WO2014203767A1 - Composition pour dispositifs de stockage d'électricité, bouillie pour dispositifs de stockage d'électricité, électrode de dispositif de stockage d'électricité, procédé de production d'électrode de dispositif de stockage d'électricité, film de protection, procédé de production de film de protection, et de dispositif de stockage d'électricité - Google Patents

Composition pour dispositifs de stockage d'électricité, bouillie pour dispositifs de stockage d'électricité, électrode de dispositif de stockage d'électricité, procédé de production d'électrode de dispositif de stockage d'électricité, film de protection, procédé de production de film de protection, et de dispositif de stockage d'électricité Download PDF

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WO2014203767A1
WO2014203767A1 PCT/JP2014/065311 JP2014065311W WO2014203767A1 WO 2014203767 A1 WO2014203767 A1 WO 2014203767A1 JP 2014065311 W JP2014065311 W JP 2014065311W WO 2014203767 A1 WO2014203767 A1 WO 2014203767A1
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Prior art keywords
storage device
electricity storage
slurry
polymer
group
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English (en)
Japanese (ja)
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一聡 伊藤
巧治 大塚
智隆 篠田
伸行 藤原
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JSR Corp
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JSR Corp
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Priority to KR1020157035133A priority patent/KR20160021771A/ko
Priority to CN201480035131.1A priority patent/CN105340113A/zh
Publication of WO2014203767A1 publication Critical patent/WO2014203767A1/fr
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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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a composition for an electricity storage device, a slurry for an electricity storage device, an electricity storage device electrode produced by applying and drying the slurry to a current collector, a method for producing the electrode, a protective film formed from the slurry, and a method for producing the same And an electricity storage device including the electrode and / or the protective film.
  • lithium ion batteries and lithium ion capacitors are expected as power storage devices having high voltage and high energy density.
  • An electrode used for such an electricity storage device is usually produced by applying and drying a mixture of an electrode active material and polymer particles functioning as a binder on the surface of a current collector.
  • the properties required for the polymer particles include the ability to bind electrode active materials and the ability to bind the electrode active material and the current collector, the abrasion resistance in the process of winding the electrode, and subsequent cutting. Examples thereof include powder-off resistance in which fine powder of the electrode active material is not generated from the applied electrode composition layer (hereinafter also simply referred to as “active material layer”).
  • the term “adhesiveness” may be used in a comprehensive manner.
  • the electrode binder when producing a positive electrode, it is advantageous to use a fluorine-containing organic polymer which is slightly inferior in adhesiveness such as polyvinylidene fluoride but excellent in oxidation resistance.
  • a fluorine-containing organic polymer which is slightly inferior in adhesiveness such as polyvinylidene fluoride but excellent in oxidation resistance.
  • a negative electrode when producing a negative electrode, it is advantageous to use a (meth) acrylic acid polymer which is slightly inferior in oxidation resistance but excellent in adhesion.
  • Patent Document 4 and Patent Document 5 improve battery characteristics by forming a porous layer containing a resin binder containing polyamide, polyimide, and polyamideimide on a porous separator substrate. Technology to do is being studied.
  • some aspects of the present invention provide a composition for an electricity storage device and a slurry for an electricity storage device capable of producing an electricity storage device electrode excellent in adhesion and charge / discharge characteristics by solving at least a part of the problems. Is to provide.
  • some embodiments according to the present invention provide a composition for an electricity storage device and a slurry for an electricity storage device capable of producing a protective film having excellent adhesion and charge / discharge characteristics by solving at least a part of the problems. It is to provide.
  • the present invention has been made to solve at least a part of the above-described problems, and can be realized as the following aspects or application examples.
  • composition for an electricity storage device comprising a polymer (A1), a polymer (A2), and a liquid medium (B),
  • the polymer (A1) contains at least one functional group selected from the group consisting of a sulfo group, a carboxy group, and a group of these salts in a total amount of 0.001 to 1 per 100 g of the polymer (A1). Containing 2 moles,
  • the polymer (A1) has a repeating unit represented by the following general formula (1), In 100 parts by mass of the polymer (A2), the content of the repeating unit derived from the monomer having a fluorine atom is 80 parts by mass or more.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group or a cycloalkyl group having 1 to 16 carbon atoms.
  • the monomer having a fluorine atom may be at least one selected from the group consisting of vinylidene fluoride, propylene hexafluoride, and tetrafluoroethylene.
  • composition for an electricity storage device of Application Example 2 In 100 parts by mass of the polymer (A2), the content of the repeating unit derived from vinylidene fluoride may be 50 to 99 parts by mass.
  • a slurry for producing an electricity storage device containing a polymer (A1), a liquid medium (B), and inorganic particles (C),
  • the polymer (A1) contains at least one functional group selected from the group consisting of a sulfo group, a carboxy group, and a group of these salts in a total amount of 0.001 to 1 per 100 g of the polymer (A1). Containing 2 moles,
  • the polymer (A1) has a repeating unit represented by the following general formula (1), The spinnability is 30 to 80%. (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group or a cycloalkyl group having 1 to 16 carbon atoms.)
  • the inorganic particles (C) may be an electrode active material.
  • One aspect of the electricity storage device electrode according to the present invention is: It is characterized by comprising: a current collector; and a layer formed by applying and drying the electricity storage device slurry of Application Example 5 on the surface of the current collector.
  • the inorganic particles (C) may be at least one kind of particles selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide and magnesium oxide.
  • One aspect of the protective film according to the present invention is: It is produced using the slurry for electricity storage devices of Application Example 7.
  • Application Example 9 One aspect of the electricity storage device according to the present invention is: The power storage device electrode of Application Example 6 is provided.
  • Application Example 10 One aspect of the electricity storage device according to the present invention is: The protective film according to Application Example 8 is provided.
  • a protective film can be produced using the slurry for power storage device of Application Example 7.
  • composition for an electricity storage device and the slurry for an electricity storage device according to the present invention a coating film having excellent adhesion can be produced and uneven coating of the coating film can be suppressed.
  • Device electrodes and protective films can be produced.
  • FIG. 1 is a schematic view showing a cross section of an electricity storage device according to a first specific example.
  • FIG. 2 is a schematic diagram illustrating a cross section of the electricity storage device according to the second specific example.
  • FIG. 3 is a schematic view showing a cross section of the electricity storage device according to the third specific example.
  • (meth) acrylic acid is a concept encompassing both “acrylic acid” and “methacrylic acid”.
  • ⁇ (meth) acrylate is a concept encompassing both “ ⁇ acrylate” and “ ⁇ methacrylate”.
  • (Meth) allyl” is a concept encompassing both “allyl” and “methallyl”.
  • the power storage device slurry according to the present embodiment is a slurry used for manufacturing a power storage device containing a polymer (A1), a liquid medium (B), and inorganic particles (C). .
  • This slurry for an electricity storage device is suitable for an application for producing an electricity storage device electrode used for an electricity storage device or an application for producing a protective film used for an electricity storage device.
  • the storage device slurry according to the present embodiment can be roughly classified into “sludge for storage device electrode” and “slurry for protective film”.
  • slurry for electricity storage device electrode is used to form an active material layer on the surface of the current collector after being applied to the surface of the current collector to form a coating film and then dried. Refers to a dispersion.
  • the slurry for an electricity storage device electrode contains an electrode active material as inorganic particles (C).
  • the “slurry for protective film” is used to form a coating film on the surface of the electricity storage device electrode or the separator or both, and then dry to form a protective film on the surface.
  • the slurry for protective films contains an inorganic filler as inorganic particles (C).
  • composition for an electricity storage device in the present specification is a composition for preparing the above slurry for an electricity storage device electrode or a slurry for a protective film, and refers to a composition containing a polymer and a liquid medium. .
  • the polymer (A1) contained in the electricity storage device slurry according to the present embodiment is selected from the group consisting of a sulfo group, a carboxy group, and a group of these salts (hereinafter also referred to as “specific functional group”). At least one functional group in a total amount of 0.001 to 1.2 mol per 100 g of the polymer (A1) and having a repeating unit represented by the following general formula (1).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group or a cycloalkyl group having 1 to 16 carbon atoms.
  • the content of the specific functional group in the polymer (A1) is 0.001 to 1.2 mol in total per 100 g of the polymer (A1), preferably 0.005 to 1 mol, more preferably 0.01 to 0 mol. .9 moles.
  • an electricity storage device having excellent dispersibility of the inorganic particles (C) and good charge / discharge rate characteristics can be obtained.
  • Content of the specific functional group in a polymer (A1) can be calculated
  • a method for producing the polymer (A1) for example, a method of copolymerizing a monomer containing a sulfo group, a carboxy group, or a salt thereof and a polymerizable monomer copolymerizable therewith (hereinafter referred to as “polymer”).
  • Polymer a method of copolymerizing a monomer containing a sulfo group, a carboxy group, or a salt thereof and a polymerizable monomer copolymerizable therewith
  • first method a method of adding a compound containing a sulfo group, a carboxy group, or a salt group thereof to a polymer obtained from the polymerizable monomer
  • second method A method of polymerizing the polymerizable monomer using a radical initiator containing a sulfo group, a carboxy group, or a group of these salts (hereinafter referred to as “third method”). Can be mentioned.
  • Examples of the monomer containing a sulfo group, a carboxy group, or a salt group thereof used in the first method include an ethylenically unsaturated sulfonic acid monomer and an ethylenically unsaturated carboxylic acid monomer. Is mentioned.
  • Examples of the ethylenically unsaturated sulfonic acid monomer include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamide. -2-Methylpropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, (meth) acrylic acid-2-ethyl sulfate, 3-allyloxy-2-hydroxypropanesulfonic acid, and alkali metal salts and ammonium thereof Salt.
