WO2014157715A1 - 蓄電デバイス用バインダー組成物 - Google Patents

蓄電デバイス用バインダー組成物 Download PDF

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WO2014157715A1
WO2014157715A1 PCT/JP2014/059388 JP2014059388W WO2014157715A1 WO 2014157715 A1 WO2014157715 A1 WO 2014157715A1 JP 2014059388 W JP2014059388 W JP 2014059388W WO 2014157715 A1 WO2014157715 A1 WO 2014157715A1
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Prior art keywords
storage device
mass
electricity storage
polymer
binder composition
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English (en)
French (fr)
Japanese (ja)
Inventor
巧治 大塚
伸行 藤原
裕之 宮内
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JSR Corp
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JSR Corp
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Priority to KR1020157019955A priority Critical patent/KR20150135207A/ko
Priority to JP2014532161A priority patent/JP5673987B1/ja
Priority to US14/779,840 priority patent/US9966606B2/en
Priority to CN201480018491.0A priority patent/CN105103349A/zh
Publication of WO2014157715A1 publication Critical patent/WO2014157715A1/ja
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
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    • H—ELECTRICITY
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F222/30—Nitriles
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
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    • 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
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    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
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    • 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
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Definitions

  • the present invention relates to a binder composition for an electricity storage device.
  • a power storage device having a high voltage and a high energy density has been required as a power source for driving electronic devices.
  • As an electricity storage device for this application lithium ion batteries, lithium ion secondary batteries, lithium ion capacitors and the like are expected.
  • the electrode used for such an electrical storage device is normally manufactured by apply
  • 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 referred to as “electrode active material layer” or simply “active material layer”).
  • electrode active material layer or simply “active material layer”.
  • the degree of freedom in designing the structure of the electricity storage device such as the method of folding the obtained electrode and setting the winding radius, is increased, and the miniaturization of the device is achieved. Can do.
  • the bonding ability between the electrode active materials and the adhesion ability between the electrode active material layer and the current collector, and the powder fall resistance it has been empirically revealed that the performance is almost proportional. . Therefore, in the present specification, hereinafter, the term “adhesiveness” may be used in a comprehensive manner.
  • binder materials The required performance for binder materials is becoming more severe year by year.
  • the material In addition to being highly resistant to oxidation when applied to the positive electrode and when applied to the negative electrode, the material should be highly swelled by contact with the electrolyte, for example, and easily move the electrolyte. It is required for the binder material that the property to be converted and the property that does not cause an increase in electrode resistance and a decrease in adhesiveness due to the swelling should be compatible with each other in an extraordinar balance.
  • an electricity storage device capable of high-speed discharge that can respond to rapid acceleration when mounted as a drive power source for an electric vehicle.
  • Patent Document 1 Japanese Laid-Open Patent Publication No. 2006-48932
  • Patent Document 1 is based on the idea of improving the temporal durability of the electricity storage device by improving the electrolyte solution resistance of the binder material.
  • the affinity of the binder component for the electrolyte solution is impaired, and the high-speed discharge characteristics do not reach the required level.
  • Patent Documents 2 and 3 are intended to realize high-speed discharge characteristics by improving the electrolyte solution affinity of the binder material.
  • this material has an excessively large swellability when it comes into contact with an electrolytic solution, so that the power storage device is particularly deteriorated when used or stored at a high temperature, and there is a problem in durability.
  • the durability of the electricity storage device and the charge / discharge characteristics are in a trade-off relationship.
  • Patent Document 4 proposes materials composed of metal oxide fine particles and a binder containing a fluorine resin and a rubber resin, respectively.
  • Patent Documents 4 to 6 certainly have a certain effect in preventing a short circuit due to dendrite in an electricity storage device using a metal ion conductor.
  • these protective films have insufficient electrolyte permeability and liquid retention, the internal resistance of the electricity storage device increases, resulting in a loss of charge / discharge characteristics.
  • an object of the present invention is to provide a binder material that provides an electricity storage device that is excellent in oxidation-reduction resistance and has both durability and charge / discharge characteristics (particularly, high-speed discharge characteristics).
  • the above objects and advantages of the present invention are as follows: When the total repeating unit is 100% by mass, it is derived from 3 to 40% by mass of the first repeating unit derived from an unsaturated carboxylic acid ester having at least an alicyclic hydrocarbon group and an ⁇ , ⁇ -unsaturated nitrile compound. It is achieved by a binder composition for an electricity storage device, comprising a polymer having 1 to 40% by mass of a second repeating unit.
  • the binder composition for an electricity storage device is: As a slurry for an electrode of an electricity storage device by blending an electrode active material; As a slurry for a protective film of an electricity storage device by blending a filler, Each can be suitably used.
  • FIG. 1 is a schematic cross-sectional view showing a basic structure of an electricity storage device.
  • FIG. 2 is a schematic cross-sectional view illustrating an example of the structure of an electricity storage device having a protective film.
  • FIG. 3 is a schematic cross-sectional view illustrating another example of the structure of the electricity storage device having a protective film.
  • FIG. 4 is a schematic cross-sectional view showing still another example of the structure of the electricity storage device having a protective film.
  • FIG. 5 is a schematic cross-sectional view showing the structure of an electricity storage device having a protective film instead of the separator.
  • (meth) acrylic acid is a concept encompassing both “acrylic acid” and “methacrylic acid”.
  • ⁇ (meth) acrylate is a concept encompassing both “ ⁇ acrylate” and “ ⁇ methacrylate”.
  • the binder composition for an electricity storage device of the present embodiment is As a slurry for an electrode of an electricity storage device by blending an electrode active material; As a slurry for a protective film of an electricity storage device by blending a filler, Each is preferably used.
  • the polymer contained in the binder composition for an electricity storage device of the present invention is a first repeat derived from an unsaturated carboxylic acid ester having at least an alicyclic hydrocarbon group (hereinafter referred to as “compound (a1)”).
  • the electrolytic solution it succeeded in balancing swelling and adhesiveness, and successfully achieved both good charge / discharge characteristics (especially high-speed discharge characteristics) and durability.
  • the polymer A repeating unit derived from an unsaturated carboxylic acid (hereinafter referred to as “compound (a3)”), A repeating unit derived from a monomer having a fluorine atom (hereinafter referred to as “compound (a4)”); A repeating unit derived from an unsaturated carboxylic acid ester (excluding those corresponding to the compounds (a1) and (a4) above; hereinafter the same; hereinafter referred to as “compound (a5)”); A repeating unit derived from at least one selected from the group consisting of a conjugated diene compound and an aromatic vinyl compound (hereinafter referred to as “compound (a6)”); A repeating unit derived from a crosslinkable monomer (hereinafter referred to as “compound (a7)”), and Repeating unit derived from ⁇ -olefin (hereinafter referred to as “compound (a8)”) You may have 1 or more types of repeating units selected from the group which consists of.
  • the polymer contained in the binder composition for an electricity storage device of the present invention preferably does not have a repeating unit derived from a monomer other than the compounds (a1) to (a8).
  • 1.1.1 Polymer repeat units 1.1.1.1 Repeating unit derived from compound (a1) Compound (a1) is an unsaturated carboxylic acid ester having an alicyclic hydrocarbon group.
  • the compound (a1) is an unsaturated carboxylic acid monocyclic cycloalkyl ester, bicyclic cycloalkyl ester, cyclic hydrocarbon ester having three or more rings, and spirocyclic cycloalkyl ester. It is preferable that it is at least one selected.
  • the content ratio of the repeating unit derived from the compound (a1) in the polymer contained in the binder composition for an electricity storage device of the present invention is 3 to 40% by mass when the total repeating unit is 100% by mass. This value is preferably 3 to 30% by mass, and more preferably 3 to 25% by mass.
  • the polymer having the repeating unit derived from the compound (a1) in the above range can suppress dissolution by the electrolyte when functioning as a binder in the active material layer or the protective film. For this reason, it is possible to minimize performance deterioration particularly during use or storage at high temperatures, which is preferable.
  • the monocyclic cycloalkyl ester of unsaturated carboxylic acid is preferably an ester compound having a monocyclic cycloalkyl group having 5 to 12 carbon atoms.
  • Specific examples thereof include, for example, cyclopentyl (meth) acrylate, (Meth) acrylic acid cyclohexyl, (Meth) acrylic acid cycloheptyl, (Meth) acrylic acid 4-methylcyclohexyl, (Meth) acrylic acid 3,3,5-trimethylcyclohexyl, (Meth) cyclooctyl acrylate, (Meth) cyclodecyl acrylate, Menthyl (meth) acrylate And so on.
  • the bicyclic cycloalkyl ester of unsaturated carboxylic acid is preferably an ester compound having a bicyclic cycloalkyl group having 6 to 20 carbon atoms.
  • an ester compound having a bicyclic cycloalkyl group having 6 to 20 carbon atoms for example Norbornyl (meth) acrylate, (Meth) acrylic acid decahydronaphthyl, (Meth) acrylic acid bicycloundecyl, Isobornyl (meth) acrylate And so on.
  • Examples of the cyclic hydrocarbon ester having three or more rings of unsaturated carboxylic acid include (Meth) acrylic acid tricyclo [5.2.1.0 2,6 ] Decyl, (Meth) acrylic acid tricyclo [5.2.1.0 2,6 ] Dec-3-yl, (Meth) acrylic acid 2-adamantyl, (Meth) acrylic acid 2- (2-methyladamantyl), (Meth) acrylic acid 2- (2-ethyladamantyl) Other than that;
  • An unsaturated carboxylic acid ester having a steroid skeleton can be preferably used.
