazole, 5-carboxybenzotriazole, and 4-carboxybenzotriazole, with carboxybenzotriazole and 5-carboxybenzotriazole being preferred.
  • its content is preferably 0.05 to 200 parts by mass, more preferably 0.1 to 150 parts by mass, and even more preferably The amount is 5 to 130 parts by weight, more preferably 10 to 110 parts by weight, and most preferably 10 to 100 parts by weight.
  • the above nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.
  • Hydrophilic solvents are organic solvents that mix arbitrarily with water, such as ethers such as tetrahydrofuran (THF); N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl Amides such as -2-pyrrolidone (NMP); Ketones such as acetone; Alcohols such as methanol, ethanol, n-propanol, 2-propanol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc. glycol ethers; organic solvents such as glycols such as ethylene glycol and propylene glycol; These solvents may be used alone or in combination of two or more.
  • ethers such as tetrahydrofuran (THF); N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl Amides such as -2-pyrroli
  • the solvent contains water, and it is more preferable that the solvent contains 70% by mass or more of water (30% by mass or less of organic solvent).
  • the method for preparing the composition of the present invention is not particularly limited, and the conductive carbon material, the polymer having an oxazoline group in the side chain, the hydroxyl group-containing polymer, and the solvent are prepared in any order.
  • the first liquid can be prepared by mixing a conductive carbon material, a polymer having an oxazoline group in a side chain, and a solvent
  • the second liquid is prepared by mixing a hydroxyl group-containing polymer and a solvent.
  • a method of mixing with a liquid is suitable.
  • dispersion processing examples include mechanical processing, such as wet processing using a ball mill, bead mill, jet mill, etc., and ultrasonic processing using a bath-type or probe-type sonicator, but in particular, wet processing using a jet mill. or ultrasonic treatment are suitable.
  • the time for the dispersion treatment is arbitrary, but is preferably about 1 minute to 10 hours, more preferably about 5 minutes to 5 hours. Note that heat treatment or cooling treatment may be performed as necessary.
  • the solid content concentration of the composition is not particularly limited, but in consideration of forming a primer layer with a desired basis weight and film thickness, it is preferably 20% by mass or less, and 15% by mass or less. is more preferable, 10% by mass or less is even more preferable, and even more preferably 5% by weight or less. Further, the lower limit is arbitrary, but from a practical standpoint, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. Note that the solid content refers to components other than the solvent that constitute the composition.
  • Primer layer and energy storage device electrode The composition described above is applied to at least one surface of the current collector or the surface of the electrode mixture layer, and the resulting thin film is dried naturally or by heating. can be suitably used as a primer layer of an energy storage device electrode.
  • energy storage devices include various energy storage devices such as electric double layer capacitors, lithium secondary batteries, lithium ion secondary batteries, proton polymer batteries, nickel metal hydride batteries, aluminum solid capacitors, electrolytic capacitors, and lead acid batteries.
  • the composition of the present invention can be particularly suitably used in electric double layer capacitors and lithium ion secondary batteries.
  • the current collector those conventionally used as current collectors for electrodes for energy storage devices can be used.
  • copper, aluminum, titanium, stainless steel, nickel, gold, silver, and alloys thereof, carbon materials, metal oxides, conductive polymers, etc. can be used;
  • the metal foil is preferred.
  • the thickness of the current collector is not particularly limited, but in the present invention, it is preferably 1 to 100 ⁇ m.
  • the electrode composite layer is formed by applying an electrode slurry (composition for forming an electrode composite layer) prepared by combining an active material, a binder polymer, and a solvent as necessary onto a base material, and drying it naturally or by heating. can.
  • an electrode slurry composition for forming an electrode composite layer
  • the active material various active materials conventionally used in electrodes for energy storage devices can be used.
  • chalcogen compounds capable of adsorbing and desorbing lithium ions, chalcogen compounds containing lithium ions, polyanionic compounds, elemental sulfur, and compounds thereof can be used as positive electrode active materials. can.