  • Examples of the ethylenically unsaturated carboxylic acid monomer include (meth) acrylic acid, crotonic acid, isocrotonic acid, and ethylenically unsaturated monocarboxylic acids (salts) having 3 to 10 carbon atoms such as alkali metal salts thereof. ) Monomer; Itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, and ethylenically unsaturated dicarboxylic acid (salt) monomers having 4 to 10 carbon atoms such as alkali metal salts thereof Is mentioned. Of these, salts of ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms such as acrylic acid and methacrylic acid are preferred.
  • the polymer (A1) contains a repeating unit represented by the following general formula (1).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group or a cycloalkyl group having 1 to 16 carbon atoms.
  • the content ratio of the repeating unit represented by the general formula (1) is 50 to 99.9% by mass when the mass of all the repeating units of the polymer (A1) is based on (100% by mass). Is more preferable, 55 to 90% by mass is more preferable, and 60 to 80% by mass is particularly preferable.
  • R 2 is an alkyl group having 1 to 6 carbon atoms. It is preferable that the content rate of the repeating unit represented by Formula (1) is 50 mass% or more.
  • the polymerizable monomer used in the first method, the second method, and the third method is bonded to a non-carbonyl oxygen atom.
  • (meth) acrylic acid alkyl esters having 1 to 6 carbon atoms in the alkyl group to be synthesized include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid.
  • Examples include (meth) acrylic acid alkyl esters such as t-butyl and hexyl (meth) acrylate.
  • the resulting polymer (A1) can be made into a polymer having a repeating unit in which R 2 is an alkyl group having 1 to 6 carbon atoms in the general formula (1). it can.
  • Examples of the polymerizable monomer also include (meth) acrylic acid alkyl esters in which the alkyl group bonded to the non-carbonyl oxygen atom has 7 to 16 carbon atoms.
  • Specific examples thereof include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, and lauryl (meth) acrylate.
  • the resulting polymer (A1) can be made into a polymer having a repeating unit in which R 2 is an alkyl group having 7 to 16 carbon atoms in the general formula (1). it can.
  • polymerizable monomers include, for example, alkyl esters of unsaturated polycarboxylic acids such as dimethyl fumarate, diethyl maleate, butylbenzyl maleate, diethyl itaconate, diisopropyl itaconate; (meth) acrylic acid 2 -Unsaturated carboxylic acid ester having an alkoxyl group such as methoxyethyl; ⁇ , ⁇ -unsaturated nitrile such as acrylonitrile, methacrylonitrile; styrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, etc.
  • alkyl esters of unsaturated polycarboxylic acids such as dimethyl fumarate, diethyl maleate, butylbenzyl maleate, diethyl itaconate, diisopropyl itaconate
  • Styrene monomers Vinyl acetates such as vinyl acetate and vinyl propionate; Vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride, ethylene trifluoride, ethylene tetrafluoride, hexafluoride Halogenated olefins such as propylene; methyl vinyl ether Vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acid amides such as acrylamide, methacrylamide, N, N-dimethylacrylamide and N, N-dimethylmethacrylamide; ⁇ -olefins such as ethylene and propylene; vinylidene cyanide; Etc.
  • a polymerizable monomer having a crosslinkable group is used as the polymerizable monomer.
  • the binder can be crosslinked when the coating film is heated and dried, and a tough and flexible active material layer or protective film is obtained. Thereby, melt
  • Examples of such a crosslinkable group include an epoxy group, a hydroxyl group, an N-methylolamide group, and an oxazoline group, and among these, an epoxy group and a hydroxyl group are preferable.
  • Examples of the polymerizable monomer having a crosslinkable group used in the first method, the second method, and the third method include an epoxy group-containing monomer, a hydroxyl group-containing monomer, and an N-methylolamide group-containing monomer. And oxazoline group-containing monomers.
  • Epoxy group-containing monomers include glycidyl ethers of unsaturated alcohols such as (meth) allyl glycidyl ether; glycidyl (meth) acrylate, glycidyl-p-vinylbenzoate, methyl glycidyl itaconate, glycidyl ethyl malate, glycidyl vinyl Glycidyl esters of unsaturated carboxylic acids such as sulfonate, glycidyl allyl sulfonate, glycidyl (meth) allyl sulfonate; epoxide olefins such as butadiene monooxide, vinylcyclohexene monooxide, 2-methyl-5,6-epoxyhexene; Can be mentioned.
  • N-methylolamide group-containing monomer examples include (meth) acrylamides having a methylol group such as N-methylol (meth) acrylamide.
  • Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.
  • the polymerization method in the first method is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used.
  • the polymerization initiator used for the polymerization include lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoylperoxide.
  • Organic peroxides such as oxides; azo compounds such as ⁇ , ⁇ ′-azobisisobutyronitrile; and persulfates such as ammonium persulfate and potassium persulfate.
  • suspending agent used in suspension polymerization examples include synthetic polymer substances such as polyvinyl alcohol, partially saponified polyvinyl acetate, cellulose derivatives such as methylcellulose, polyvinylpyrrolidone, maleic anhydride-vinyl acetate polymer, and polyacrylamide. And natural polymer substances such as starch and gelatin.
  • emulsifier used in the emulsion polymerization include anionic emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfate, and nonionic emulsifiers such as polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid partial ester.
  • a molecular weight adjusting agent such as trichlorethylene, thioglycol, dodecyl mercaptan can be used as necessary.
  • the above-described polymerization initiator, monomer, suspending or emulsifying agent, molecular weight adjusting agent, etc. may be added to the polymerization system all together at the start of polymerization, or may be added in portions during the polymerization.
  • the polymerization is usually performed at a temperature of 35 to 80 ° C. with stirring.
  • a polymer is first formed, and then a compound containing an acid containing a nitrogen element or a chalcogen element or a salt group thereof is added to the polymer.
  • the polymerization method any of the solution polymerization method, the suspension polymerization method, and the emulsion polymerization method can be used as described above, and it is optimal depending on the conditions of the subsequent addition reaction and the characteristics of the polymer to be obtained.
  • a suitable manufacturing method may be selected. For example, when the addition reaction is carried out in an aqueous system, it is advantageous to obtain the polymer as fine aqueous dispersion particles by emulsion polymerization.
  • a solution polymerization method or a suspension polymerization method using a lower alcohol such as methanol as a polymerization medium is preferable, but a normal suspension polymerization method can also be used.
  • the reaction for adding the above compound is usually performed in a solvent.
  • a solvent either water or an organic solvent can be used.
  • a monomer having a specific functional group used in the addition reaction is often water-soluble, water or an organic solvent containing water is used. It is advantageous to use
  • the reaction is usually carried out by heating at a temperature of about 40 to 120 ° C. for 2 to 24 hours. However, if the reaction temperature is too high, the polymer is deteriorated. A catalyst can be used for this addition reaction.
  • the catalyst examples include quaternary ammonium salts such as tetrabutylammonium bisulfate, tetrabutylammonium bromide, trimethyllauryl ammonium chloride, and benzyltriethylammonium chloride, and boron fluorides such as boron tetrafluoride zinc.
  • the addition reaction can be allowed to proceed simultaneously with the polymerization by preparing the polymer with a monomer or catalyst necessary for the addition reaction.
  • Examples of the radical initiator containing the specific functional group used in the third method include ammonium persulfate and potassium persulfate.
  • a functional group that easily undergoes an addition reaction with a radical-cleavable initiator is introduced into the polymer.
  • the said radical initiator can be introduce
  • the functional group is preferably an epoxy group, and an epoxy group can be introduced into the polymer by copolymerizing the epoxy group-containing monomer.
  • any of solution polymerization method, suspension polymerization method and emulsion polymerization method can be used, and there is no particular limitation.
  • the polymer (A1) preferably has a glass transition temperature (Tg) of 5 ° C. or less from the viewpoint of improving adhesion.
  • the weight average molecular weight (Mw) of the polymer (A1) is usually 10,000 or more and 1,000,000 or less, preferably 20,000 or more and 500,000 or less. When the weight average molecular weight is within this range, a slurry for an electricity storage device having excellent strength of the active material layer and protective film to be formed and high dispersibility of the inorganic particles (C) can be obtained.
  • a weight average molecular weight can be calculated
  • the slurry for an electricity storage device contains the polymer (A1) as an essential component, but may contain a mixture obtained by blending the polymer (A1) and the polymer (A2).
  • a mixture obtained by blending the polymer (A1) and the polymer (A2) is suitable in that it can impart further better oxidation resistance.
  • a polymer with low oxidation resistance is used, it may not be able to obtain good charge / discharge characteristics because it undergoes oxidative decomposition due to repeated charge / discharge. is there.
  • the composition for an electricity storage device includes the polymer (A1) and the polymer (A2) described above. And a liquid medium (B) to be described later, and the content ratio of the repeating unit derived from the monomer having a fluorine atom is 100 parts by mass or more in 100 parts by mass of the polymer (A2).
  • Examples of the monomer having a fluorine atom include an olefin compound having a fluorine atom and a (meth) acrylic acid ester having a fluorine atom.
  • Examples of the olefin compound having a fluorine atom include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, ethylene trifluoride chloride, and perfluoroalkyl vinyl ether.
  • (meth) acrylic acid ester having a fluorine atom for example, a compound represented by the following general formula (1), (meth) acrylic acid 3 [4 [1-trifluoromethyl-2,2-bis [bis (tri Fluoromethyl) fluoromethyl] ethynyloxy] benzooxy] 2-hydroxypropyl and the like.