  • an unsaturated carboxylic acid ester having a saturated or unsaturated steroid skeleton can be used, for example, (Meth) acrylic acid 3-cholestanyl, (Meth) acrylic acid 3-cholesteryl, (Meth) acrylic acid 3-lanostanyl, 3-methanyl (meth) acrylate And so on.
  • spirocyclic cycloalkyl esters of unsaturated carboxylic acids include: (Meth) acrylic acid spiro [5,5] undecyl And so on.
  • the compound (a1) in the present invention is expressed as RCOOR ′, one or more hydrogen atoms of the compound corresponding to the R ′ group or the group corresponding to the R ′ group, wherein the group corresponding to the R ′ group is interrupted by one or more ether bonds.
  • a compound in which is substituted with a hydroxyl group may be used. Examples of such compounds include 1,4-cyclohexanedimethanol mono (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, (Meth) acrylic acid 1- (3-hydroxyadamantyl), (Meth) acrylic acid 1- (5-hydroxyadamantyl), (Meth) acrylic acid 1- (3,5-dihydroxyadamantyl) And so on.
  • the structural unit derived from the compound (a1) may be present alone or in combination of two or more.
  • Repeating unit derived from compound (a2) Compound (a2) is an ⁇ , ⁇ -unsaturated nitrile compound.
  • the content of the repeating unit derived from the compound (a2) in the polymer contained in the binder composition for an electricity storage device of the present invention is 1 to 40% by mass when all the repeating units are 100% by mass. This value is preferably 2 to 25% by mass, and more preferably 3 to 15% by mass.
  • the polymer having the repeating unit derived from the compound (a2) in the above range exhibits an appropriate swelling property when in contact with the electrolytic solution, and as a result, the adhesion can be maintained for a long time. ,preferable.
  • Specific examples of the compound (a2) include (meth) acrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, vinylidene cyanide and the like. Of these, (meth) acrylonitrile is preferably used, and acrylonitrile is particularly preferable.
  • the structural unit derived from the compound (a2) may be present alone or in combination of two or more.
  • Repeating unit derived from compound (a3) is an unsaturated carboxylic acid.
  • the polymer contained in the binder composition for an electricity storage device of the present invention may have a repeating unit derived from the compound (a3), and preferably has this.
  • the content ratio of the repeating unit derived from the compound (a3) in the polymer contained in the binder composition for an electricity storage device of the present invention is preferably 15% by mass or less when the total repeating unit is 100% by mass.
  • the content is more preferably 1 to 12% by mass, and further preferably 3 to 10% by mass.
  • a polymer having a repeating unit derived from the compound (a3) is excellent in dispersibility of the active material and the filler.
  • the active material does not agglomerate when preparing the electrode slurry;
  • the filler does not aggregate,
  • a slurry excellent in uniformity and stability can be prepared, which is preferable. Therefore, the electrode and the protective film produced using the slurry for an electricity storage device are excellent in adhesion and uniformity since the binding defects are reduced as much as possible.
  • the compound (a3) unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and the like can be used.
  • Examples of unsaturated monocarboxylic acids include (meth) acrylic acid and crotonic acid; Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like. You may use the anhydride of these unsaturated dicarboxylic acids.
  • the compound (a3) one or more selected from the group consisting of (meth) acrylic acid and itaconic acid are particularly preferable.
  • the structural unit derived from the compound (a3) may be present alone or in combination of two or more.
  • the compound (a4) is a monomer having a fluorine atom.
  • the polymer contained in the binder composition for an electricity storage device of the present invention may have a repeating unit derived from the compound (a4).
  • the content ratio of the repeating unit derived from the compound (a4) in the polymer contained in the binder composition for an electricity storage device of the present invention is preferably 50% by mass or less when the total repeating unit is 100% by mass.
  • the content is more preferably 5 to 40% by mass, and further preferably 15 to 30% by mass.
  • the polymer contained in the binder composition for an electricity storage device of the present invention has a repeating unit derived from the compound (a6) described later, the polymer has a repeating unit derived from the compound (a4). It is preferable that it is not.
  • the polymer having a repeating unit derived from the compound (a4) is excellent in oxidation resistance, an electricity storage device comprising a positive electrode or a protective film produced using the binder composition for an electricity storage device containing the polymer, The durability against overcharge is expected to be improved, which is preferable.
  • the compound (a4) include an olefin compound having a fluorine atom and a (meth) acrylic acid ester having a fluorine atom.
  • the olefin compound having a fluorine atom include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, trifluorochloroethylene, and perfluoroalkyl vinyl ether.
  • Examples of the (meth) acrylic acid ester having a fluorine atom include 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 1 Is a hydrogen atom or a methyl group
  • R 2 Is a C1-C18 hydrocarbon group containing a fluorine atom.
  • R in the general formula (1) 2 examples thereof include a fluorinated alkyl group having 1 to 12 carbon atoms, a fluorinated aryl group having 6 to 16 carbon atoms, and a fluorinated aralkyl group having 7 to 18 carbon atoms.
  • An alkyl group is preferable.
  • R in the general formula (1) 2 Preferable specific examples of are, for example, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoropropane- 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 and the like can be mentioned.
  • the monomer having a fluorine atom is preferably an olefin compound having a fluorine atom, particularly preferably at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene.
  • the structural unit derived from the compound (a4) may be present alone or in combination of two or more.
  • 1.1.1.5 Repeating unit derived from compound (a5) Compound (a5) is an unsaturated carboxylic acid ester. However, those corresponding to the compounds (a1) and (a4) are excluded.
  • the polymer contained in the binder composition for an electricity storage device of the present invention may have a repeating unit derived from the compound (a5).
  • the content ratio of the repeating unit derived from the compound (a5) in the polymer contained in the binder composition for an electricity storage device of the present invention is 95% by mass or less when the total repeating unit is 100% by mass.
  • the content is 30 to 90% by mass, and more preferably 40 to 85% by mass.
  • the polymer having a repeating unit derived from the compound (a5) can arbitrarily adjust the glass transition temperature Tg of the polymer obtained by appropriately selecting the type and ratio of the compound (a5).
  • the binder composition for an electricity storage device containing the polymer is preferable in that it can provide an electrode and a protective film exhibiting high adhesion.
  • the compound (a5) include alkyl esters of unsaturated carboxylic acids, hydroxyalkyl esters of unsaturated carboxylic acids, polyhydric alcohol esters of unsaturated carboxylic acids, and the like.
  • the number of carbon atoms of the alkyl group of the unsaturated carboxylic acid alkyl ester is preferably 1-18;
  • the number of carbon atoms in the hydroxyalkyl group of the hydroxyalkyl ester of unsaturated carboxylic acid is preferably 1-8, more preferably 2-4;
  • the number of carbon atoms in the polyhydric alcohol moiety of the polyhydric alcohol ester of unsaturated carboxylic acid is preferably 2 to 12, and more preferably 3 to 6.
  • alkyl ester of the unsaturated carboxylic acid examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic acid n.
  • the alkyl group contained in these unsaturated carboxylic acid alkyl esters preferably has 1 to 12 carbon atoms.
  • the hydroxyalkyl ester of the unsaturated carboxylic acid include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (Meth) acrylic acid 4-hydroxybutyl and the like;
  • As said polyhydric alcohol ester of unsaturated carboxylic acid (meth) acrylic-acid ethylene 2,3- dihydroxypropyl, (meth) acrylic-acid 2,6-dihydroxyhexyl, etc. can be mentioned, respectively.
  • the structural unit derived from the compound (a5) may be present alone or in combination of two or more.
  • Repeating unit derived from compound (a6) The compound (a6) is at least one selected from the group consisting of a conjugated diene compound and an aromatic vinyl compound. However, a compound corresponding to the compound (a7) described later is excluded from the aromatic vinyl compound.
  • the polymer contained in the binder composition for an electricity storage device of the present invention may have a repeating unit derived from the compound (a6).
  • the content ratio of the repeating unit derived from the compound (a6) in the polymer contained in the binder composition for an electricity storage device of the present invention is 90% by mass or less when the total repeating unit is 100% by mass. It is preferably 30 to 85% by mass, more preferably 40 to 80% by mass. However, when the polymer contained in the binder composition for an electricity storage device of the present invention has a repeating unit derived from the compound (a4), the polymer has a repeating unit derived from the compound (a6). It is preferable that it is not.
  • the binder composition for an electricity storage device containing the polymer produces a negative electrode and a protective film in contact with the negative electrode Therefore, it can be used suitably.
  • the compound (a6) include conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1, 3-butadiene and the like;
  • the aromatic vinyl compound include styrene, ⁇ -methylstyrene, p-methylstyrene, chlorostyrene, and hydroxystyrene.
  • the structural unit derived from the compound (a6) may be present alone or in combination of two or more.
  • Compound (a7) is a crosslinkable monomer.
  • the polymer contained in the binder composition for an electricity storage device of the present invention may have a repeating unit derived from the compound (a7).
  • the content ratio of the repeating unit derived from the compound (a7) in the polymer contained in the binder composition for an electricity storage device of the present invention is preferably 5% by mass or less when the total repeating unit is 100% by mass. More preferably, it is 3 mass% or less.