  • Examples of chalcogen compounds capable of adsorbing and desorbing lithium ions include FeS 2 , TiS 2 , MoS 2 , V 2 O 6 , V 6 O 13 , MnO 2 and the like.
  • Examples of lithium ion-containing chalcogen compounds include LiCoO 2 , LiMnO 2 , LiMn 2 O 4 , LiMo 2 O 4 , LiV 3 O 8 , LiNiO 2 , Li x Ni y M 1-y O 2 (where M is Represents at least one metal element selected from Co, Mn, Ti, Cr, V, Al, Sn, Pb, and Zn, 0.05 ⁇ x ⁇ 1.10, 0.5 ⁇ y ⁇ 1.0 ) etc.
  • Examples of the polyanionic compound include LiFePO 4 and the like.
  • Examples of the sulfur compound include Li 2 S and rubeanic acid.
  • the negative electrode active material constituting the negative electrode at least one element, oxide, sulfide, or nitride selected from alkali metals, alkali alloys, and elements of groups 4 to 15 of the periodic table that occlude and release lithium ions is used.
  • a carbon material that can reversibly absorb and release lithium ions can be used.
  • Examples of the alkali metal include Li, Na, and K, and examples of the alkali metal alloy include Li-Al, Li-Mg, Li-Al-Ni, Na-Hg, and Na-Zn.
  • Examples of the simple substance of at least one element selected from the elements of groups 4 to 15 of the periodic table that absorb and release lithium ions include silicon, tin, aluminum, zinc, arsenic, and the like.
  • oxides include silicon monoxide (SiO), silicon dioxide (SiO 2 ), tin silicon oxide (SnSiO 3 ), lithium bismuth oxide (Li 3 BiO 4 ), lithium zinc oxide (Li 2 ZnO 2 ), and lithium.
  • Examples include titanium oxide (Li 4 Ti 5 O 12 ) and titanium oxide.
  • examples of the sulfide include lithium iron sulfide (Li x FeS 2 (0 ⁇ x ⁇ 3)), lithium copper sulfide (Li x CuS (0 ⁇ x ⁇ 3)), and the like.
  • Examples of carbon materials capable of reversibly occluding and releasing lithium ions include graphite, carbon black, coke, glassy carbon, carbon fibers, carbon nanotubes, and sintered bodies thereof.
  • a carbonaceous material can be used as the active material.
  • this carbonaceous material include activated carbon, and for example, activated carbon obtained by carbonizing a phenol resin and then performing an activation treatment.
  • the binder polymer can be appropriately selected from known materials, such as polyvinylidene fluoride (PVdF), polyvinylpyrrolidone, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, and vinylidene fluoride.
  • PVdF polyvinylidene fluoride
  • polyvinylpyrrolidone polyvinylpyrrolidone
  • polytetrafluoroethylene polytetrafluoroethylene-hexafluoropropylene copolymer
  • vinylidene fluoride vinylidene fluoride
  • Hexafluoropropylene copolymer [P(VDF-HFP)], vinylidene fluoride-trifluoroethylene chloride copolymer [P(VDF-CTFE)], polyvinyl alcohol, polyimide, ethylene-propylene-diene ternary copolymer
  • examples include rubber, styrene-butadiene rubber, carboxymethylcellulose (CMC), polyacrylic acid (PAA), ammonium polyacrylate, polyaniline, polyimide, and polyamide.
  • the amount of the binder polymer added is preferably 0.1 to 40 parts by weight, particularly 1 to 30 parts by weight, based on 100 parts by weight of the active material.
  • the solvent examples include the solvents exemplified as solvents for the composition, and may be appropriately selected from among them depending on the type of binder. However, in the case of a water-insoluble binder such as PVdF, NMP is preferable. In the case of a water-soluble binder such as PAA, water is suitable.
  • the electrode slurry may contain a conductive material.
  • the conductive material include carbon black, Ketjenblack, acetylene black, carbon whiskers, carbon fibers, natural graphite, artificial graphite, titanium oxide, ruthenium oxide, aluminum, and nickel.