  • R 4 is a hydrogen atom or a methyl group
  • R 5 is a C 1-18 hydrocarbon group containing a fluorine atom.
  • R 5 in the general formula (2) examples include fluorinated alkyl groups having 1 to 12 carbon atoms, fluorinated aryl groups having 6 to 16 carbon atoms, and fluorinated aralkyl groups having 7 to 18 carbon atoms. Among these, a fluorinated alkyl group having 1 to 12 carbon atoms is preferable.
  • R 5 in the general formula (2) include, for example, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1, 3,3,3-hexafluoropropan-2-yl group, ⁇ - (perfluorooctyl) ethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,4,4,4- Hexafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 9H-perfluoro-1-nonyl group, 1H, 1H, 11H-perfluoroundecyl group, perfluorooctyl group, etc.
  • the monomer having a fluorine atom is preferably an olefin compound having a fluorine atom, more preferably at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. preferable.
  • the monomer having a fluorine atom may be used alone or in combination of two or more.
  • the polymer (A2) may further have a repeating unit derived from another unsaturated monomer in addition to the repeating unit derived from the monomer having a fluorine atom.
  • the other unsaturated monomer the above-exemplified unsaturated carboxylic acid, unsaturated carboxylic acid ester, ⁇ , ⁇ -unsaturated nitrile compound and other monomers can be used.
  • the content of the repeating unit derived from the monomer having a fluorine atom is 80 parts by mass or more, and preferably 90 parts by mass or more.
  • the monomer having a fluorine atom is more preferably at least one selected from vinylidene fluoride, ethylene tetrafluoride and propylene hexafluoride.
  • the more preferable aspect of a polymer (A2) is as follows. That is, the content of the repeating unit derived from vinylidene fluoride in 100 parts by mass of the polymer (A2) is preferably 50 to 99 parts by mass, more preferably 80 to 98 parts by mass; The content of the repeating unit derived from is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 20 parts by mass; and the repetition derived from propylene hexafluoride The content ratio of the unit is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 2 to 25 parts by mass.
  • the polymer (A2) is most preferably composed of only a repeating unit derived from at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene.
  • the content of the repeating unit derived from the monomer having a fluorine atom in the total 100 parts by mass of the polymer (A1) and the polymer (A2) is preferably 1 to 50 parts by mass.
  • the amount is more preferably part by mass, further preferably 15 to 35 parts by mass, and particularly preferably 20 to 30 parts by mass.
  • the electricity storage device slurry according to the present embodiment contains the liquid medium (B).
  • the liquid medium (B) may be an aqueous medium containing water or a non-aqueous medium substantially not containing water, but is preferably an aqueous medium.
  • the aqueous medium can contain a non-aqueous medium other than water from the viewpoint of improving the applicability of the slurry for the electricity storage device.
  • the non-aqueous medium is preferably a non-aqueous medium having a normal boiling point of 80 to 350 ° C., for example, amide compounds such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide; toluene, xylene, n-dodecane, tetralin Hydrocarbons such as 2-ethyl-1-hexanol, 1-nonanol, lauryl alcohol, etc .; ketones such as methyl ethyl ketone, cyclohexanone, phorone, acetophenone, isophorone; benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate, butyl lactate Esters such as o-toluidine, m-toluidine and p-toluidine; lactones such as ⁇ -butyrolactone and ⁇ -butyrolactone; sulfoxides and sulf
  • the liquid medium (B) contains water and a non-aqueous medium other than water, 90% by mass or more is preferably water, and 98% by mass or more is water in 100% by mass of the total amount of the liquid medium (B). It is more preferable that By using an aqueous medium as the liquid medium (B), the slurry for the electricity storage device according to the present embodiment has a low degree of adverse effects on the environment, and the safety for handling workers is also increased.
  • the content ratio of the non-aqueous medium contained in the aqueous medium is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and substantially no content with respect to 100 parts by mass of the aqueous medium. Is particularly preferred.
  • substantially does not contain means that a non-aqueous medium is not intentionally added as a liquid medium, and a non-aqueous medium inevitably mixed when producing a slurry for an electricity storage device is used. May be included.
  • the electricity storage device slurry according to the present embodiment contains inorganic particles (C).
  • the inorganic particles (C) can be appropriately selected depending on the use of the slurry for the electricity storage device.
  • the slurry for the electricity storage device is used for the production of the active material layer (that is, when used as the slurry for the electricity storage device electrode), it is inorganic. It is necessary to select an electrode active material as the particles (C).
  • the slurry for power storage devices is used for production of a protective film (that is, when used as a slurry for protective film), it is necessary to select an insulating inorganic filler.
  • an electrode active material and an inorganic filler that can be used as the inorganic particles (C) will be described.
  • Electrode Active Material When the power storage device slurry according to the present embodiment is used as a power storage device electrode slurry, it is necessary to select an electrode active material as the inorganic particles (C). There is no restriction
  • a lithium atom-containing oxide when producing a positive electrode of a lithium ion secondary battery, it is preferably a lithium atom-containing oxide.
  • Oxide in the present specification is a concept that means a compound or salt composed of oxygen and an element having an electronegativity lower than that of oxygen.
  • metal oxide metal phosphate, nitrate , Halogen oxo acid salts, sulfonic acid salts and the like.
  • lithium atom-containing oxide examples include a composite metal oxide represented by the following general formula (3a) or (3b), and a lithium atom-containing oxide represented by the following general formula (4) and having an olivine crystal structure. It is preferable to use at least one selected from the group consisting of these.
  • M 1 is at least one metal atom selected from the group consisting of Co, Ni and Mn
  • M 2 is at least one selected from the group consisting of Al and Sn) Is a metal atom of the species
  • O is an oxygen atom
  • x, y and z are in the range of 0.10 ⁇ x ⁇ 0, 4.00 ⁇ y ⁇ 0.85 and 2.00 ⁇ z ⁇ 0, respectively Is the number of Li 1-x M 3 x (XO 4 ) (4)
  • M 3 is a metal selected from the group consisting of Mg, Ti, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, Ge, and Sn.
  • X is at least one selected from the group consisting of Si, S, P and V; x is a number and satisfies the relationship 0 ⁇ x ⁇ 1.)
  • the value of x in the general formula (4) is selected so that the valence of the entire general formula (4) is 0 in accordance with the valences of M 3 and X, respectively.
  • the lithium atom-containing oxide represented by the general formula (4) and having an olivine crystal structure has different electrode potentials depending on the type of the metal element M 3 . Therefore, the battery voltage can be arbitrarily set by selecting the type of the metal element M.
  • the lithium atom-containing oxide having an olivine crystal structure LiFePO 4 , LiCoPO 4 , Li 0.90 Ti 0.05 Nb 0.05 Fe 0.30 Co 0.30 Mn 0.30 PO 4 And so on.
  • LiFePO 4 is particularly preferable because it is easy to obtain an iron compound as a raw material and is inexpensive.
  • the compound which substituted Fe ion in said compound by Co ion, Ni ion, or Mn ion also has the same crystal structure as said each compound, it has the same effect as an electrode active material.
  • carbon when producing a negative electrode of a lithium ion secondary battery, for example, carbon can be used as the electrode active material (negative electrode active material).
  • specific examples of carbon include carbon materials obtained by firing organic polymer compounds such as phenol resin, polyacrylonitrile, and cellulose; carbon materials obtained by firing coke and pitch; artificial graphite; natural graphite and the like Can be mentioned.
  • activated carbon activated carbon fiber, silica, alumina or the like can be used as the electrode active material.
  • carbon materials such as graphite, non-graphitizable carbon, hard carbon, coke, polyacene organic semiconductor (PAS), or the like can be used.
  • the average particle diameter of the electrode active material is preferably in the range of 0.4 to 10 ⁇ m for the positive electrode, and more preferably in the range of 0.5 to 7 ⁇ m.
  • the negative electrode it is preferably in the range of 3 to 30 ⁇ m, more preferably in the range of 5 to 25 ⁇ m.
  • the contact area between the electrode active material and the conductivity-imparting agent is sufficiently ensured when the average particle diameter of the electrode active material is within the above range.
  • the electronic conductivity of the electrode is improved and the electrode resistance is further reduced.
  • the average particle diameter of the electrode active material means that the cumulative frequency of the number of particles when the particle size distribution is measured using a particle size distribution measuring apparatus based on a laser diffraction method and the particles are accumulated from small particles is 50. % Particle diameter (D50).
  • a laser diffraction particle size distribution measuring apparatus examples include HORIBA LA-300 series, HORIBA LA-920 series (above, manufactured by Horiba, Ltd.), and the like. This particle size distribution measuring apparatus is not intended to evaluate only the primary particles of the electrode active material, but also evaluates the secondary particles formed by aggregation of the primary particles.
  • the average particle diameter obtained by this particle size distribution measuring apparatus can be used as an indicator of the dispersion state of the electrode active material contained in the slurry for the electricity storage device electrode.
  • the average particle diameter of the electrode active material is determined by centrifuging the slurry for the electricity storage device electrode to precipitate the electrode active material, then removing the supernatant and measuring the precipitated electrode active material by the above method. Can also be measured.
  • the slurry for protective film can improve the toughness of the protective film formed by containing an inorganic filler.
  • the inorganic filler silicon dioxide (silica), titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), magnesium oxide (magnesia), or the like can be used.
  • the inorganic filler silicon dioxide (silica), titanium oxide (titania), aluminum oxide (alumina), zirconium oxide (zirconia), magnesium oxide (magnesia), or the like can be used.