  • the compound (a7) include, for example, divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetra Examples thereof include pentaerythritol (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
  • the structural unit derived from the compound (a7) may be present alone or in combination of two or more.
  • Compound (a8) is an ⁇ -olefin.
  • the polymer contained in the binder composition for an electricity storage device of the present invention may have a repeating unit derived from the compound (a8).
  • the content ratio of the repeating unit derived from the compound (a6) in the polymer contained in the binder composition for an electricity storage device of the present invention is preferably 5% by mass or less when the total repeating unit is 100% by mass. More preferably, it is 3 mass% or less.
  • Specific examples of the compound (a8) include ethylene, propylene, 1-butene and the like.
  • polymer (A) As a polymer contained in the binder composition for an electricity storage device of the present invention, It has a repeating unit derived from each of compound (a1), compound (a2), compound (a3), compound (a4) and compound (a5), and optionally further has a repeating unit derived from compound (a7).
  • a polymer hereinafter referred to as “polymer (A)”), or The compound (a1), the compound (a2), the compound (a3), the compound (a5) and the compound (a6) each have a repeating unit, and optionally further have a repeating unit derived from the compound (a7). It is preferably a polymer (hereinafter referred to as “polymer (B)”).
  • the polymer (A) may be a polymer obtained by polymerizing a mixture of the above compounds; or A polymer (Aa) having a repeating unit (only) derived from the compound (a4) among the above; Polymer (Ab) having repeating units derived from compound (a1), compound (a2), compound (a3) and compound (a5), and optionally further having a repeating unit derived from compound (a7) When The polymer alloy particle which consists of may be sufficient.
  • polymer (A) is a polymer alloy
  • Polymer alloy is a “generic name for multi-component polymers obtained by mixing or chemical bonding of two or more components” according to the definition in “Iwanami Physical and Chemical Dictionary 5th edition. Iwanami Shoten”. “Polymer blends physically mixed with different polymers, block and graft copolymers in which different polymer components are covalently bonded, polymer complexes in which different polymers are associated by intermolecular forces, and different polymers entangled with each other IPN (Interpenetrating Polymer Network, etc.).
  • the polymer alloy contained in the binder composition for an electricity storage device of the present invention is preferably a particle made of IPN among “a polymer alloy in which different types of polymer components are not bonded by a covalent bond”.
  • the polymer (Aa) constituting the polymer alloy is excellent in ionic conductivity, and the hard segment of the crystalline resin is aggregated to give a pseudo-crosslinking point such as C—H... It is considered a thing. For this reason, when the polymer (Aa) is used alone as the binder resin, its ionic conductivity and oxidation resistance are good, but the adhesion and flexibility are insufficient, and therefore the adhesion is low.
  • the polymer (Ab) constituting the polymer alloy is excellent in adhesion and flexibility, but has low oxidation resistance. Therefore, when this is used alone as a binder resin, it is repeatedly charged and discharged. Since it is deteriorated by oxidative decomposition, good charge / discharge characteristics cannot be obtained.
  • the polymer alloy containing the polymer (Aa) and the polymer (Ab) ionic conductivity and oxidation resistance and adhesion can be expressed at the same time, and good charge / discharge characteristics can be obtained. It becomes possible to produce a positive electrode and a protective film having the same.
  • the polymer alloy preferably has only one endothermic peak in the temperature range of ⁇ 50 to 250 ° C.
  • the temperature of this endothermic peak is more preferably in the range of ⁇ 30 to + 30 ° C.
  • the polymer (Aa) constituting the polymer alloy generally has an endothermic peak (melting temperature) at ⁇ 50 to 250 ° C. when it exists alone.
  • the polymer (Ab) constituting the polymer alloy generally has an endothermic peak (glass transition temperature) different from that of the polymer (Aa). For this reason, when the polymer (Aa) and the polymer (Ab) in the polymer are present in phase separation as in, for example, a core-shell structure, two endothermic peaks are observed at ⁇ 50 to 250 ° C. It should be.
  • the polymer alloy as the polymer (A1) in the binder composition for an electricity storage device of the present invention contains a polymer (Aa) having a repeating unit derived from the compound (a4).
  • the monomer for deriving the repeating unit constituting the polymer (Aa) is preferably at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, and propylene hexafluoride. Most preferably.
  • the preferable content ratio of the repeating unit derived from each monomer in the polymer (Aa) is as follows based on the total mass of the polymer (Aa).
  • the polymer alloy as the polymer (A) in the present invention has a repeating unit derived from another copolymerizable unsaturated monomer other than the compound (a4).
  • a component such as a polymer (Ab) has good adhesion, but is considered to have poor ionic conductivity and oxidation resistance, and has not been used for a positive electrode.
  • a polymer (Ab) as a polymer alloy together with the polymer (Aa)
  • sufficient ionic conductivity and oxidation resistance are expressed while maintaining good adhesion.
  • the content ratio of the repeating unit derived from each monomer in the polymer (Ab) is as follows. The following are values when the mass of the polymer (Ab) is 100% by mass.
  • the polymer alloy as the polymer (A) contained in the binder composition for an electricity storage device of the present invention is not particularly limited as long as the polymer alloy has the above-described configuration.
  • known emulsion polymerization It can be easily synthesized by combining the steps or appropriately. For example, first, particles composed of a polymer (Aa) having a repeating unit derived from the compound (a4) are synthesized by a known method, and then A monomer for constituting the polymer (Ab) is added to the particles made of the polymer (Aa), and the monomer is sufficiently absorbed in the stitch structure of the particles made of the polymer (Aa).
  • polymer alloy particles can be easily produced by a method of synthesizing the polymer (Ab) by polymerizing the absorbed monomer in the stitch structure of the polymer (Aa).
  • the absorption temperature is too low or the absorption time is too short, only a core-shell type polymer or a part of the surface layer becomes a polymer having an IPN type structure, and the polymer alloy in the present invention may not be obtained. Many.
  • the absorption temperature is preferably 30 to 100 ° C., more preferably 40 to 80 ° C .;
  • the absorption time is preferably 1 to 12 hours, more preferably 2 to 8 hours. At this time, it is preferable to lengthen the absorption time when the absorption temperature is low, and a short absorption time is sufficient when the absorption temperature is high.
  • Appropriate conditions are such that the value obtained by multiplying the absorption temperature (° C.) and the absorption time (h) is generally in the range of 120 to 300 (° C. ⁇ h), preferably 150 to 250 (° C. ⁇ h).
  • the operation of absorbing the monomer of the polymer (Ab) in the network structure of the particles made of the polymer (Aa) is preferably performed in a known medium used for emulsion polymerization, for example, in water.
  • the content of the polymer (Aa) in the polymer alloy is preferably 3 to 60% by mass, more preferably 5 to 55% by mass, and more preferably 10 to 50% by mass in 100% by mass of the polymer alloy. More preferably, it is particularly preferably 20 to 40% by mass.
  • the polymer alloy contains the polymer (Aa) in the above range, the balance between the ionic conductivity and the oxidation resistance and the adhesion becomes better.
  • the polymer (Ab) in which the content ratio of the repeating unit derived from each monomer is in the above preferred range is used, the polymer alloy contains the polymer (Aa) in the above range, It becomes possible to set the content ratio of each repeating unit in the entire polymer alloy within the above-mentioned preferable range, and this ensures that the charge / discharge characteristics of the electricity storage device are good.
  • the polymerization conditions will be described later.
  • the content ratio of the repeating unit derived from each monomer in the polymer (B) is as follows.
  • Repeating unit derived from compound (a1) preferably 3 to 40% by mass, more preferably 5 to 25% by mass;
  • Repeating unit derived from compound (a3) preferably 1 to 15% by mass, more preferably 2 to 10% by mass;
  • Repeating unit derived from compound (a6) preferably 90% by mass or less, more preferably 85% by mass or less.
  • this polymer particle (B) When this polymer particle (B) is measured by DSC, it preferably has only one endothermic peak in the temperature range of ⁇ 40 to + 25 ° C.
  • the temperature of this endothermic peak is more preferably in the range of ⁇ 30 to + 20 ° C., and further preferably in the range of ⁇ 25 to + 10 ° C.
  • the polymer particle (B) When the polymer particle (B) has only one endothermic peak in the DSC analysis and the peak temperature is in the above range, the polymer exhibits good adhesion and has a moderate flexibility in the thick material layer. Therefore, it is possible to impart the property.
  • the emulsifier examples include sulfate esters of higher alcohols, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietic acid salts, naphthalene sulfonic acid / formalin condensates, Anionic surfactants such as sulfate salts of ionic surfactants; Nonionic surfactants such as alkyl esters of polyethylene glycol, alkyl phenyl ethers of polyethylene glycol, alkyl ethers of polyethylene glycol; Fluorosurfactants such as perfluorobutyl sulfonate, perfluoroalkyl group-containing phosphate ester, perfluoroalkyl group-containing carboxylate, and perfluoroalkylethylene oxide adducts can be mentioned, and selected from these More than one kind can be used.
  • the proportion of the emulsifier used is the sum of the monomers used (in the production of the polymer (Aa), the sum of the monomers leading to the polymer (Aa), the polymer (Ab) in the presence of the polymer (Aa)).
  • the content is preferably 0.01 to 10 parts by mass, and more preferably 0.02 to 5 parts by mass.