  • Examples of methods for applying the electrode slurry include spin coating, dip coating, flow coating, inkjet, casting, spray coating, bar coating, gravure coating, slit coating, roll coating, and flexographic printing.
  • method transfer printing method, brush coating method, blade coating method, air knife coating method, die coating method, etc.; however, from the point of view of work efficiency, inkjet method, casting method, dip coating method, bar coating method, blade coating method, etc. , a roll coating method, a gravure coating method, a flexographic printing method, a spray coating method, and a die coating method are suitable.
  • the temperature for heating and drying is also arbitrary, but is preferably about 50 to 400°C, more preferably about 80 to 150°C.
  • the temperature for heating and drying is also arbitrary, but is preferably about 50 to 200°C, more preferably about 80 to 150°C.
  • the thickness of the primer layer is preferably 1 nm to 10 ⁇ m, more preferably 1 nm to 5 ⁇ m, and even more preferably 1 nm to 3 ⁇ m, in consideration of reducing the internal resistance of the resulting device.
  • the thickness can be determined, for example, by cutting a test piece of an appropriate size from the laminate on which the primer layer has been formed, exposing the cross section by tearing it by hand, and observing the cross section with a microscope such as a scanning electron microscope (SEM). It can be determined from the parts where the primer layer is exposed.
  • the basis weight of the primer layer per surface of the current collector or electrode composite layer is not particularly limited as long as it satisfies the above film thickness, but it is preferably 3,000 mg/m 2 or less, and 2,500 mg/m 2 The following is more preferable, and 2,000 mg/m 2 or less is even more preferable.
  • the basis weight of the primer layer per surface is preferably 500 mg/m 2 or more, more preferably 750 mg/m 2 or more, More preferably 1,000 mg/m 2 or more.
  • the basis weight of the primer layer is the ratio of the mass (mg) of the primer layer to the area (m 2 ) of the primer layer, and if the primer layer is formed in a pattern, the area is the area of only the primer layer. This does not include the area of the lower layer such as the current collector exposed between the patterned primer layers.
  • the above-mentioned basis weight may be an assumed basis weight. Assumed basis weight means the expected basis weight when a composition with a predetermined solid content concentration is coated on a base layer using a predetermined wire bar coater. For example, if the composition has a solid content concentration of 5% by mass The composition can be expressed as the expected basis weight when coated using OSP-30 with a wire bar coater.
  • the mass of the primer layer can be determined by, for example, cutting out a test piece of an appropriate size from the laminate on which the primer layer has been formed, measuring its mass W0, and then peeling off the primer layer from the laminate.
  • the subsequent mass W1 is measured and calculated from the difference (W0-W1), or the mass W2 of the current collector is measured in advance, and then the mass W3 of the laminate on which the primer layer is formed is measured, It can be calculated from the difference (W3-W2).
  • Examples of the method for peeling off the primer layer include a method of immersing the primer layer in a solvent that dissolves or swells the primer layer, and wiping off the primer layer with a cloth or the like.
  • the basis weight and film thickness can be adjusted using known methods. For example, when forming a primer layer by coating, the solid content concentration of the coating liquid (primer layer forming composition) for forming the primer layer, the number of coatings, the clearance of the coating liquid inlet of the coating machine, etc. You can adjust it by changing it. If you want to increase the basis weight or film thickness, increase the solid content concentration, increase the number of applications, or increase the clearance. If you want to reduce the basis weight or film thickness, lower the solid content concentration, reduce the number of applications, or reduce the clearance.
  • the electrode slurry is applied to the surface of the primer layer and dried naturally or by heating to form an electrode composite layer to produce an energy storage device electrode.
  • the primer layer of the present invention can also be applied to a dry method, so an electrode composite sheet can be laminated on the primer layer and bonded under heat and pressure to produce an energy storage device electrode.
  • the electrode composite sheet may be one obtained by applying the above-mentioned electrode slurry onto a base layer and drying it naturally or by heating to form a sheet.