  • it is preferably at least one selected from the group consisting of titanium oxide, aluminum oxide, zirconium oxide and magnesium oxide, and is titanium oxide and aluminum oxide. Is more preferable.
  • the titanium oxide rutile type titanium oxide is particularly preferable.
  • the average particle diameter of the inorganic filler is preferably 1 ⁇ m or less, and more preferably in the range of 0.1 to 0.8 ⁇ m.
  • the average particle diameter of an inorganic filler is larger than the average hole diameter of the separator which is a porous film.
  • the average particle diameter of the inorganic filler can be measured by the same method as the above-described method for measuring the average particle diameter of the electrode active material.
  • the said slurry for electrical storage devices can contain components other than the component mentioned above as needed.
  • examples of such components include a conductivity-imparting agent and a thickener.
  • the slurry for an electricity storage device When the slurry for an electricity storage device according to the present embodiment is used as a slurry for an electricity storage device electrode, it may further contain a conductivity-imparting agent.
  • the conductivity-imparting agent include carbon in a lithium ion secondary battery; cobalt nickel in a positive electrode; nickel powder, cobalt oxide, titanium oxide, and carbon in a negative electrode; Used.
  • examples of carbon include graphite, activated carbon, acetylene black, furnace black, graphite, carbon fiber, and fullerene. Among these, acetylene black or furnace black can be preferably used.
  • the use ratio of the conductivity-imparting agent is preferably 20 parts by mass or less, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the electrode active material.
  • the slurry for an electricity storage device may further contain a thickener from the viewpoint of improving its coatability.
  • the thickener include celluloses such as carboxymethylcellulose, methylcellulose, and hydroxypropylcellulose, and ammonium salts or alkali metal salts thereof; polycarboxylic acids such as poly (meth) acrylic acid and modified poly (meth) acrylic acid Acids, and alkali metal salts thereof; polyvinyl alcohol (co) polymers such as polyvinyl alcohol, modified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, and fumaric acid Water-soluble polymers such as a saponified product of a copolymer of an acid and a vinyl ester; Among these, particularly preferred thickeners are alkali metal salts of carboxymethyl cellulose, alkali metal salts of poly (meth) acrylic acid, and the like.
  • the use ratio of the thickener is preferably 20% by mass or less, more preferably 0.1 to 15%, based on the total solid content of the electricity storage device slurry. % By mass, particularly preferably 0.5 to 10% by mass.
  • the slurry for power storage device includes a polymer (A1), a liquid medium (B), inorganic particles (C), and additives used as necessary. It can manufacture by mixing. These can be mixed by stirring by a known method. For example, a stirrer, a defoaming machine, a bead mill, a high-pressure homogenizer, or the like can be used.
  • the preparation of the slurry for the electricity storage device is preferably performed at least part of the process under reduced pressure. Thereby, it can prevent that a bubble arises in the electrode layer obtained.
  • the degree of pressure reduction is preferably about 5.0 ⁇ 10 3 to 5.0 ⁇ 10 5 Pa as an absolute pressure.
  • the mixing and stirring for producing the slurry for the electricity storage device it is necessary to select a mixer that can stir to such an extent that the aggregate of the inorganic particles (C) does not remain in the slurry, and a necessary and sufficient dispersion condition. is there.
  • the degree of dispersion can be measured with a particle gauge, but it is preferable to mix and disperse so that aggregates larger than at least 100 ⁇ m are eliminated.
  • the mixer that meets such conditions include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, and a Hobart mixer.
  • the solid content concentration (the total mass of components other than the liquid medium (B) in the slurry is The ratio to the total mass) is preferably 20 to 80% by mass, more preferably 30 to 75% by mass.
  • the power storage device slurry according to the present embodiment when used as the protective film slurry, 0.1 to 20 parts by mass of the polymer (A1) is contained with respect to 100 parts by mass of the inorganic particles (C).
  • the content is preferably 1 to 10 parts by mass.
  • the slurry for an electricity storage device has a spinnability in the range of 30 to 80%, preferably 33 to 79%, and more preferably 35 to 78%.
  • spinnability is less than the above range, the leveling property is insufficient when applying the slurry for an electricity storage device, and thus it may be difficult to obtain a uniform coating film thickness.
  • an electricity storage device electrode or a protective film having an active material layer having a non-uniform thickness is used, an in-plane distribution of charge / discharge reaction occurs, making it difficult to achieve stable battery performance.
  • the “threadability” in the present invention is measured as follows. First, a Zaan cup (made by Dazai Equipment Co., Ltd., Zaan Bisco City Cup No. 5) having an opening with a diameter of 5.2 mm at the bottom is prepared. With this opening closed, 40 g of slurry for an electricity storage device is poured into the Zahn cup. Thereafter, when the opening is opened, the slurry for the electricity storage device flows out from the opening.
  • T 0 is the time when the opening is opened
  • T A is the time when the spinning of the slurry for the electricity storage device is finished
  • TB is the time when the outflow of the slurry for the electricity storage device is finished
  • the power storage device electrode according to the present embodiment includes a current collector and a layer formed by applying and drying the power storage device slurry on the surface of the current collector. .
  • Such an electricity storage device electrode is formed by applying the above-mentioned slurry for an electricity storage device on the surface of an appropriate current collector such as a metal foil to form a coating film, and then drying the coating film to form an active material layer.
  • an active material layer containing the polymer (A1) and the electrode active material described above and an optional component added as necessary is bound on the current collector. It will be.
  • Such an electricity storage device electrode has excellent binding properties between the current collector and the active material layer, and has good charge / discharge rate characteristics, which is one of the electrical characteristics.
  • the current collector is not particularly limited as long as it is made of a conductive material.
  • a current collector made of metal such as iron, copper, aluminum, nickel, and stainless steel is used.
  • aluminum is used for the positive electrode and copper is used for the negative electrode, The effect is most apparent.
  • a punching metal, an expanded metal, a wire mesh, a foam metal, a mesh metal fiber sintered body, a metal plated resin plate, or the like is used.
  • the shape and thickness of the current collector are not particularly limited, but it is preferable that the current collector be a sheet having a thickness of about 0.001 to 0.5 mm.
  • the coating can be performed by an appropriate method such as a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a dipping method, or a brush coating method.
  • the coating amount of the power storage device slurry is not particularly limited, but the thickness of the active material layer formed after removing the liquid medium (a concept including both water and a non-aqueous medium that is optionally used) is not limited. The amount is preferably 0.005 to 5 mm, and more preferably 0.01 to 2 mm.
  • the active material layer When the thickness of the active material layer is within the above range, the active material layer can be effectively infiltrated with the electrolytic solution. As a result, since metal ions accompanying charge / discharge between the electrode active material and the electrolytic solution in the active material layer can be easily transferred, the electrode resistance can be further reduced, which is preferable. In addition, since the thickness of the active material layer is within the above range, the active material layer does not peel from the current collector even when it is processed by folding or winding the electrode. And it is preferable at the point from which the electrical storage device electrode rich in a flexibility is obtained.
  • drying method from the coated film after coating (method for removing water and optionally used non-aqueous medium); for example, drying with warm air, hot air, low humidity air; vacuum drying; (far) infrared , Drying by irradiation with an electron beam or the like.
  • the drying speed is appropriately set so that the liquid medium can be removed as quickly as possible within a speed range in which the active material layer does not crack due to stress concentration or the active material layer does not peel from the current collector. be able to.
  • the pressing method includes a die press and a roll press.
  • the press conditions should be set appropriately depending on the type of press equipment used and the desired values of the porosity and density of the active material layer. This condition can be easily set by a few preliminary experiments by those skilled in the art.
  • the linear pressure of the roll press machine is 0.1 to 10 (t / cm), preferably 0.
  • the current collector feed speed (roll rotation speed) after drying is 1 to 80 m / min, preferably 5 to 50 m / min. It can be performed in min.
  • the density of the electrode active material layer after pressing is preferably 1.5 to 5.0 g / cm 3 , more preferably 1.5 to 4.0 g / cm 3, and 1.6 to 3. Particularly preferred is 8 g / cm 3 .
  • the density of the active material layer is preferably 2.0 to 4.0 g / cm 3 , More preferably, it is 3.0 to 3.5 g / cm 3 .
  • the electrode active material is a compound represented by the above general formula (4) and having an olivine type crystal structure
  • the density of the active material layer is preferably 1.5 to 2.5 g / cm 3.
  • the density of the active material layer is within the above range, the binding property between the current collector and the active material layer is improved, and an electricity storage device electrode having excellent powdering property and excellent electrical characteristics can be obtained. It will be. If the density of the active material layer is less than the above range, the polymer (A1) in the active material layer does not sufficiently function as a binder, and the active material layer is agglomerated and peeled off, resulting in a decrease in powder-off properties.
  • the “density of the active material layer” in the present invention is a value indicating the bulk density of the active material layer, and can be known from the following measurement method.
  • the mass of the current collector is A (g) and the mass of the electricity storage device electrode is B
  • the porosity of the active material layer after pressing is preferably 10 to 50%, more preferably 15 to 45%, and particularly preferably 20 to 40%.
  • the porosity of the active material layer is in the above range, the binding property between the current collector and the active material layer is improved, and an electricity storage device electrode having excellent powdering property and electrical characteristics can be obtained.
  • the porosity of the active material layer is within the above range, the electrolytic solution can be sufficiently infiltrated into the active material layer, and the surface of the electrode active material and the electrolytic solution can be sufficiently in contact with each other. As a result, transfer of lithium ions between the electrode active material and the electrolytic solution is facilitated, and good charge / discharge characteristics can be achieved.