  • polymerization initiator examples include water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate; Cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, azobisisobutyronitrile, 1, Oil-soluble polymerization initiators such as 1′-azobis (cyclohexanecarbonitrile) can be appropriately selected and used.
  • water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate
  • Cumene hydroperoxide benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, 1,
  • the use ratio of the polymerization initiator is not particularly limited, but is appropriately set in consideration of the monomer composition, the pH of the polymerization reaction system, a combination of other additives, and the like.
  • the use ratio of the polymerization initiator is preferably 0.3 to 3 parts by mass with respect to 100 parts by mass in total of the monomers used.
  • the molecular weight modifier examples include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-stearyl mercaptan; Xanthogen compounds such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide; Thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; Phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol and styrenated phenol; Allyl compounds such as allyl alcohol; Halogenated hydrocarbon compounds such as dichloromethane, dibromomethan
  • the use ratio of the molecular weight regulator is preferably 5 parts by mass or less with respect to 100 parts by mass in total of the monomers used.
  • Emulsion polymerization is preferably carried out in a suitable aqueous medium, particularly preferably in water.
  • the total content of the monomers in the aqueous medium can be 10 to 50% by mass, and preferably 20 to 40% by mass.
  • the polymerization temperature is preferably 40 to 95 ° C, more preferably 50 to 85 ° C.
  • the polymerization time is preferably 1 to 24 hours, more preferably 2 to 18 hours.
  • Each of the above polymerizations may be carried out as a single-stage polymerization or by a two-stage polymerization method.
  • the proportion of the monomer used for the first-stage polymerization is the total mass of the monomer (the mass of the monomer used for the first-stage polymerization and the second-stage polymerization used.
  • the total amount is preferably in the range of 20 to 80% by mass, and preferably in the range of 40 to 75% by mass with respect to the total mass of the monomers.
  • the type of monomer used in the first-stage polymerization and its use ratio may be the same as or different from the type of monomer used in the second-stage polymerization and its use ratio.
  • 1.1.4 Mode particle size of polymer The polymer contained in the binder composition for an electricity storage device of the present invention is preferably latex polymer particles dispersed in a liquid medium.
  • the mode particle diameter of the polymer particles is preferably in the range of 50 to 800 nm, more preferably in the range of 75 to 500 nm, and particularly preferably in the range of 100 to 250 nm. Since the mode particle diameter of the polymer particles is within the above range, the polymer particles are effectively adsorbed on the surface of the electrode active material or the filler.
  • the polymer particles follow the movement of these particles. Will be able to move. As a result, it is possible to suppress the migration of only one of the two particles alone, and thus it is possible to suppress the deterioration of electrical characteristics.
  • the most frequent particle size is a particle whose particle count is 50% when the particle size distribution is measured using a particle size distribution measuring apparatus based on the light scattering method and the particles are accumulated in order of increasing particle size. This is the value of the diameter (D50).
  • Examples of such a particle size distribution measuring apparatus include Coulter LS230, LS100, LS13320 (above, manufactured by Beckman Coulter. Inc), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), and the like.
  • the particle size distribution measuring devices are not intended to evaluate only the primary particles of the polymer particles, but can also evaluate the secondary particles formed by aggregation of the primary particles. Therefore, the particle size distribution measured by these particle size distribution measuring devices can be used as an indicator of the dispersion state of the polymer particles contained in the binder composition for an electricity storage device.
  • the mode particle diameter of the polymer particles can be determined by a method in which the electrode slurry or the protective film slurry, which will be described later, is centrifuged to settle the electrode active material, and then the supernatant is measured by the above particle size distribution measuring apparatus. Can be measured.
  • the binder composition for an electricity storage device of the present invention preferably contains a liquid medium.
  • the liquid medium preferably contained in the binder composition for an electricity storage device of the present invention is preferably an aqueous medium containing water.
  • This aqueous medium may contain a non-aqueous medium other than water.
  • the non-aqueous medium include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, sulfone compounds, and the like. One or more selected from these can be used. it can.
  • the proportion of water in the total amount of 100% by mass of the liquid medium is preferably 90% by mass or more, More preferably, it is 98 mass% or more.
  • the binder composition for an electricity storage device of the present invention has a low degree of adverse effects on the environment, and is also safer for handling workers.
  • the use ratio of the liquid medium refers to the solid content concentration of the binder composition for an electricity storage device (the ratio of the total mass of components other than the liquid medium in the binder composition for an electricity storage device to the total mass of the binder composition for an electricity storage device). The same shall apply hereinafter) is preferably in a proportion of 5 to 80% by mass, more preferably in a proportion of 10 to 60% by mass.
  • the binder composition for an electricity storage device of the present invention is preferably in a latex form in which the polymer is in the form of particles and dispersed in a liquid medium. Since the binder composition for an electricity storage device is in a latex form, the stability of the slurry for the electrode prepared by blending the electrode active material and the like, and the slurry for the protective film prepared by blending the filler is improved, and Since the applicability of these slurries becomes good, it is preferable.
  • it is a particle which consists of a polymer (A) as a polymer contained in this.
  • the binder composition for electrical storage devices of this invention when using the binder composition for electrical storage devices of this invention in order to manufacture the negative electrode of an electrical storage device, it is preferable that it is a particle which consists of a polymer (B) as a polymer contained in this.
  • the binder composition for an electricity storage device of the present invention is used to produce a protective film for an electricity storage device, the preferred polymer type varies depending on the position where the protective film is disposed.
  • the binder composition for an electricity storage device used for producing the protective film preferably contains particles made of the polymer (A).
  • the binder composition for an electricity storage device includes, in addition to the polymer and the liquid medium, a polymerization catalyst used for the synthesis of the polymer or its residue, a remaining monomer, an emulsifier, a surfactant, a neutralizer.
  • the content ratio of the components derived from the production of these polymers is preferably as small as possible. It is preferably 5% by mass or less, more preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably not containing any of these, based on the solid content. is there.
  • the binder composition for an electricity storage device of the present invention preferably has a liquidity in the vicinity of neutrality, more preferably pH 6.0 to 8.5, and particularly preferably pH 7.0 to 8.0. preferable. A known acid or base can be used to adjust the liquidity of the composition.
  • the binder composition for an electricity storage device of the present invention may contain the above acid or base in a range necessary for adjusting the liquidity.
  • Slurry for electrode An electrode slurry can be produced using the binder composition for an electricity storage device of the present invention as described above.
  • the electrode slurry refers to a dispersion used for forming an electrode active material layer on the surface of a current collector.
  • the slurry for an electrode in the present invention contains at least the binder composition for an electricity storage device of the present invention and an electrode active material.
  • Electrode active material examples of the electrode active material used in the electrode slurry produced using the binder composition for an electricity storage device of the present invention include carbon materials, oxides containing lithium atoms, compounds containing silicon atoms, lead compounds, and tin compounds. Arsenic compounds, antimony compounds, aluminum compounds, polyacenic organic semiconductors (PAS), and the like. Examples of the carbon material include amorphous carbon, graphite, natural graphite, mesocarbon microbeads (MCMB), pitch-based carbon fibers, and the like.
  • Examples of the oxide containing lithium atoms include lithium cobaltate, lithium nickelate, lithium manganate, ternary nickel cobalt lithium manganate, LiFePO 4 , LiCoPO 4 , LiMnPO 4 , Li 0.90 Ti 0.05 Nb 0.05 Fe 0.30 Co 0.30 Mn 0.30 PO 4 And so on.
  • Examples of the compound containing a silicon atom include a silicon simple substance, a silicon oxide, a silicon alloy, and the like, and a silicon material described in JP-A No. 2004-185810 can be used.
  • As the silicon oxide the composition formula SiO x A silicon oxide represented by (0 ⁇ x ⁇ 2, preferably 0.1 ⁇ x ⁇ 1) is preferable.
  • the silicon alloy is preferably an alloy of silicon and at least one transition metal selected from the group consisting of titanium, zirconium, nickel, copper, iron and molybdenum. These transition metal silicides are preferably used because they have high electronic conductivity and high strength. Moreover, since the transition metal existing on the surface of the active material is oxidized and becomes an oxide having a hydroxyl group on the surface when the active material contains these transition metals, the binding force with the binder is also improved. preferable.
  • the silicon alloy it is more preferable to use a silicon-nickel alloy or a silicon-titanium alloy, and it is particularly preferable to use a silicon-titanium alloy.
  • the silicon content in the silicon alloy is preferably 10 mol% or more, more preferably 20 to 70 mol%, based on all the metal elements in the alloy.
  • the compound containing a silicon atom may be single crystal, polycrystalline, or amorphous.
  • Oxide in the above is a concept that means a compound or salt composed of oxygen and an element having an electronegativity smaller than that of oxygen. In addition to metal oxide, metal phosphate, nitrate, halogen It is a concept including oxo acid salts, sulfonic acid salts and the like.
  • the active material contained in the electrode slurry is preferably an oxide containing lithium atoms.
  • the active material contained in the electrode slurry preferably contains a compound containing a silicon atom. Since silicon atoms have a large occlusion capacity for lithium, the active material containing a compound containing silicon atoms can increase the storage capacity of the resulting storage device, and as a result, increase the output and energy density of the storage device. can do.
  • the active material for the negative electrode is preferably composed of a mixture of a compound containing a silicon atom and a carbon material. Since the carbon material has a small volume change due to charge / discharge, the influence of the volume change of the compound containing silicon atoms can be mitigated by using a mixture of the compound containing silicon atoms and the carbon material as the negative electrode active material. And the adhesion between the active material layer and the current collector can be further improved.