  • the electrode slurry described above is applied onto the base material and dried to form an electrode composite material layer, and then the composition of the present invention is applied onto this electrode composite material layer and dried to form a primer layer.
  • An energy storage device electrode can be produced by forming a current collecting substrate, further laminating a current collecting substrate thereon, heat-pressing the current collecting substrate, and then peeling off the base material and transferring the electrode composite material layer.
  • the primer layer of the present invention can exhibit high adhesion.
  • the base material is arbitrary, but a base material made of the same material as the current collector can be used, and copper foil is preferable.
  • the temperature during thermocompression bonding is not particularly limited, but in consideration of further increasing the adhesion of the primer layer, it is preferably a temperature equal to or higher than the melting point of the hydroxyl group-containing polymer.
  • the above temperature varies depending on the type of hydroxyl group-containing polymer, but is preferably less than 115°C, more preferably 110°C or less, and even more preferably 105°C or less. Further, the lower limit thereof is preferably 50°C or higher, more preferably 55°C or higher, and even more preferably 60°C or higher.
  • the pressure during heat compression bonding is also not particularly limited, but the linear pressure is preferably 1 kN/cm or more, more preferably 5 kN/cm or more, and even more preferably 10 kN/cm or more.
  • any commonly used method can be used, but a mold press method or a roll press method is particularly preferred.
  • the energy storage device is equipped with the above-mentioned electrode for an energy storage device, and more specifically, at least a pair of positive and negative electrodes and a separator interposed between each of these electrodes. and an electrolyte, and at least one of the positive and negative electrodes is comprised of the above-mentioned electrode for an energy storage device.
  • this energy storage device is characterized by using the above-mentioned electrode for energy storage devices as an electrode, other device components such as a separator and an electrolyte can be appropriately selected from known materials.
  • the separator include cellulose separators, polyolefin separators, and the like.
  • the electrolyte may be either a liquid electrolyte made by dissolving an electrolyte salt in a solvent or a solid electrolyte, and may be either an aqueous or non-aqueous electrolyte. It is particularly preferable to apply the present invention to all-solid-state batteries (for example, all-solid lithium ion batteries).
  • electrolyte salt examples include LiPF 6 , LiBF 4 , LiN(SO 2 F) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiAsF 6 , LiSbF 6 , LiAlF 4 , LiGaF 4 , LiInF 4 , LiClO 4 , Lithium salts such as LiN(CF 3 SO 2 ) 2 , LiCF 3 SO 3 , LiSiF 6 , LiN(CF 3 SO 2 ), (C 4 F 9 SO 2 ), LiI, NaI, KI, CsI, CaI 2 etc.
  • Examples include metal iodides, iodide salts of quaternary imidazolium compounds, iodide salts and perchlorates of tetraalkylammonium compounds, and metal bromides such as LiBr, NaBr, KBr, CsBr, and CaBr2 . These electrolyte salts may be used alone or in combination of two or more.
  • the electrolyte solvent is not particularly limited as long as it does not cause corrosion or decomposition of the materials constituting the battery and degrade its performance, and it dissolves the electrolyte salt.
  • non-aqueous solvents include cyclic esters such as ethylene carbonate, propylene carbonate, butylene carbonate, and ⁇ -butyrolactone, ethers such as tetrahydrofuran and dimethoxyethane, and chains such as methyl acetate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. esters, nitriles such as acetonitrile, etc. are used. These solvents may be used alone or in combination of two or more.
  • solid electrolyte inorganic solid electrolytes such as sulfide-based solid electrolytes and oxide-based solid electrolytes, and organic solid electrolytes such as polymer-based electrolytes can be suitably used. By using these solid electrolytes, it is possible to obtain an all-solid-state battery that does not use an electrolyte.
  • Sulfide-based solid electrolytes include Li 2 S--SiS 2 -lithium compounds (here, the lithium compound is at least one selected from the group consisting of Li 3 PO 4 , LiI and Li 4 SiO 4 ), Li 2 Thiolisicone materials such as SP 2 S 5 , Li 2 SP 2 O 5 , Li 2 SB 2 S 5 , Li 2 SP 2 S 5 -GeS 2 and the like can be mentioned.