  • the “porosity of the active material layer” refers to the volume of the pores (excluding the volume occupied by solids (electrode active material, conductivity-imparting agent, binder, etc.) from the volume of the active material layer).
  • (Quantity) is the ratio of the total volume of the active material layer. That is, in an electricity storage device electrode having an active material layer with an area C (cm 2 ) and a thickness D ( ⁇ m) on one side of the current collector, the mass of the active material layer was measured by B (g), a mercury intrusion method.
  • V (cm 3 / g) it is a value defined by the following formula (7).
  • Porosity (%) of active material layer ((V [cm 3 / g] ⁇ B [g]) / (C [cm 2 ] ⁇ D [ ⁇ m] ⁇ 10 ⁇ 4 )) ⁇ 100 ⁇ (7)
  • the pore volume can be measured, for example, by a mercury intrusion method using a mercury porosimeter.
  • the mercury porosimeter for example, the product name “PoreMaster” manufactured by Quantachrome, the product name “Autopore IV” manufactured by Shimadzu Corporation can be used.
  • the protective film according to the present embodiment can be formed by applying and drying the above-described slurry for an electricity storage device on the surface of the positive electrode, the negative electrode, or the separator.
  • the coating can be performed by an appropriate method such as a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a dipping method, or a brush coating method.
  • the coating amount of the protective film slurry is not particularly limited, but the thickness of the protective film formed after removing the liquid medium is preferably 0.5 to 4 ⁇ m, and preferably 0.5 to 3 ⁇ m. It is more preferable to use the amount. When the thickness of the protective film is in the above range, the permeability of the electrolytic solution into the electrode and the liquid retaining property are improved, and an increase in the internal resistance of the electrode can be suppressed.
  • drying method from the coated film after coating (method for removing water and optionally used non-aqueous medium); for example, drying with warm air, hot air, low humidity air; vacuum drying; (far) infrared , Drying by irradiation with an electron beam or the like.
  • the drying speed is appropriately set so that the liquid medium can be removed as quickly as possible within a speed range in which the active material layer does not crack due to stress concentration or the active material layer does not peel from the current collector. be able to.
  • the coating film is preferably dried at a temperature of 20 to 250 ° C., more preferably 50 to 150 ° C., preferably for 1 to 120 minutes, more preferably 5 to 60 minutes. be able to.
  • Electric storage device 4.1. 1st Embodiment The electrical storage device which concerns on one Embodiment of this invention is equipped with the above-mentioned electrical storage device electrode, contains an electrolyte solution, and can manufacture according to a conventional method using components, such as a separator. it can. As a specific manufacturing method, for example, a negative electrode and a positive electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery, put into a battery container, an electrolyte is injected into the battery container, and sealing is performed. The method of doing is mentioned.
  • the shape of the battery can be an appropriate shape such as a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, or a flat shape.
  • the electrolytic solution may be liquid or gel, and a material that effectively expresses the function as a battery may be selected from known electrolytic solutions used for the electricity storage device according to the type of the electrode active material.
  • the electrolytic solution can be a solution in which an electrolyte is dissolved in a suitable solvent.
  • any conventionally known lithium salt can be used, and specific examples thereof include, for example, LiClO 4 , LiBF 4 , LiPF 6 , LiCF 3 CO 2 , LiAsF. 6 , LiSbF 6 , LiB 10 Cl 10 , LiAlCl 4 , LiCl, LiBr, LiB (C 2 H 5 ) 4 , LiCF 3 SO 3 , LiCH 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 N, lithium of lower fatty acid carboxylate etc.
  • an aqueous potassium hydroxide solution having a conventionally known concentration of 5 mol / liter or more can be used.
  • the solvent for dissolving the electrolyte is not particularly limited, and specific examples thereof include carbonate compounds such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate; Lactone compounds such as butyrolactone; ether compounds such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran; sulfoxide compounds such as dimethyl sulfoxide, etc. One or more selected from among them can be used.
  • the concentration of the electrolyte in the electrolytic solution is preferably 0.5 to 3.0 mol / L, more preferably 0.7 to 2.0 mol / L.
  • the type and concentration of the electrolyte in the case of manufacturing a lithium ion capacitor are the same as in the case of the lithium ion secondary battery.
  • an electricity storage device includes a positive electrode, a negative electrode, a protective film disposed between the positive electrode and the negative electrode, and an electrolytic solution, and the protective film Is the above-mentioned protective film. Specific examples will be described below with reference to the drawings.
  • FIG. 1 is a schematic diagram illustrating a cross section of an electricity storage device according to a first specific example.
  • the positive electrode 10 having the positive electrode active material layer 14 formed on the surface of the positive electrode current collector 12 and the negative electrode active material layer 24 formed on the surface of the negative electrode current collector 22.
  • no separator is provided between the positive electrode 10 and the negative electrode 20. This is because if the positive electrode 10 and the negative electrode 20 are completely fixed with a solid electrolyte or the like, the positive electrode 10 and the negative electrode 20 do not come into contact with each other to cause a short circuit.
  • the positive electrode 10 shown in FIG. 1 is formed so that the positive electrode active material layer 14 is not provided on one surface along the longitudinal direction and the positive electrode current collector 12 is exposed. A layer 14 may be provided.
  • the negative electrode 20 shown in FIG. 1 is formed such that the negative electrode active material layer 24 is not provided on one surface along the longitudinal direction and the negative electrode current collector 22 is exposed, A negative electrode active material layer 24 may be provided.
  • Electrode active material As the positive electrode active material and the negative electrode active material, the materials described in the above “1.3.1. Electrode active material” can be used as necessary. As the positive electrode current collector 12 and the negative electrode current collector 22, the materials described in the above “2. Power storage device electrode” can be used as necessary. The positive electrode active material layer 14 and the negative electrode active material layer 24 can be manufactured as necessary under the conditions described in the above “2. Power storage device electrode”.
  • the protective film 30 can be formed, for example, by applying the slurry for an electricity storage device described above on the surface of the positive electrode 10 (or the negative electrode 20) and drying it.
  • the slurry for the electricity storage device on the surface of the positive electrode 10 (or the negative electrode 20)
  • Protective film" can be used.
  • the protective film 30 is disposed between the positive electrode 10 and the negative electrode 20. 1, the protective film 30 is disposed between the positive electrode 10 and the negative electrode 20 so as to be in contact with the positive electrode active material layer 14, but is disposed so as to be in contact with the negative electrode active material layer 24. May be.
  • the protective film 30 may be disposed as a self-supporting film between the positive electrode 10 and the negative electrode 20 without being in contact with the positive electrode 10 or the negative electrode 20. Thereby, even if it is a case where dendrites precipitate by repeating charging / discharging, since it is guarded by the protective film 30, a short circuit does not occur. Therefore, the function as an electricity storage device can be maintained.
  • the thickness of the protective film 30 is not particularly limited, but is preferably in the range of 0.5 to 4 ⁇ m, and more preferably in the range of 0.5 to 3 ⁇ m. When the thickness of the protective film 30 is within the above range, the permeability of the electrolytic solution into the electrode and the liquid retaining property are improved, and an increase in the internal resistance of the electrode can be suppressed.
  • the electrolytic solution 40 is appropriately selected and used according to the type of the target electricity storage device.
  • the materials described in “4.1. First Embodiment” can be used as necessary.
  • FIG. 2 is a schematic view showing a cross section of an electricity storage device according to a second specific example.
  • the positive electrode 110 having the positive electrode active material layer 114 formed on the surface of the positive electrode current collector 112 and the negative electrode active material layer 124 formed on the surface of the negative electrode current collector 122.
  • the electricity storage device 2 is different from the electricity storage device 1 described above in that the protective film 130 is disposed between the positive electrode 110 and the separator 150. 2, the protective film 130 is sandwiched between the positive electrode 110 and the separator 150, but the protective film 130 is sandwiched between the negative electrode 120 and the separator 150. It may be arranged so that. By adopting such a configuration, even when dendrite is deposited by repeated charge and discharge, the protective film 130 guards and no short circuit occurs. Therefore, the function as an electricity storage device can be maintained.
  • the protective film 130 can be formed, for example, by applying and drying the above slurry for an electricity storage device on the surface of the positive electrode 110 (or the negative electrode 120) or the separator 150.
  • the protective film-forming slurry to the surface of the positive electrode 110 (or the negative electrode 120) or the separator 150, the conditions and means described in “4. Protective film” can be used.
  • Any separator 150 may be used as long as it is electrically stable, chemically stable with respect to the positive electrode active material, the negative electrode active material, or the solvent, and has no electrical conductivity.
  • a polymer nonwoven fabric, a porous film, glass or ceramic fibers in a paper shape can be used, and a plurality of these may be laminated.
  • a porous polyolefin film is preferably used, and a composite of this with a heat-resistant material made of polyimide, glass, ceramic fibers or the like may be used.
  • FIG. 3 is a schematic diagram illustrating a cross section of an electricity storage device according to a third specific example.
  • the positive electrode 210 having the positive electrode active material layer 214 formed on the surface of the positive electrode current collector 212 and the negative electrode active material layer 224 formed on the surface of the negative electrode current collector 222.
  • the electricity storage device 3 is different from the electricity storage device 1 and the electricity storage device 2 described above in that the protective film 230 is formed so as to cover the surface of the separator 250.
  • the protective film 230 guards the short circuit. Therefore, the function as an electricity storage device can be maintained.
  • the protective film 230 can be formed, for example, by applying the above-described slurry for an electricity storage device on the surface of the separator 250 and drying it.
  • a method for applying the slurry for the electricity storage device to the surface of the separator 250 the conditions and means described in the above "4. Protective film" can be used.