  • the negative electrode active material is particularly preferably composed of a mixture of a compound containing a silicon atom and graphite. The proportion of the compound containing silicon atoms in the active material is preferably 1% by mass or more, more preferably 1 to 50% by mass, still more preferably 5 to 45% by mass, particularly 10%.
  • the binder composition for an electricity storage device of the present invention is used to produce an electrode for an electric double layer capacitor
  • the active material contained in the electrode slurry for example, a carbon material, an aluminum compound, a silicon oxide, or the like is used. It is preferable.
  • the binder composition for an electricity storage device of the present invention is used for producing an electrode for a lithium ion capacitor
  • examples of the active material contained in the electrode slurry include a carbon material, a polyacene organic semiconductor (PAS), and the like. Is preferably used.
  • the shape of the active material is preferably granular.
  • the particle diameter (average median particle diameter) of the particles is preferably from 0.1 to 100 ⁇ m, and more preferably from 1 to 20 ⁇ m.
  • the proportion of the active material used is preferably such that the amount of the polymer in the binder composition for an electricity storage device is 0.1 to 25 parts by mass with respect to 100 parts by mass of the active material. It is more preferable to set it as the ratio which becomes a mass part. By setting it as such a usage rate, it is possible to produce an electrode that is excellent in adhesiveness and has low electrode resistance and excellent charge / discharge characteristics.
  • the slurry for electrodes in the present invention may contain other components as necessary in addition to the components described above.
  • Examples of such other components include a conductivity-imparting agent, a thickener, and a liquid medium (however, excluding a part brought in from the binder composition for an electricity storage device).
  • a conductivity-imparting agent examples include carbon in a lithium ion secondary battery. Examples of carbon include activated carbon, acetylene black, ketjen black, furnace black, graphite, carbon fiber, and fullerene. Among these, acetylene black or furnace black can be preferably used.
  • the 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 active material.
  • the electrode slurry can contain a thickener from the viewpoint of improving the coatability.
  • the thickener include cellulose derivatives such as carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose, and hydroxyethylmethylcellulose; An ammonium salt or an alkali metal salt of the cellulose derivative; Polycarboxylic acids such as poly (meth) acrylic acid, modified poly (meth) acrylic acid; An alkali metal salt of the polycarboxylic acid; Polyvinyl alcohol (co) polymers such as polyvinyl alcohol, modified polyvinyl alcohol, and ethylene-vinyl alcohol copolymer; Examples thereof include water-soluble polymers such as saponified products of copolymers of unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid and fumaric acid and vinyl esters.
  • the use ratio of the thickener is such that the ratio (Wv / Wa) of the weight (Wv) of the thickener to the weight (Wa) of the active material in the electrode slurry is 0.001 to 0.1. is there.
  • This ratio (Wv / Wa) is preferably 0.005 to 0.05.
  • 2.2.3 Liquid medium Since the slurry for electrodes contains the binder composition for electrical storage devices, it contains the liquid medium contained in the binder composition for electrical storage devices. However, the slurry for electrodes may contain an additional liquid medium in addition to the liquid medium brought from the binder composition for an electricity storage device. The liquid medium additionally contained in the electrode slurry may be the same as or different from the liquid medium contained in the binder composition for an electricity storage device.
  • the usage ratio of the liquid medium (including the amount brought in from the binder composition for the electricity storage device) in the electrode slurry is the solid content concentration of the electrode slurry (the total mass of components other than the liquid medium in the electrode slurry is for the electrode)
  • the ratio to the total mass of the slurry, the same shall apply hereinafter) is preferably 30 to 70% by mass, more preferably 40 to 60% by mass.
  • the electrode slurry may be produced by any method as long as it contains the above-described components.
  • the active material and optional additive components used as necessary in the binder composition for an electricity storage device can be produced by mixing them.
  • the binder composition for an electricity storage device and other components it can be carried out by stirring by a known method.
  • the preparation of the electrode slurry (mixing operation of each component) is preferably performed at least part of the process under reduced pressure. Thereby, it can prevent that a bubble arises in the active material layer obtained.
  • the absolute pressure is 5.0 ⁇ 10 4 ⁇ 5.0 ⁇ 10 5 It is preferable to be about Pa.
  • a mixer that can stir to such an extent that no agglomerates of active material particles remain in the slurry and sufficient dispersion conditions as necessary.
  • the degree of dispersion can be measured by 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 bead mill, a sand mill, a defoamer, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, and a Hobart mixer. it can.
  • the electrode for an electricity storage device is formed by applying a slurry for an electrode produced using the binder composition for an electricity storage device of the present invention to the surface of an appropriate current collector such as a metal foil, and then forming the coating film. It can be produced by removing the liquid medium from the membrane.
  • the electrode produced in this manner is formed by binding an active material layer containing the above-described polymer and active material, and optional additional components used as necessary, on a current collector. .
  • An electrode having a layer formed from the above-described electrode slurry on the surface of the current collector has excellent binding properties between the current collector and the active material layer, and also has excellent charge / discharge characteristics (especially high-speed discharge characteristics). Give device.
  • 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, it is used for the positive electrode of the present invention.
  • the effect of the slurry 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 as the current collector in the nickel metal hydride secondary battery.
  • the shape and thickness of the current collector are not particularly limited, but are preferably in the form of a sheet having a thickness of about 0.001 to 0.5 mm.
  • the coating method 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 electrode slurry is not particularly limited, but the thickness of the active material layer formed after removing the liquid medium is preferably 0.005 to 5 mm, and preferably 0.01 to 2 mm. It is more preferable to use the amount.
  • the method for removing the liquid medium from the coated film after coating is not particularly limited, and may be, for example, drying with hot air, hot air, low-humidity air; vacuum drying; (far) drying by irradiation with infrared rays, electron beams, 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 press conditions should be set appropriately depending on the type of press equipment used and the desired 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 0.5 to 5 t.
  • the coating film feed speed (roll rotation speed) after removal of the dispersion medium is 1 to 80 m / min, preferably 5 to 50 m / min. it can.
  • the density of the active material layer after pressing cannot be generally discussed because the specific gravity differs depending on the type of active material, but it is preferable to set the density so that the porosity of the active material layer is 10 to 50%.
  • the density of the active material layer is 1.5 to 2.5 g / cm when, for example, lithium iron phosphate is used as the active material. 3 Preferably, 1.7 to 2.1 g / cm 3 And more preferably; When using, for example, graphite as the active material, 1.2 to 1.9 g / cm 3 Preferably, 1.3 to 1.8 g / cm 3 More preferably. It is preferable that the pressed coating film is further heated under reduced pressure to completely remove the liquid medium.
  • the degree of pressure reduction is preferably 200 Pa or less, more preferably 150 Pa or less as an absolute pressure.
  • the heating temperature is preferably 100 to 200 ° C, more preferably 120 to 180 ° C.
  • the heating time is preferably 1 to 24 hours, more preferably 2 to 12 hours.
  • the electrode for an electricity storage device manufactured in this way is excellent in adhesion between the current collector and the active material layer. 3.
  • Slurry for protective film The slurry for protective films can be manufactured using the binder composition for electrical storage devices of the present invention as described above.
  • the slurry for protective film is a dispersion used for forming a protective film on the surface of a suitable base material.
  • the slurry for protective films in this invention contains the binder composition for electrical storage devices and filler of this invention at least.
  • the filler used in the slurry for a protective film produced using the binder composition for an electricity storage device of the present invention may be either inorganic particles or organic particles. Of these, inorganic particles are preferred.
  • the filler in the slurry for a protective film of the present invention it is preferable to use a metal oxide or a semimetal oxide. Specifically, for example, silicon oxide (silica), titanium oxide (titania), aluminum oxide (alumina) ), Zirconium oxide (zirconia), magnesium oxide (magnesia), and the like.
  • titanium oxide rutile type titanium oxide is preferable. Among these, it is preferable to use titanium oxide or aluminum oxide because the toughness of the protective film to be formed is increased.
  • the mode particle diameter (Dc) of the filler in the present invention is preferably 1 ⁇ m or less, and more preferably 0.1 to 0.8 ⁇ m.
  • the separator is usually a porous body. When forming a protective film on the surface of the separator which is a porous body, it is preferable that the mode diameter of the filler is larger than the average pore diameter of the pores of the separator. This can prevent the filler from being clogged in the pores of the separator, and therefore does not hinder the movement of ions in the electrolytic solution.
  • the mode particle size (Dc) of the filler is a D50 value measured by the same method as the mode particle size of the polymer particles in the binder composition for an electricity storage device of the present invention.
  • the mode particle size of the filler may be measured with respect to the settled filler after removing the supernatant liquid after centrifuging the protective film slurry to settle the filler.
  • the proportion of the filler used is preferably such that the amount of the polymer in the binder composition for an electricity storage device is 0.1 to 20 parts by mass with respect to 100 parts by mass of the filler. It is more preferable to set it as a ratio. By setting it as such a use rate, the protective film which is excellent in adhesiveness and has low resistance can be manufactured.
  • the slurry for protective film in the present invention may contain other components as necessary in addition to the components described above.
  • Such other components include a surfactant thickener and a liquid medium (however, excluding a part brought in from the binder composition for an electricity storage device).
  • the surfactant may be contained in the protective film slurry of the present invention for the purpose of further improving the dispersibility and dispersion stability of the protective film slurry.