  • examples include oxyacid compounds based on a PO 4 structure, perovskite type, Li 3.3 PO 3.8 N 0.22 collectively referred to as LIPON, and sodium/alumina.
  • Polymeric solid electrolytes include polyethylene oxide materials, hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile, vinylidene chloride, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, Examples include polymer compounds obtained by polymerizing or copolymerizing monomers such as styrene and vinylidene fluoride.
  • the polymer solid electrolyte may contain a supporting salt and a plasticizer.
  • the supporting salt include lithium (fluorosulfonylimide), and examples of the plasticizer include succinonitrile.
  • the apparatus used in the examples is as follows. (1) Probe type ultrasonic irradiation device (dispersion of conductive carbon) Manufactured by Hielscher Ultrasonics, UIP1000 (2) Wire bar coater (primer layer formation) Manufactured by SMT Co., Ltd., PM-9050MC (3) Roll press machine (compression of electrodes) Manufactured by Takumi Giken Co., Ltd., SA-602 (4) Adhesion/film peeling analysis device (adhesion force measurement) VPA-3 manufactured by Kyowa Interface Science Co., Ltd.
  • the raw materials used are as follows.
  • AB Acetylene black, manufactured by Denka Corporation, Denka Black Li435 WS-700: Nippon Shokubai Co., Ltd., aqueous solution containing oxazoline polymer, Epocross (registered trademark) WS-700, weight average molecular weight: 4.0 ⁇ 10 4 , solid content concentration: 25.0% by mass WS-300: Nippon Shokubai Co., Ltd., aqueous solution containing oxazoline polymer, Epocross (registered trademark) WS-300, weight average molecular weight: 1.2 x 10 5 , solid content concentration: 10.0% by mass Polyvinylpyrrolidone: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Pitzcor (registered trademark) K90, weight average molecular weight 1,200,000 E-45: manufactured by Meisei Chemical Industry Co., Ltd., polyethylene oxide, Alcox (registered trademark) E-45,
  • PEG10k manufactured by Sanyo Kasei Co., Ltd., polyethylene glycol, PEG10,000, weight average molecular weight: 10,000, mass proportion of hydroxyl groups in molecule: 3.4 ⁇ 10 -3 , melting point: 62 ° C.
  • PEG6k manufactured by Sanyo Kasei Co., Ltd., polyethylene glycol, PEG6,000, weight average molecular weight: 6,000, mass proportion of hydroxyl groups in molecule: 5.67 ⁇ 10 -3 , melting point: 61°C 2-Propanol: Manufactured by Junsei Kagaku Co., Ltd.
  • CBT-1 Manufactured by Johoku Chemical Co., Ltd., carboxybenzotriazole (CAS RN: 60932-58-3) A-30: Toagosei Co., Ltd., ammonium polyacrylate, Aron (registered trademark) A-30, weight average molecular weight 100,000, solid content concentration 31.6% by mass
  • Dispersion B 1.5 g (100 parts by mass) of AB, which is a conductive carbon material, 7.5 g (50 parts by mass as solid content) of WS-300, which is an aqueous solution containing an oxazoline polymer, and pure 33.86 g of water and 2.14 g of 2-propanol were mixed. The obtained mixture was subjected to ultrasonic treatment for 15 minutes using a probe-type ultrasonic irradiation device to prepare a dispersion liquid B in which the conductive carbon material was uniformly dispersed.
  • Dispersion C 1.4 g (100 parts by mass) of AB which is a conductive carbon material, 0.7 g (50 parts by mass) of polyvinylpyrrolidone K90, 37.90 g of pure water, and 2-propanol 2 .00g was mixed. The obtained mixture was subjected to ultrasonic treatment for 15 minutes using a probe-type ultrasonic irradiation device to prepare a dispersion liquid C in which the conductive carbon material was uniformly dispersed.