  • the shape of the battery can be an appropriate shape such as a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, or a flat shape.
  • the power storage device described above is suitable as a secondary battery or capacitor mounted on an automobile such as an electric vehicle, a hybrid car, or a truck, and also used as a secondary battery or capacitor for AV equipment, OA equipment, communication equipment, etc. It is also suitable.
  • polymer A a polymer having a total content of specific functional groups per 100 g of solid content of 0 mol.
  • Synthesis example 2 In an autoclave equipped with a stirrer, 300 parts by mass of ion-exchanged water, 80 parts by mass of n-butyl acrylate, 15 parts by mass of acrylonitrile, 1 part by mass of ethyl 2-methylammonium sulfate, 4 parts by mass of glycidyl methacrylate, 0. 5 parts by weight, 3 parts by weight of sodium dodecylbenzenesulfonate and 0.7 parts by weight of ⁇ , ⁇ '-azoisobutyronitrile were added and stirred sufficiently, followed by polymerization by heating to 80 ° C. to obtain a latex. It was. The polymerization conversion rate determined from the solid content concentration was about 99%.
  • polymer B a polymer (hereinafter referred to as “polymer B”).
  • polymer B a polymer having a total content of specific functional groups per 100 g of solid content of 0.005 mol.
  • Synthesis Examples 3 to 9 A dispersion containing 40% of each of polymers C to I was prepared in the same manner as in Synthesis Example 2 except that the monomer composition shown in Table 1 was used.
  • polyoxyethylene dodecyl ether sulfonate 1.5 parts by mass was dissolved in ion-exchanged water (92 parts by mass).
  • a monomer component of the polymer a mixture of ethyl acrylate (65 parts by mass) and methacrylic acid (35 parts by mass) was added to prepare a pre-emulsion.
  • 5% of the pre-emulsion containing the monomer component was put into a reaction vessel and stirred, and then sodium bisulfite (0.017 part by mass) was added.
  • ammonium persulfate (0.23 parts by mass) was dissolved in ion-exchanged water (23 parts by mass) to prepare a polymerization initiator aqueous solution.
  • polymer J aqueous solution containing 40% of a polymer
  • Synthesis Examples 11-12 An aqueous solution containing 40% of each of polymers K to L was prepared in the same manner as in Synthesis Example 10 except that the monomer composition shown in Table 1 was used.
  • Table 1 shows the polymerizable monomer composition and the total content (mole) of specific functional groups per 100 g of the polymers A to L synthesized in Synthesis Examples 1 to 12.
  • the notation “-” in Table 1 indicates that the corresponding component was not used.
  • Synthesis Example 13 After the inside of an autoclave having an internal volume of about 6 L equipped with an electromagnetic stirrer was sufficiently purged with nitrogen, 2.5 L of deoxygenated pure water and 25 g of ammonium perfluorodecanoate as an emulsifier were charged and stirred at 350 rpm at 60 ° C. The temperature was raised to. Next, a mixed gas composed of 70% of vinylidene fluoride (VDF) as a monomer and 30% of propylene hexafluoride (HFP) was charged until the internal pressure reached 20 kg / cm 2 .
  • VDF vinylidene fluoride
  • HFP propylene hexafluoride
  • NMP corresponding to 300 parts by mass is added to 50 parts by mass of the composition thus obtained, and water and a part of NMP are distilled off under reduced pressure conditions using a rotary evaporator.
  • An NMP solution containing 10% of A1) and the polymer (A2) was prepared.
  • the residual moisture content of the prepared NMP solution was measured with Karl Fischer (Mitsubishi Chemical Analytic, model “CA-200”) and found to be 350 ppm.
  • ether sulfate type emulsifier (trade name “ADEKA rear soap SR1025”, manufactured by ADEKA Corporation) as an emulsifier, 1.3 parts by mass in terms of solid content, and 2, A monomer emulsion containing 85 parts by mass of 2,2-trifluoroethyl methacrylate, 5 parts by mass of methyl methacrylate and 10 parts by mass of 2-ethylhexyl acrylate and sufficiently stirring was prepared.
  • the temperature inside the separable flask was started, and when the temperature inside the separable flask reached 60 ° C., 0.5 parts by mass of ammonium persulfate was added as a polymerization initiator. Then, when the temperature inside the separable flask reaches 70 ° C., the addition of the monomer emulsion prepared above is started, and the monomer emulsion is added while maintaining the temperature inside the separable flask at 70 ° C. Slowly added over time. Thereafter, the temperature inside the separable flask was raised to 85 ° C., and this temperature was maintained for 3 hours to carry out the polymerization reaction.
  • the separable flask was cooled to stop the reaction, and then ammonium water was added to adjust the pH to 7.6 to obtain a composition containing the polymer (A2). Furthermore, with respect to 40 parts by mass of the polymer (A2), the polymer B synthesized in the previous Synthesis Example 2 corresponding to the polymer (A1) is added to 100 parts by mass, and the polymer (A1) and the polymer (A1) are combined. A composition having a total of combined (A2) of 30% by mass was obtained.
  • NMP corresponding to 300 parts by mass is added to 50 parts by mass of the composition thus obtained, and water and a part of NMP are distilled off under reduced pressure conditions using a rotary evaporator.
  • An NMP solution containing 10% of A1) and the polymer (A2) was prepared.
  • the residual moisture content of the prepared NMP solution was measured by Karl Fischer (Mitsubishi Chemical Analytic, model “CA-200”), and was 300 ppm.
  • Synthesis Examples 19-21 An NMP solution containing 10% of the polymer (A1) and the polymer (A2) was prepared in the same manner as in Synthesis Example 18 except that the monomer composition shown in Table 2 was used. Table 2 below shows the polymerizable monomer composition and the total content (mole) of specific functional groups per 100 g of the polymers (A1) and (A2) synthesized in Synthesis Examples 13 to 21. In Table 2, the notation “-” indicates that the corresponding component was not used.
  • Example 1 5.2.1. Preparation and Evaluation of Storage Device Electrode Slurry Biaxial Planetary Mixer (product name “TK Hibismix 2P-03” manufactured by PRIMIX Co., Ltd.) 1 part by mass of carboxymethyl cellulose (product name “CMC2200” manufactured by Daicel Corporation) (Solid content conversion)
  • TK Hibismix 2P-03 manufactured by PRIMIX Co., Ltd.
  • CMC2200 carboxymethyl cellulose
  • Solid content conversion As a negative electrode active material, 100 parts by mass of graphite (in terms of solid content) and 68 parts by mass of water were added and stirred at 60 rpm for 1 hour. Thereafter, 2 parts by mass (in terms of solid content) of the polymer B synthesized in the above “5.1.2. Synthesis Example 2” was added, and the mixture was further stirred for 1 hour to obtain a paste.
  • the spinnability of the obtained slurry for electricity storage device electrodes was measured as follows. First, a Zaan cup (made by Dazai Equipment Co., Ltd., Zaan Biscocity Cup No. 5) having an opening with a diameter of 5.2 mm at the bottom of the container was prepared. With the opening of the Zahn cup closed, 40 g of the slurry for the electricity storage device electrode prepared above was poured. When the opening was opened, the slurry flowed out. In this case, the time instant of opening the opening and T0, the time continued to flow out so as to draw the yarn when the slurry flows measured visually, the time was T A.
  • the slurry for electricity storage device electrode prepared above is uniformly applied to the surface of a current collector made of copper foil having a thickness of 20 ⁇ m by a doctor blade method so that the film thickness after drying becomes 80 ⁇ m. And dried at 120 ° C. for 20 minutes. Then, the electrical storage device electrode (negative electrode) was obtained by pressing with a roll-press machine so that the density of an active material layer may be 1.5 g / cm ⁇ 3 >.
  • a test piece having a width of 2 cm and a length of 12 cm was cut out from the obtained electricity storage device electrode, and the active material layer side surface of the test piece was attached to an aluminum plate using a double-sided tape.
  • a 18 mm wide tape manufactured by Nichiban Co., Ltd., trade name “Cello Tape (registered trademark)”, prescribed in JIS Z1522 was attached to the surface of the current collector of the test piece.
  • a lithium ion secondary battery cell (electric storage device) is assembled by placing the positive electrode manufactured in step 16 with a diameter of 16.16 mm and placing the outer body of the two-pole coin cell with a screw and sealing. It was.
  • charging is started at a constant current (3C) for the same cell, and when the voltage reaches 4.2V, charging is continued at a constant voltage (4.2V).
  • the charging capacity at 3C was measured with the time point of becoming the completion of charging (cut-off).
  • discharge was started at a constant current (3C), and when the voltage reached 2.7 V, the discharge was completed (cut off), and the discharge capacity at 3C was measured.
  • 1C in the measurement condition indicates a current value at which discharge is completed in one hour after constant-current discharge of a cell having a certain electric capacity.
  • 0.1 C is a current value at which discharge is completed over 10 hours
  • 10 C is a current value at which discharge is completed over 0.1 hours.
  • Example 11 5.5.1. Preparation and Evaluation of Protective Film Slurry Titanium oxide (product name “KR380”, manufactured by Titanium Industry Co., Ltd., rutile type, number average particle size 0.38 ⁇ m) is used as inorganic particles (C) with respect to 100 parts by mass of ion-exchanged water. 20 parts by mass, 5 parts by mass in terms of solid content of polymer B prepared above with respect to 100 parts by mass of inorganic particles, and carboxymethyl cellulose (trade name “manufactured by Daicel Corporation, trade name“ CMC1120 ”) is added and T.C. K. Using a Mixmix (R) type 56-50 (manufactured by PRIMIX Co., Ltd.), a mixture dispersion treatment was performed to prepare a slurry for a protective film in which titanium oxide was dispersed.