  • the surfactant in the protective film slurry include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
  • Examples of these are: Examples of the anionic surfactant include fatty acid salts, monoalkyl sulfates, monoalkyl phosphates, alkylbenzene sulfonates, and the like; Examples of the cationic surfactant include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl benzyl dimethyl ammonium salt, and the like; Examples of the amphoteric surfactant include alkyl dimethylamine oxide and alkyl carboxybetaine; Examples of the nonionic surfactant include fatty acid sorbitan esters, fatty acid diethanolamides, alkyl polyglucosides, alkyl monoglyceryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyvinyl alcohol polymers, and the like.
  • the use ratio of the surfactant is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the filler.
  • a thickener and a liquid medium it is the same as that of the place mentioned above about the optional addition component in the slurry for electrodes.
  • the use ratio of the liquid medium (including the carry-in from the binder composition for an electricity storage device) in the protective film slurry is determined based on the solid content concentration of the protective film slurry (components other than the liquid medium in the protective film slurry).
  • the ratio of the total mass to the total mass of the protective film slurry, the same shall apply hereinafter)) is preferably 10 to 80% by mass, more preferably 15 to 60% by mass. . 3.3 Method for producing protective film slurry
  • a filler and an optional additive component used as necessary in the binder composition for an electricity storage device And can be produced by mixing them. Mixing of the binder composition for an electricity storage device and other components can be carried out using an apparatus similar to that described above as a method for producing an electrode slurry.
  • the protective film for an electricity storage device in the present invention is produced by applying the above slurry for protective film on the surface of the positive electrode, negative electrode or separator to form a coating film, and then removing the liquid medium from the coating film. can do.
  • Each of the positive electrode and the negative electrode may have an active material layer produced using an electrode slurry prepared from the binder composition for an electricity storage device of the present invention, or the positive electrode and the negative electrode in the prior art. It may be.
  • the separator is a porous body having a large number of pores.
  • Examples of the material constituting the separator include polyolefin polymers such as polyethylene and polypropylene; Polyvinylidene fluoride polymers such as polyvinylidene fluoride and vinylidene fluoride-hexafluoropropylene copolymer; Polyester polymers such as polyethylene terephthalate; Polyamide polymer; Polyimide polymer; Polystyrene polymer; Polysulfone polymer; Polyvinyl alcohol polymer; polyphenylene ether polymer; Polyphenylene sulfide polymer; cellulose acetate polymer; Examples include polyacrylonitrile-based polymers.
  • the average pore diameter of the pores of the separator is preferably smaller than the mode particle diameter of the filler contained in the protective film slurry. Accordingly, the average pore diameter of the pores of the separator is preferably 1 ⁇ m or less, and more preferably 0.01 to 0.5 ⁇ m. By using a separator having a pore diameter in this range, it is possible to prevent the filler from being clogged in the pores of the separator.
  • the porosity of the separator is preferably 20 to 80% by volume, more preferably 30 to 75% by volume. By using a separator having a porosity in this range, even when a protective film is formed, the output characteristics of the electricity storage device are not impaired, which is preferable.
  • the thickness of the separator is preferably 2 to 50 ⁇ m, more preferably 5 to 40 ⁇ m.
  • a separator having a thickness in this range there is an advantage that workability when forming a protective film is improved. Further, by using a separator having a thickness in this range, the occupied volume of the separator after the formation of the protective film is not excessive, and thus the storage capacity per volume of the obtained storage device is not impaired.
  • the coating amount of the protective film slurry is preferably such that the thickness of the protective film formed after removing the liquid medium is 0.5 to 3 ⁇ m.
  • the removal of the liquid medium from the coated film after coating can be performed by, for example, drying with hot air, hot air or low-humidity air; vacuum drying; drying by irradiation with (far) infrared rays or electron beams.
  • the coating film is preferably dried in a temperature range of 20 to 150 ° C., more preferably 50 to 150 ° C., preferably for 1 to 120 minutes, more preferably for 5 to 60 minutes. 4).
  • the electricity storage device of the present invention comprises at least one selected from the electrode for electricity storage device (positive electrode and negative electrode) and the protective film for electricity storage device produced as described above, and further contains an electrolytic solution. Further, it can be produced according to a conventional method using other appropriate parts. As a specific manufacturing method, for example, a negative electrode and an electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery, and stored in a battery container, and an electrolytic solution is injected into the battery container. Can be mentioned.
  • the shape of the battery can be an appropriate shape such as a coin shape, a cylindrical shape, a square shape, or a laminate shape.
  • the electrolyte solution may be liquid or gel, and the one that effectively expresses the function as a battery is selected from the known electrolyte solutions used for the electricity storage device depending on the type of the negative electrode active material and the electrode active material. That's fine.
  • 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.
  • 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, lower fatty acid lithium carboxylate and the like can be exemplified.
  • 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 ⁇ -butyl lactone; Ether compounds such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran; Examples thereof include sulfoxide compounds such as dimethyl sulfoxide, and one or more selected from these can be used.
  • carbonate compounds such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate
  • Lactone compounds such as ⁇ -butyl lactone
  • Ether compounds such as trimethoxymethane, 1,2-dimethoxyethane, die
  • FIG. 1 shows a cross-sectional schematic view of the most basic structure of the electricity storage device.
  • a separator 3 is sandwiched between a positive electrode 1 and a negative electrode 2.
  • the positive electrode 1 has a structure in which a positive electrode active material layer 12 is laminated on the surface of a positive electrode current collector 11.
  • the negative electrode 2 has a structure in which a negative electrode active material layer 22 is laminated on the surface of a negative electrode current collector 21.
  • FIG. 2 shows a cross-sectional schematic view of an example of the structure of an electricity storage device having a protective film.
  • a protective film 101 is formed between the positive electrode 1 and the separator 3 in the electricity storage device of FIG. 1.
  • the protective film 101 may be formed on the surface of the positive electrode active material layer 12 or may be formed on the positive electrode side surface of the separator 3.
  • 3 to 5 are other examples of power storage devices each having a protective film.
  • Each of the positive electrode active material layer 12 and the negative electrode active material layer 22 in FIGS. 3 to 5 may be formed from an electrode slurry prepared using the binder composition for an electricity storage device of the present invention, It may be of the prior art.
  • a protective film 102 is formed between the negative electrode 2 and the separator 3 in the electricity storage device of FIG. 1. This protective film 102 may be formed on the surface of the negative electrode active material layer 22 or may be formed on the negative electrode side surface of the separator 3.
  • a protective film 101 is disposed between the positive electrode 1 and the separator 3.
  • a protective film 102 is provided between the negative electrode 2 and the separator 3.
  • the protective films 101 and 102 may be formed on the surface of the active material, respectively, but it is convenient in the process to form the protective films 101 and 102 on both surfaces of the separator 3.
  • the thicknesses of the protective films 101 and 102 in the electricity storage devices of FIGS. 2 to 4 are each preferably 0.5 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m.
  • the power storage device in FIG. 5 has a structure in which a protective film 103 is sandwiched between a positive electrode 1 and a negative electrode 2.
  • This electricity storage device does not have a separator, and the protective film 103 has the function of a separator.
  • the thickness of the protective film 103 is preferably 5 to 30 ⁇ m, and more preferably 7 to 20 ⁇ m.
  • An electricity storage device having such a protective film 103 can be manufactured, for example, by forming the protective film on the surface of the positive electrode active material layer 12 or the surface of the negative electrode active material layer 22.
  • Example C1 [Preparation of binder composition] (1) Polymerization of polymer (Aa) 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.
  • VdDF vinylidene fluoride
  • HFP propylene hexafluoride
  • the weight (Y (g)) of the residue obtained by evaporating and removing the dissolved EC / DEC was used to calculate the following formula (1 ), The electrolyte solution insoluble matter was found to be 98% by mass. Further, after EC / DEC attached to the surface of the insoluble matter (film) separated by the above filtration was absorbed by paper and removed, the weight of the insoluble matter film (Z (g)) was measured, and the following formula ( When the electrolytic solution swelling degree was measured by 2), the electrolytic solution swelling degree of the polymer particles was 300% by mass.
  • FPAR-1000 particle size distribution measuring apparatus
  • the mode particle size obtained from the particle size distribution was 300 nm.
  • Examples C2 to 11 and Comparative Examples c1 to c7 Types and amounts of monomers for synthesizing the polymer (Aa) in “1.
  • (2) Preparation of the binder composition The amount of the polymer (Aa) used and the kind and amount of the monomer for synthesizing the polymer (Ab), and the stirring time for allowing the polymer (Aa) to absorb the monomer (Table 1)
  • the “stirring time for monomer absorption” is as shown in Table 1, and the solid content concentration was the same as in Example C1 except that the amount of emulsifier was adjusted as necessary.
  • Aqueous dispersions (binder compositions for power storage devices (C2) to (C11) and (rc1) to (rc7)) containing 40% by mass of the polymer (A) particles were prepared. Using these binder compositions, various evaluations were performed in the same manner as in Example C1. The evaluation results are shown in Table 1. In Examples C6 and C8 and Comparative Example c4, since the polymer (Aa) was not subjected to the operation of absorbing the monomer, the DSC analysis showed a melting point Tm in addition to the glass transition temperature Tg. . In the DSC analysis of Example C5 and Comparative Examples c5 and c7, the glass transition temperature Tg is not observed because the polymer (Ab) forms a strong crosslinked structure.