  • Example 1-1 Preparation of thin film forming composition for energy storage device electrode
  • Example 1-1 Preparation of thin film forming composition A 0.5 g of E-45, a hydroxyl group-containing polymer, was dissolved in 9.5 g of water, and E-45 was dissolved in 9.5 g of water. A 5% by mass aqueous solution of No. 45 was prepared. 6.0 g of the dispersion A prepared in Production Example 1 and 2.0 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition A with a solid content concentration of 5% by mass.
  • Thin film forming composition A was a black ink in which AB was uniformly dispersed.
  • Example 1-2 Preparation of thin film forming composition B 0.5 g of E-45, which is a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 6.0 g of dispersion A prepared in Production Example 1 and 1.2 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition B with a solid content concentration of 5% by mass. Thin film forming composition B was a black ink in which AB was uniformly dispersed.
  • Example 1-3 Preparation of Thin Film Forming Composition C 0.5 g of E-45, a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 6.0 g of dispersion A prepared in Production Example 1 and 1.6 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition C with a solid content concentration of 5% by mass. Thin film forming composition C was a black ink in which AB was uniformly dispersed.
  • Example 1-4 Preparation of Thin Film Forming Composition D 0.5 g of E-45, a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 6.0 g of dispersion A prepared in Production Example 1 and 2.4 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition D having a solid content concentration of 5% by mass. Thin film forming composition D was a black ink in which AB was uniformly dispersed.
  • Example 1-5 Preparation of thin film forming composition E 0.5 g of E-45, which is a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 6.0 g of the dispersion A prepared in Production Example 1 and 2.8 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition E with a solid content concentration of 5% by mass. Thin film forming composition E was a black ink in which AB was uniformly dispersed.
  • Example 1-6 Preparation of thin film forming composition F 0.5 g of E-45, a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 6.0 g of dispersion A prepared in Production Example 1 and 4.0 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition F with a solid content concentration of 5% by mass. Thin film forming composition F was a black ink in which AB was uniformly dispersed.
  • Example 1-7 Preparation of thin film forming composition G 0.5 g of E-45, which is a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 3.0 g of the dispersion A prepared in Production Example 1 and 4.0 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition G with a solid content concentration of 5% by mass. Thin film forming composition G was a black ink in which AB was uniformly dispersed.
  • Example 1-8 Preparation of Thin Film Forming Composition H 0.5 g of R-150, a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of R-150. 6.0 g of the dispersion liquid A prepared in Production Example 1 and 4.0 g of a 5% by mass aqueous solution of R-150 were mixed to prepare a thin film-forming composition H having a solid content concentration of 5% by mass. Thin film forming composition H was a black ink in which AB was uniformly dispersed.
  • Example 1-9 Preparation of Thin Film Forming Composition I 0.5 g of E-45, a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 6.0 g of the dispersion B prepared in Production Example 2 and 2.0 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition I with a solid content concentration of 5% by mass. Thin film forming composition I was a black ink in which AB was uniformly dispersed.
  • Example 1-10 Preparation of Thin Film Forming Composition J 0.5 g of E-45, a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 6.0 g of dispersion B prepared in Production Example 2 and 4.0 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition J having a solid content concentration of 5% by mass. Thin film forming composition J was a black ink in which AB was uniformly dispersed.
  • Example 1-11 Preparation of thin film forming composition K 0.5 g of E-45, a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of CP-A2H. 6.0 g of the dispersion A prepared in Production Example 1 and 2.0 g of a 5% by mass aqueous solution of CP-A2H were mixed to prepare a thin film-forming composition K with a solid content concentration of 5% by mass. Thin film forming composition K was a black ink in which AB was uniformly dispersed.
  • Example 1-12 Preparation of thin film forming composition L 0.5 g of E-45, which is a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 6.0 g of the dispersion A prepared in Production Example 1 and 0.8 g of a 5% by mass aqueous solution of E-45 were mixed to prepare a thin film-forming composition L having a solid content concentration of 5% by mass. Thin film forming composition L was a black ink in which AB was uniformly dispersed.