  • R Mixmix
  • a biaxial planetary mixer (product name “TK Hibismix 2P-03” manufactured by PRIMIX Corporation), 4 parts by mass of polyvinylidene fluoride (PVDF) (in terms of solid content), 100 parts by mass of the above active material particles, and acetylene black 5 Part by mass and 68 parts by mass of N-methylpyrrolidone (NMP) were added and stirred at 60 rpm for 1 hour. Further, 32 parts by mass of NMP was added and stirred for 1 hour to obtain a paste.
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • the resulting paste was stirred at 200 rpm for 2 minutes, 1,800 rpm for 5 minutes, and further under vacuum (5.0 ⁇ ) using a stirring defoaming machine (trade name “Awatori Nertaro” manufactured by Shinky Co., Ltd.).
  • the slurry for positive electrode was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes at 10 3 Pa).
  • the positive electrode slurry was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 100 ⁇ m, and dried at 120 ° C. for 20 minutes. Then, the positive electrode with the positive electrode active material layer formed on the surface of the current collector was obtained by pressing with a roll press so that the density of the film (active material layer) was 2.0 g / cm 3 .
  • the negative electrode slurry was uniformly applied to the surface of a current collector made of copper foil by a doctor blade method so that the film thickness after drying was 150 ⁇ m, and dried at 120 ° C. for 20 minutes. Then, the negative electrode in which the negative electrode active material layer was formed on the surface of the current collector was obtained by pressing using a roll press machine so that the film density was 1.5 g / cm 3 .
  • a separator made of a polypropylene porous membrane punched into a diameter of 24 mm (trade name “Celguard # 2400” manufactured by Celgard Co., Ltd.) was placed, and after injecting 500 ⁇ L of an electrolyte solution so that air did not enter,
  • the positive electrode with a protective film manufactured in the above is punched into a shape of 16.16 mm and placed so that the separator and the protective film formed on the positive electrode face each other, and the outer body of the bipolar coin cell is closed with a screw.
  • the lithium ion battery cell (electric storage device) was assembled by sealing.
  • the charge / discharge rate characteristics were evaluated in the same manner as in “5.2.3. Production and evaluation of electricity storage device” in Example 1 above. The results are also shown in Table 4.
  • the positive electrode with a protective film was peeled off from the separator and evaluated as follows. ⁇ : There is resistance when the positive electrode is peeled off, and a part or all of the active material layer is adhered and transferred to the protective film. X: There is no resistance when the positive electrode is peeled off, and the active material layer is transferred to the protective film. If not
  • Example 21 5.8.1. Production of Positive Electrode and Negative Electrode A positive electrode and a negative electrode were produced in the same manner as in Example 11 above. Note that the positive electrode has no protective film formed on the surface of the positive electrode active material layer.
  • the lithium ion battery cell (power storage device) was assembled by placing the product and sealing the outer body of the bipolar coin cell with a screw.
  • Examples 22 to 27, Comparative Examples 15 to 19 In the above “5.5.1. Preparation and Evaluation of Slurry for Protective Film”, the type of polymer is changed to that shown in Table 5, and the addition amount of carboxymethyl cellulose is adjusted as appropriate to adjust the spinnability in Table 5.
  • the protective film slurries of Examples 22 to 27 and Comparative Examples 15 to 19 were prepared in the same manner as in Example 11 except that the changes were made to be.
  • a positive electrode, a negative electrode, a separator with a protective film, and an electricity storage device were produced and evaluated in the same manner as in Example 21 using the obtained slurry for protective film. The evaluation results are also shown in Table 5.
  • Examples 28-30, Comparative Examples 20-21 In “5.5. 1. Preparation and Evaluation of Slurry for Protective Film” above, the type of polymer is changed to that shown in Table 5, and the amount of ion-exchanged water is adjusted as appropriate to adjust the yarn in Table 5
  • Each of the protective film slurries of Examples 28 to 30 and Comparative Examples 20 to 21 was prepared in the same manner as in Example 11 except that the properties were changed so as to be suitable.
  • a positive electrode, a negative electrode, a separator with a protective film, and an electricity storage device were produced and evaluated in the same manner as in Example 21 using the obtained slurry for protective film. The evaluation results are also shown in Table 5.
  • Titanium oxide Product name “KR380” (manufactured by Titanium Industry Co., Ltd., rutile type, number average particle size 0.38 ⁇ m)
  • Aluminum oxide Product name “AKP-3000” (manufactured by Sumitomo Chemical Co., Ltd., number average particle size 0.74 ⁇ m)
  • Zirconium oxide Product name “UEP zirconium oxide” (manufactured by Daiichi Elemental Chemical Co., Ltd., number average particle diameter 0.67 ⁇ m)
  • Magnesium oxide Product name “PUREMAG® FNM-G” (manufactured by Tateho Chemical Co., Ltd., number average particle size 0.50 ⁇ m)
  • Example 31 5.11.1. Production of negative electrode ⁇ Preparation of slurry for negative electrode> In a biaxial planetary mixer (product name “TK Hibismix 2P-03” manufactured by PRIMIX Co., Ltd.), 4 parts by mass of the polymer obtained in Synthesis Example 13 (in terms of solid content) and graphite as a negative electrode active material 100 parts by mass (in terms of solid content) and 80 parts by mass of N-methylpyrrolidone (NMP) were added and stirred at 60 rpm for 1 hour.
  • NMP N-methylpyrrolidone
  • the negative electrode slurry was uniformly applied to the surface of a current collector made of copper foil by a doctor blade method so that the film thickness after drying was 150 ⁇ m, and dried at 120 ° C. for 20 minutes. Then, the negative electrode in which the negative electrode active material layer was formed on the surface of the current collector was obtained by pressing using a roll press machine so that the film density was 1.5 g / cm 3 .
  • Example 32 5.12.1. Production of positive electrode ⁇ Preparation of positive electrode active material>
  • Commercially available lithium iron phosphate (LiFePO 4 ) was pulverized in an agate mortar and classified using a sieve to prepare active material particles having a particle diameter (D50 value) of 0.5 ⁇ m.
  • the resulting paste was stirred at 200 rpm for 2 minutes, 1,800 rpm for 5 minutes, and further under vacuum (5.0 ⁇ ) using a stirring defoaming machine (trade name “Awatori Nertaro” manufactured by Shinky Co., Ltd.).
  • the slurry for positive electrode was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes at 10 3 Pa).
  • the positive electrode slurry was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 100 ⁇ m, and dried at 120 ° C. for 20 minutes. Then, the positive electrode with the positive electrode active material layer formed on the surface of the current collector was obtained by pressing with a roll press so that the density of the film (active material layer) was 2.0 g / cm 3 .
  • the counter electrode (negative electrode) slurry prepared above was uniformly applied to the surface of the current collector made of copper foil by the doctor blade method so that the film thickness after drying was 150 ⁇ m, and dried at 120 ° C. for 20 minutes. . Then, the counter electrode (negative electrode) was obtained by pressing using a roll-press machine so that the density of a film
  • Example 33 5.13.1. Manufacture of Positive Electrode 4.0 parts by mass (converted to solid content) of the polymer obtained in Synthesis Example 15 above in a biaxial planetary mixer (trade name “TK Hibismix 2P-03” manufactured by PRIMIX Corporation), conductive Auxiliary agent (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “Denka Black 50% Pressed Product”) 3.0 parts by mass, LiCoO 2 having a particle size of 5 ⁇ m (made by Hayashi Kasei Co., Ltd.) 100 parts by mass (solid content) Conversion), 36 parts by mass of N-methylpyrrolidone (NMP) was added and stirred at 60 rpm for 2 hours.
  • NMP N-methylpyrrolidone
  • the slurry for positive electrode was prepared by stirring and mixing for 5 minutes at 1800 rpm for 1 minute at 1800 rpm.
  • the prepared positive electrode slurry was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 80 ⁇ m, followed by drying treatment at 120 ° C. for 20 minutes.
  • the positive electrode was obtained by pressing with a roll press so that the density of an active material layer might be set to 3.0 g / cm ⁇ 3 >.
  • the counter electrode (negative electrode) slurry prepared above was uniformly applied to the surface of the current collector made of copper foil by the doctor blade method so that the film thickness after drying was 150 ⁇ m, and dried at 120 ° C. for 20 minutes. . Then, the counter electrode (negative electrode) was obtained by pressing using a roll-press machine so that the density of a film
  • Example 34 Comparative Examples 22 to 26
  • the type of polymer is changed to that shown in Table 6, and the amount of NMP added is adjusted as appropriate to achieve the spinnability shown in Table 6.
  • a slurry for an electricity storage device electrode was prepared in the same manner as in Example 31 except that the above changes were made.
  • Example 34 and Comparative Examples 23 and 25 using lithium iron phosphate as the inorganic particles (C) the type of polymer was changed to that shown in Table 6, and the amount of NMP added was adjusted as appropriate.
  • a slurry for an electricity storage device electrode was prepared in the same manner as in Example 32 except that the spinnability was changed to 6.
  • Example 26 using lithium cobaltate as the inorganic particles (C), the type of polymer was changed to that shown in Table 6, and the amount of NMP added was adjusted as appropriate to achieve the spinnability shown in Table 6.
  • a slurry for an electricity storage device electrode was prepared in the same manner as in Example 33 except that the above changes were made. Using the thus obtained slurry for an electricity storage device electrode, “5.2.2. Production and evaluation of electricity storage device electrode”, “5.2.3. Production and evaluation of electricity storage device” in Example 1 above. In the same manner as described above, an electricity storage device electrode and an electricity storage device were produced and evaluated. The results are also shown in Table 6.