  • Example C12 A separable flask having a volume of 7 liters was charged with 150 parts by mass of water and 0.2 parts by mass of sodium dodecylbenzenesulfonate, and the inside of the separable flask was sufficiently purged with nitrogen.
  • ether sulfate type emulsifier (trade name “Adekaria soap SR1025”, manufactured by ADEKA Co., Ltd.) as an emulsifier, 0.8 parts by mass in terms of solid content and 2 as a monomer , 2,2-trifluoroethyl methacrylate (TFEMA) 20 parts by mass, cyclohexyl methacrylate (CHMA) acrylonitrile (AN) 8 parts by mass, methyl methacrylate (MMA) 5 parts by mass, 2-ethylhexyl acrylate (EHA) 40 parts by mass And 5 parts by mass of acrylic acid (AA) were added and sufficiently stirred to prepare a monomer emulsion containing a mixture of the above monomers.
  • TFEMA 2,2-trifluoroethyl methacrylate
  • CHMA cyclohexyl methacrylate
  • AN cyclohexyl methacrylate
  • MMA methyl methacrylate
  • EHA 2-eth
  • Example C12 Binder composition for electricity storage device (C12)
  • Various evaluations were performed in the same manner as in Example C1, using the binder composition (C12). The evaluation results are shown in Table 2. Examples C13 and C14 and Comparative Examples c8 to c10 In Example C12, except that the types and amounts of the respective monomers are set as shown in Table 2, the polymer (B) having a solid content concentration of 30% by mass was obtained in the same manner as in Example C12.
  • Aqueous dispersions containing the particles (Binder compositions for power storage devices (C13), (C14) and (rc8) to (rc10)) were prepared, and various evaluations were performed in the same manner as in Example C1. The evaluation results are shown in Table 2.
  • Example C15 In a temperature-controllable autoclave equipped with a stirrer, water 200 parts by mass, sodium dodecylbenzenesulfonate 0.6 parts by mass, potassium persulfate 1.0 part by mass, sodium bisulfite 0.5 part by mass, ⁇ -methylstyrene 0.2 parts by mass of dimer, 0.2 parts by mass of dodecyl mercaptan and the first stage polymerization component shown in Table 3 were charged all at once, and the temperature was raised to 70 ° C. to conduct a polymerization reaction for 2 hours. After confirming that the polymerization addition rate was 80% by mass or more, the second-stage polymerization component shown in Table 3 was added over 6 hours while maintaining the reaction temperature at 70 ° C.
  • Example C15 aqueous dispersion (binder composition (C15)) containing 50% by mass of the polymer (B) particles.
  • Various evaluations were performed in the same manner as in Example C1, using the binder composition (C15). The evaluation results are shown in Table 3.
  • Examples C16 and C17 In the above Example C15, except that the types and amounts of the respective monomers are set as shown in Table 3, the solid content concentration of 50% by mass was obtained by the same two-stage polymerization method as in Example C15.
  • Aqueous dispersions (binder compositions for power storage devices (C16) and (C17)) containing particles composed of the combined body (B) were prepared, and various evaluations were performed in the same manner as in Example C1.
  • the evaluation results are shown in Table 3.
  • Abbreviations of monomers in Tables 1 to 3 have the following meanings, respectively. “ ⁇ ” In the monomer column indicates that the monomer was not used or the evaluation value of the monomer was not observed.
  • the power storage device binder composition (C1) obtained in Example C1 is added to the polymer so that the ratio of the polymer particles contained in the composition is 4 parts by mass, and water 85 mass is further added. After adding a part, it stirred for 1 hour and obtained the paste. After adding water to the obtained paste to adjust the solid content concentration to 40% by mass, the mixture was stirred at 200 rpm for 2 minutes at 200 rpm using a defoaming machine (manufactured by Shinky Co., Ltd., trade name “Awatori Nertaro”). 5 minutes at 1,800 rpm and further under reduced pressure (approximately 5 ⁇ 10 3 The slurry for positive electrode was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes at Pa).
  • the binder composition for an electricity storage device (C1) obtained in Example C1 was added so that the ratio of the polymer particles contained in the composition was 2 parts by mass, and further 35 parts by mass of ion-exchanged water. After adding, the mixture was stirred for 1 hour to obtain a paste. After adding ion-exchanged water to the obtained paste to adjust the solid content concentration to 50% by mass, using a stirring defoaming machine (trade name “Awatori Neritaro” manufactured by Shinkey Co., Ltd.) at 200 rpm 2 minutes, then at 1,800 rpm for 5 minutes, further under reduced pressure (approximately 5 ⁇ 10 3 In Pa), the slurry for negative electrode was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes.
  • a stirring defoaming machine trade name “Awatori Neritaro” manufactured by Shinkey Co., Ltd.
  • 5C rate characteristics (%) (C2) / (C1) ⁇ 100 (3) It can be determined that the larger the value of the 5C rate characteristic, the better the output characteristic can be obtained even in high-speed discharge. In particular, when the value of the 5C rate characteristic is 60% or more, it can be determined that this characteristic is good.
  • “1C” indicates a current value at which discharge is completed in one hour after constant current discharge of a cell having a certain electric capacity. For example, “0.1 C” is a current value at which discharge is completed over 10 hours, and 10 C is a current value at which discharge is completed over 0.1 hours (hereinafter the same).
  • the charging was continued at 1 V), and the time when the current value reached 0.01 C was defined as charging completion (cut-off).
  • discharging was started at a constant current (0.2 C), and the time when the voltage reached 2.5 V was regarded as completion of discharging (cut-off).
  • EIS measurement was performed on this cell, and EISb, which is a resistance value after application of thermal stress and overcharge stress, was measured.
  • the remaining capacity rate obtained by substituting the above measured values into the following formula (4) is 96%
  • the resistance increase rate obtained by substituting the above measured values into the following formula (5) is 35%. there were.
  • the rate of increase in resistance is preferably 225% or less, more preferably 150% or less, and even more preferably 100% or less.
  • Example E1 the binder compositions (C2) to (C17) and (rc1) to (rc1) to (c) obtained in Examples C2 to C17 and Comparative Examples c1 to c10, instead of the binder composition (C1) for the electricity storage device, An electricity storage device was produced in the same manner as in Example 1 except that rc10) was used, and various evaluations were performed. The evaluation results are shown in Table 4. As apparent from the above examples, when the binder composition for an electricity storage device of the present invention is applied to an electrode, an electrode having excellent adhesion is provided.
  • an electricity storage device lithium ion secondary battery including the electrode is excellent in high-speed discharge characteristics and excellent in resistance to thermal stress and overcharge.
  • the electricity storage devices (Comparative Examples e1 to e3) produced using the electricity storage device binder compositions obtained in Comparative Examples c1 to c3 were inferior in durability against thermal stress and overcharge. This is thought to be due to the insufficient resistance of these binder compositions to the electrolyte.
  • the electricity storage devices (Comparative Examples e4 to e6, e8 and e10) produced using the binder compositions for electricity storage devices of Comparative Examples c4 to c6, c8 and c10 were inferior in high-speed discharge characteristics.
  • binder compositions are considered to be due to insufficient affinity for the electrolytic solution.
  • the electrode formed from the binder composition for an electricity storage device of Comparative Example c7 was inferior in adhesion, and the electricity storage device comprising the electrode was inferior in both fast discharge characteristics and durability against thermal stress and overcharge (Comparative Example e7). . It is considered that the structural deterioration of the electrode is remarkable due to insufficient adhesion of the electrode.
  • the electricity storage devices produced using the binder compositions for electricity storage devices of Comparative Examples c8 to c10 were inferior in durability against thermal stress and overcharge (Comparative Examples e8 to e10). It is considered that the electrodes manufactured using these binder compositions are insufficient in oxidation resistance.
  • slurry for protective film In 500 parts by mass of water, 100 parts by mass of titanium oxide (made by Titanium Industry Co., Ltd., trade name “KR380”, rutile type, number average particle size 0.38 ⁇ m) as a filler, An amount corresponding to 5 parts by mass in terms of solid content of the binder composition for an electricity storage device (C1) obtained in Example C1 above, and 1 part by mass of the product name “CMC1120” manufactured by Daicel Corporation as a thickener Then, a slurry for protective film was prepared by mixing and dispersing using a thin film swirl type high-speed mixer “TK Fillmix (R) 56-50” manufactured by Primix Co., Ltd. 2.
  • the slurry for positive electrode was prepared by stirring and mixing at 1,800 rpm for 1.5 minutes at ⁇ 103 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. Thereafter, the density of the film (active material layer) is 2.0 g / cm.
  • the positive electrode was manufactured by pressing with a roll press so that (2) Production of negative electrode A biaxial planetary mixer “TK Hibismix 2P-03” was charged with 4 parts by mass of polyvinylidene fluoride (PVDF), 100 parts by mass of graphite as a negative electrode active material, and 80 parts by mass of N-methylpyrrolidone (NMP). Stirring was performed at 60 rpm for 1 hour. 20 parts of NMP is added to the mixture after stirring, and the mixture is stirred and mixed for 2 minutes at 200 rpm, 5 minutes at 1,800 rpm, and 1.5 minutes at 1,800 rpm under vacuum using a stirring defoaming machine “Awatori Netaro” Thus, a slurry for negative electrode was prepared.