  • Example 1-13 Preparation of thin film forming composition M 0.5 g of E-45, which is a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 0.5 g of CBT-1, a heterocyclic compound, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of CBT-1. Furthermore, 1.6 g of A-30 was dissolved in 8.4 g of water to prepare a 5% by mass solution of A-30.
  • Example 1-14 Preparation of thin film forming composition N 0.5 g of E-45, which is a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 0.5 g of CBT-1, a heterocyclic compound, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of CBT-1. Furthermore, 1.6 g of A-30 was dissolved in 8.4 g of water to prepare a 5% by mass solution of A-30.
  • a thin film forming composition N having a solid content concentration of 5% by mass was prepared by mixing 25g of the above.
  • Thin film forming composition N was a black ink in which AB was uniformly dispersed.
  • Example 1-15 Preparation of thin film forming composition O 0.5 g of E-45, which is a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. 0.5 g of CBT-1, a heterocyclic compound, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of CBT-1. Furthermore, 1.6 g of A-30 was dissolved in 8.4 g of water to prepare a 5% by mass solution of A-30.
  • dispersion A prepared in Production Example 1 2.5 g of a 5% by mass aqueous solution of E-45, 1.0 g of a 5% by mass aqueous solution of CBT-1, and 1.0 g of a 5% by mass aqueous solution of A-30.
  • a thin film forming composition M having a solid content concentration of 5% by mass was prepared by mixing 25g of the above.
  • Thin film forming composition O was a black ink in which AB was uniformly dispersed.
  • Example 1-16 Preparation of thin film forming composition P 0.5 g of E-45, which is a hydroxyl group-containing polymer, was dissolved in 9.5 g of water to prepare a 5% by mass aqueous solution of E-45. A 5% by mass solution of A-30 was prepared by dissolving 1.6 g of A-30 in 8.4 g of water. 7.5 g of dispersion A prepared in Production Example 1, 2.5 g of a 5% by mass aqueous solution of E-45, and 1.25 g of a 5% by mass aqueous solution of A-30 were mixed, and the solid concentration was adjusted to 5% by mass. A thin film forming composition P was prepared. Thin film forming composition P was a black ink in which AB was uniformly dispersed.
  • Example 2-1 Composition A prepared in Example 1-1 was uniformly spread on a copper foil (thickness 10 ⁇ m) as a current collector using a wire bar coater using OSP-30, and then dried at 120 ° C. for 20 minutes. A thin film (primer layer) was formed, and a laminate of copper foil and the primer layer was produced. In the obtained laminate, the surface of the copper foil was uniformly covered with the conductive carbon material (estimated basis weight: 1,200 mg/m 2 ).
  • the assumed basis weight means the estimated basis weight when a thin film-forming composition having a predetermined solid content concentration is coated on a current collector using a predetermined wire bar coater.
  • the assumed basis weight when using a thin film forming composition having a solid content concentration of 5% by mass is as follows. OSP-30: 1,200mg/ m2
  • Example 2-2 to 2-16, Comparative Examples 2-1 to 2-7 Same as Example 2-1 except that Composition A was changed to Compositions B to P and a to g prepared in Examples 1-2 to 1-16 and Comparative Examples 1-1 to 1-7. A thin film (primer layer) was formed to produce a laminate.
  • compositions A to P of Examples 2-1 to 2-16 were used, a uniform thin film (primer layer) could be formed.
  • a uniform thin film (primer layer) was formed similarly to compositions A to P except for compositions c and d. did it.
  • Composition c was a non-uniform dispersion containing aggregates, so a uniform thin film (primer layer) could not be formed.
  • AB was uniformly dispersed in composition d, but the ink was highly viscous and viscous, and coating defects occurred in streaks during film formation, resulting in uneven conductivity on the surface of the copper foil. This resulted in a thin film (primer layer) covered with carbon material.
  • Example 3-1 Fabrication of transfer electrode
  • the laminate of copper foil and primer layer produced in Example 2-1 was transferred to a dry booth (temperature 22°C, dew point -50°C) within 1 hour after film formation. Thereafter, the laminate was cut into a size of 30 mm x 100 mm and processed.