  • Polyimide was synthesized by the method described in JP-A-2009-87562. That is, in a four-necked flask equipped with a cooling pipe and a nitrogen gas inlet, 1.0 mol of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, o-tolidine diisocyanate 0 .95 mol is mixed with N-methyl-2-pyrrolidone (NMP) so that the solid content concentration becomes 20% by mass, 0.01 mol of diazabicycloundecene is added as a catalyst and stirred, and the mixture is stirred at 120 ° C. for 4 minutes. Reacted for hours.
  • NMP N-methyl-2-pyrrolidone
  • Comparative Example 28 The polymer type was changed to polyamideimide synthesized by the following method, and the addition amount of NMP was adjusted as appropriate so that the spinnability shown in Table 6 was changed. A slurry for negative electrode was prepared. Using the negative electrode slurry thus obtained, “5.2.2. Production and evaluation of electricity storage device electrode”, “5.2.3. Production and evaluation of electricity storage device” in Example 1 above. Similarly, an electricity storage device electrode and an electricity storage device were produced and evaluated. The results are also shown in Table 6.
  • Polyamideimide was synthesized by the method described in JP2007-154029A. That is, 0.7 mol of trimellitic anhydride (TMA), 3,3 ′, 4,4′-benzophenone tetracarboxylic anhydride (BTDA) 0. 3 mol, 1 mol of naphthalene diisocyanate (NDI) and 0.01 mol of diazabicycloundecene (DBU) were charged together with N-methyl-2-pyrrolidone (NMP) to a solid content concentration of 15% at 80 ° C. The reaction was performed for about 3 hours.
  • TMA trimellitic anhydride
  • BTDA 4,4′-benzophenone tetracarboxylic anhydride
  • NDI naphthalene diisocyanate
  • DBU diazabicycloundecene
  • NMP N-methyl-2-pyrrolidone
  • Example 35 5.17.1. Preparation and Evaluation of Slurry for Protective Film 20 parts by mass of titanium oxide (product name “KR380”, manufactured by Titanium Industry Co., Ltd., rutile type, number average particle size 0.38 ⁇ m) as inorganic particles (C) with respect to 80 parts by mass of NMP NMP was added so that the polymer obtained in Synthesis Example 13 was 5 parts by mass in terms of solid content with respect to 100 parts by mass of inorganic particles, and the spinnability was 60%.
  • K Using a Mixmix (R) type 56-50 (manufactured by PRIMIX Co., Ltd.), a mixture dispersion treatment was performed to prepare a slurry for a protective film in which titanium oxide was dispersed.
  • the slurry for positive electrode was prepared by stirring and mixing for 5 minutes at 1800 rpm for 1 minute at 1800 rpm.
  • the prepared positive electrode slurry was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 80 ⁇ m, followed by drying treatment at 120 ° C. for 20 minutes.
  • the counter electrode positive electrode was obtained by pressing with a roll press so that the density of an active material layer might be 3.0 g / cm ⁇ 3 >.
  • a separator made of a polypropylene porous membrane punched into a diameter of 24 mm (trade name “Celguard # 2400” manufactured by Celgard Co., Ltd.) was placed, and after injecting 500 ⁇ L of an electrolyte solution so that air did not enter,
  • the negative electrode with a protective film produced in the above-mentioned process is punched and molded to a diameter of 16.16 mm and placed so that the separator and the protective film formed on the negative electrode face each other, and the outer body of the bipolar coin cell is closed with a screw.
  • the lithium ion battery cell (electric storage device) was assembled by sealing.
  • the charge / discharge rate characteristics were evaluated in the same manner as in “5.2.3. Production and evaluation of electricity storage device” in Example 1 above. The results are also shown in Table 7.
  • the negative electrode with a protective film was peeled off from the separator and evaluated as follows. ⁇ : There is resistance when the negative electrode is peeled off, and part or all of the active material layer is adhered and transferred to the protective film. ⁇ : There is no resistance when the negative electrode is peeled off, and the active material layer is transferred to the protective film. If not
  • Example 36 5.18.1. Preparation and Evaluation of Slurry for Protective Film Aluminum oxide as inorganic particles (C): 20 parts by mass of product name “AKP-3000” (manufactured by Sumitomo Chemical Co., Ltd., number average particle size 0.74 ⁇ m) with respect to 80 parts by mass of NMP, NMP was added so that the polymer obtained in Synthesis Example 14 was 5 parts by mass in terms of solid content with respect to 100 parts by mass of the inorganic particles, and the spinnability was 36%.
  • K Using a Mixmix (R) type 56-50 (manufactured by PRIMIX Co., Ltd.), a mixture dispersion treatment was performed to prepare a slurry for a protective film in which titanium oxide was dispersed.
  • a biaxial planetary mixer (product name “TK Hibismix 2P-03” manufactured by PRIMIX Corporation), 4 parts by mass of polyvinylidene fluoride (PVDF) (in terms of solid content), 100 parts by mass of the above active material particles, and acetylene black 5 Part by mass and 68 parts by mass of N-methylpyrrolidone (NMP) were added and stirred at 60 rpm for 1 hour. Further, 32 parts by mass of NMP was added and stirred for 1 hour to obtain a paste.
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • the resulting paste was stirred at 200 rpm for 2 minutes, 1,800 rpm for 5 minutes, and further under vacuum (5.0 ⁇ ) using a stirring defoaming machine (trade name “Awatori Nertaro” manufactured by Shinky Co., Ltd.).
  • the slurry for positive electrode was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes at 10 3 Pa).
  • the positive electrode slurry was uniformly applied to the surface of a current collector made of aluminum foil by a doctor blade method so that the film thickness after drying was 100 ⁇ m, and dried at 120 ° C. for 20 minutes. Then, the positive electrode with the positive electrode active material layer formed on the surface of the current collector was obtained by pressing with a roll press so that the density of the film (active material layer) was 2.0 g / cm 3 .
  • the negative electrode slurry was uniformly applied to the surface of a current collector made of copper foil by a doctor blade method so that the film thickness after drying was 150 ⁇ m, and dried at 120 ° C. for 20 minutes. Then, the negative electrode in which the negative electrode active material layer was formed on the surface of the current collector was obtained by pressing using a roll press machine so that the film density was 1.5 g / cm 3 .
  • Examples 37 to 38, Comparative Examples 29 to 35 The procedure was carried out in the same manner as in Example 36 except that the polymer type was changed to the one shown in Table 7 and the addition amount of NMP was adjusted as appropriate so that the spinnability shown in Table 7 was obtained.
  • the slurry for each protective film of Examples 37-38 and Comparative Examples 29-35 was prepared. Using each of the obtained protective film slurries, a positive electrode with a protective film, a negative electrode, and an electricity storage device were produced and evaluated in the same manner as in Example 36. The evaluation results are also shown in Table 7.
  • the polyimide used in Comparative Example 34 is the polyimide synthesized in Comparative Example 27, and the polyamideimide used in Comparative Example 35 is the polyamideimide synthesized in Comparative Example 28.
  • the present invention is not limited to the above embodiment, and various modifications can be made.
  • the present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects).
  • the present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration.
  • the present invention includes a configuration that achieves the same effect as the configuration described in the above embodiment or a configuration that can achieve the same object.
  • the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

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Abstract

La présente invention concerne une composition pour des dispositifs de stockage d'électricité et une bouillie pour des dispositifs de stockage d'électricité, dont chacune est capable de produire une électrode de dispositif de stockage d'électricité et un film de protection qui présentent une excellente adhérence et d'excellentes caractéristiques de charge/décharge. Une composition pour dispositifs de stockage d'électricité selon la présente invention est une composition pour la production d'un dispositif de stockage d'électricité, qui contient un polymère (A1), un polymère (A2) et un matériau liquide (B). Cette composition pour dispositifs de stockage d'électricité est caractérisée en ce que : le polymère (A1) contient au moins un groupe fonctionnel qui est sélectionné parmi le groupe constitué d'un groupe sulfo, d'un groupe carboxy et d'un groupe d'un sel d'un groupe sulfo ou d'un groupe carboxy dans une quantité de 0,001 à 1,2 mole au total par 100 g du polymère (A1) ; le polymère (A1) possède un motif répété représenté par la formule générale (1) ; et le rapport de contenu d'un motif répété dérivé d'un monomère qui comporte un atome de fluor est 80 parties en masse ou plus dans 100 parties en masse du polymère (A2). (Dans la formule, R1 représente un atome d'hydrogène ou un groupe méthyle ; et R2 représente un groupe alkyle qui possède 1 à 16 atomes de carbone ou un groupe cycloalkyle.)
PCT/JP2014/065311 2013-06-20 2014-06-10 Composition pour dispositifs de stockage d'électricité, bouillie pour dispositifs de stockage d'électricité, électrode de dispositif de stockage d'électricité, procédé de production d'électrode de dispositif de stockage d'électricité, film de protection, procédé de production de film de protection, et de dispositif de stockage d'électricité Ceased WO2014203767A1 (fr)

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KR1020157035133A KR20160021771A (ko) 2013-06-20 2014-06-10 축전 디바이스용 조성물, 축전 디바이스용 슬러리, 축전 디바이스 전극 및 그의 제조 방법, 보호막 및 그의 제조 방법, 및 축전 디바이스
CN201480035131.1A CN105340113A (zh) 2013-06-20 2014-06-10 蓄电设备用组合物、蓄电设备用浆料、蓄电设备电极及其制造方法、保护膜及其制造方法以及蓄电设备

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