  • Electrode composite material layer composite A in which an electrode composite material layer was formed on copper foil, was similarly cut out and processed into a size of 25 mm x 70 mm.
  • Laminate and electrode composite layer composite A in which the primer layer and electrode composite layer coated surfaces are stacked facing each other and pressed together at a linear pressure of 10 kN/cm using a roll press heated to 60°C to form a primer layer. were integrated.
  • the transfer electrode was prepared in the same manner as above, except that the laminate of the copper foil and the primer layer was left standing for 72 hours in an air-conditioned room (temperature 22°C, dew point 10-15°C). (after storage in an air-conditioned room).
  • Examples 3-2 to 3-16, Comparative Examples 3-1 to 3-6 The procedure was the same as in Example 3-1, except that the laminate was changed to the laminates produced in Examples 2-2 to 2-16, Comparative Examples 2-1, 2-2, and 2-4 to 2-7. Thus, a transfer electrode (immediately after film formation) and a transfer electrode (after storage in an air-conditioned room) were produced.
  • Adhesion force (N/m) Measured value * (N) / (Sample measurement width (mm) x 10 -3 ) * The measured value was the average value of the peeling distance from 10 mm to 35 mm.
  • compositions A to P of Examples 3-1 to 3-16 were used, the initial adhesion was high and a thin film (primer layer) with practical adhesion was obtained. Met. There was little change in adhesion before and after storage in an air-conditioned room, showing a high adhesion maintenance rate. It was confirmed that the composition of the present invention had a practical adhesion force and adhesion maintenance rate.
  • composition a of Comparative Example 3-1 when composition a of Comparative Example 3-1 was used, the initial adhesion was high and the thin film (primer layer) had a practical adhesion, but after storage in an air-conditioned room, the adhesive strength was 12.8N/ The adhesion force decreased in m, and the adhesion force maintenance rate was as low as 21.2%.
  • compositions b to g of Comparative Examples 3-2 to 3-6 had low initial adhesion and did not form a thin film (primer layer) with practical adhesion. Measurement was omitted.

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Abstract

La présente invention concerne une composition pour la formation d'un film mince destiné à une électrode de dispositif de stockage d'énergie, et qui fournit une couche primaire apte à transférer une couche de mélange d'électrode et présentant à la fois une adhérence pratique et une excellente rétention de l'adhérence après le transfert. La composition pour la formation d'un film mince destiné à une électrode de dispositif de stockage d'énergie comprend : un matériau de carbone conducteur ; un polymère ayant un groupe oxazoline dans une chaîne latérale ; un polymère contenant un groupe hydroxyle ayant un poids moléculaire moyen en poids de 50 000 à 5 000 000 ; et un solvant.
PCT/JP2023/016043 2022-04-27 2023-04-24 Composition pour la formation d'un film mince destiné à une électrode de dispositif de stockage d'énergie WO2023210558A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015070089A (ja) * 2013-09-27 2015-04-13 東洋インキＳｃホールディングス株式会社 キャパシタ電極形成用組成物、キャパシタ電極、及びキャパシタ
WO2017119287A1 (fr) * 2016-01-07 2017-07-13 日産化学工業株式会社 Électrode pour dispositifs de stockage d'énergie
WO2019188559A1 (fr) * 2018-03-29 2019-10-03 日産化学株式会社 Feuille de sous-couche pour électrode de dispositif de stockage d'énergie

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015070089A (ja) * 2013-09-27 2015-04-13 東洋インキＳｃホールディングス株式会社 キャパシタ電極形成用組成物、キャパシタ電極、及びキャパシタ
WO2017119287A1 (fr) * 2016-01-07 2017-07-13 日産化学工業株式会社 Électrode pour dispositifs de stockage d'énergie
WO2019188559A1 (fr) * 2018-03-29 2019-10-03 日産化学株式会社 Feuille de sous-couche pour électrode de dispositif de stockage d'énergie

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