  • PVDF polyvinylidene fluoride
  • 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. Thereafter, the density of the film is 1.5 g / cm 3
  • a negative electrode was manufactured by pressing using a roll press machine.
  • the thickness of the protective film was 2 ⁇ m on each side (4 ⁇ m in total on both sides).
  • the negative electrode produced in the above “(2) Production of negative electrode” is punched and molded to a diameter of 16.16 mm. (Trade name “HS flat cell”).
  • the separator with protective film produced in the above-mentioned “(3) Formation of protective film (manufacture of separator with protective film)” is placed, and the electrolytic solution is placed so that air does not enter.
  • the outer body of the bipolar coin cell is closed with a screw and sealed.
  • a lithium ion battery cell (electric storage device) was assembled.
  • the charging was continued at, and the time when the current value reached 0.01 C was regarded as charging completion (cut-off).
  • discharge was started at a constant current (0.2 C), and when the voltage reached 2.5 V, the discharge was completed (cut off), and C1 which was the value of the discharge capacity (initial) at 0.2 C was measured. did.
  • charging was started at a constant current (0.2 C) for the cells after the above discharge capacity (initial) measurement in a constant temperature bath at 25 ° C., and when the voltage reached 4.1 V, the constant voltage was continued.
  • Charging was continued at (4.1 V), and charging was completed (cut off) when the current value reached 0.01C.
  • EIS measurement Electrochemical Impedance Spectroscopy, "electrochemical impedance measurement” was performed on the charged cell, and an initial resistance value EISA was measured.
  • the cell in which the initial resistance value EISa was measured was placed in a constant temperature bath at 60 ° C., and charging was started at a constant current (0.2 C). When the voltage reached 4.4 V, the constant voltage (4. 4V) charging was continued for 240 hours (acceleration test of overcharge).
  • the charged cell was placed in a constant temperature bath at 25 ° C., and the cell temperature was lowered to 25 ° C., then discharging was started at a constant current (0.2 C), and the time when the voltage reached 2.5V.
  • C2 As a value of discharge capacity (after test) at 0.2 C was measured. Further, charging was started at a constant current (0.2 C) while the cell after the C2 measurement was placed in a constant temperature bath at 25 ° C., and when the voltage reached 4.1 V, the constant voltage (4. The charging was continued at 1 V), and the time when the current value reached 0.01 C was defined as charging completion (cut-off). Next, discharging was started at a constant current (0.2 C), and the time when the voltage reached 2.5 V was regarded as completion of discharging (cut-off). EIS measurement was performed on this cell, and EISb, which is a resistance value after application of thermal stress and overcharge stress, was measured.
  • Example P10 Preparation of slurry for protective film In 500 parts by mass of water, Magnesium oxide as a filler (manufactured by Tateho Chemical Co., Ltd., trade name “PUREMAG (R) FNM-G”, number average particle diameter 0.50 ⁇ m) 100 parts by mass, An amount corresponding to 5 parts by mass in terms of solid content of the binder composition for an electricity storage device (C10) obtained in Example C10, and 1 part by mass of the product name “CMC1120” manufactured by Daicel Corporation as a thickener Then, a slurry for protective film was prepared by mixing and dispersing using a thin film swirl type high-speed mixer “TK Fillmix (R) 56-50” manufactured by Primix Co., Ltd.
  • TK Fillmix (R) 56-50 manufactured by Primix Co., Ltd.
  • slurry for protective film Preparation of slurry for protective film” and the type and amount of binder composition for electricity storage device were as shown in Table 6, respectively. Prepared a protective film slurry in the same manner as in Example P1, and manufactured and evaluated lithium ion secondary battery cells (electric storage devices) using the protective film slurry. The evaluation results are shown in Table 6. Comparative Example p9 1.
  • Preparation of slurry for protective film (1) Preparation of polyimide solution
  • 1.0 mol of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 0.95 mol of o-tolidine diisocyanate were added to N -Dissolved in methyl-2-pyrrolidone (NMP) to give a solution with a monomer concentration of 20% by mass.
  • NMP methyl-2-pyrrolidone
  • 0.01 mol of diazabicycloundecene was added and mixed as a catalyst, and then reacted at 120 ° C. for 4 hours to obtain a solution containing polyimide (imidation rate 80%).
  • Example P10 a lithium ion secondary battery cell (electric storage device) was produced and evaluated in the same manner as in Example P10, except that the protective film slurry obtained above was used. The evaluation results are shown in Table 6. Comparative Example p10 1.
  • Preparation of slurry for protective film (1) Preparation of polyamideimide solution In a flask equipped with a condenser, a nitrogen gas inlet tube and a stirrer, 0.7 mol of trimellitic anhydride, 0.3 mol of 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, naphthalene diisocyanate 1 Mole and 0.01 mol of diazabicycloundecene were dissolved in N-methyl-2-pyrrolidone (NMP) to give a solution with a monomer concentration of 15% by mass, and the reaction was carried out at 80 ° C. for 3 hours to obtain a polyamideimide solution. Prepared.
  • NMP N-methyl-2-pyrrolidone
  • Example P10 a lithium ion secondary battery cell (electric storage device) was produced and evaluated in the same manner as in Example P10, except that the protective film slurry obtained above was used. The evaluation results are shown in Table 6.
  • Example P15 1.
  • slurry for protective film In 500 parts by mass of water, 100 parts by mass of aluminum oxide as a filler (manufactured by Sumitomo Chemical Co., Ltd., trade name “AKP-3000”, number average particle diameter 0.74 ⁇ m), An amount corresponding to 2 parts by mass in terms of solid content of the binder composition for an electricity storage device (C15) obtained in Example C15, and 1 part by mass of the product name “CMC1120” manufactured by Daicel Corporation as a thickener Then, a slurry for protective film was prepared by mixing and dispersing using a thin film swirl type high-speed mixer “TK Fillmix (R) 56-50” manufactured by Primix Co., Ltd. 2.
  • slurry for protective film Preparation of slurry for protective film” and the types and amounts of binder compositions for power storage devices were set as shown in Table 6, respectively. Prepared a protective film slurry in the same manner as in Example P15, and manufactured and evaluated lithium ion secondary battery cells (power storage devices) using the protective film slurry. The evaluation results are shown in Table 6. Abbreviations in the inorganic particle type column in Tables 5 and 6 have the following meanings, respectively.
  • TiO (1) manufactured by Titanium Industry Co., Ltd., trade name “KR380”, rutile type, number average particle size 0.38 ⁇ m
  • TiO (2) A product name “KR380” manufactured by Titanium Industry Co., Ltd., ground in an agate mortar and classified to a number average particle size of 0.12 ⁇ m using a sieve.
  • TiO (3) A product name “KR380” manufactured by Titanium Industry Co., Ltd., ground in an agate mortar and classified to a number average particle size of 0.08 ⁇ m using a sieve.
  • the invention's effect The electrode formed from the electrode slurry prepared using the binder composition for an electricity storage device of the present invention has excellent oxidation-reduction resistance and excellent adhesion, and thus maintains excellent initial charge / discharge characteristics for a long period of time. Durability.
  • An electricity storage device for example, a lithium ion secondary battery
  • the protective film formed from the slurry for the protective film prepared using the binder composition for an electricity storage device of the present invention can effectively prevent the short circuit caused by dendrites, and has the electrolyte permeability and liquid retention. High enough. Therefore, the electric storage device having the protective film is free from the risk of a short circuit without impairing the charge / discharge characteristics.
  • An electricity storage device manufactured using the binder composition for an electricity storage device of the present invention includes, for example, an electric power source for driving an electric vehicle, a hybrid vehicle, an electric tool, etc .; Batteries for personal computers, mobile phones, etc .; It can be suitably used for storage batteries attached to power generation devices such as solar power generation and wind power generation.

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Publication number Priority date Publication date Assignee Title
JP2015103482A (ja) * 2013-11-27 2015-06-04 旭化成イーマテリアルズ株式会社 蓄電デバイス用セパレータ、蓄電デバイス、リチウムイオン二次電池及び共重合体
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JP2015141840A (ja) * 2014-01-29 2015-08-03 旭化成イーマテリアルズ株式会社 蓄電デバイス用セパレータ、蓄電デバイス及びリチウムイオン二次電池
JP2016126856A (ja) * 2014-12-26 2016-07-11 三星エスディアイ株式会社Samsung SDI Co., Ltd. 二次電池用バインダ、二次電池用セパレータ、及び二次電池
WO2016111185A1 (ja) * 2015-01-05 2016-07-14 Ｎｅｃエナジーデバイス株式会社 電極およびそれを用いたリチウムイオン二次電池
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WO2018037867A1 (ja) * 2016-08-25 2018-03-01 日本ゼオン株式会社 非水系二次電池機能層用組成物、非水系二次電池用機能層、非水系二次電池、および非水系二次電池用電極の製造方法
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JP2018200838A (ja) * 2017-05-29 2018-12-20 三星エスディアイ株式会社Samsung SDI Co., Ltd. 正極活物質層、およびリチウムイオン二次電池
WO2019082660A1 (ja) 2017-10-27 2019-05-02 日本ゼオン株式会社 蓄電デバイス用接着剤組成物、蓄電デバイス用機能層、蓄電デバイス、及び蓄電デバイスの製造方法
WO2020017418A1 (ja) * 2018-07-20 2020-01-23 東亞合成株式会社 二次電池電極用バインダー及びその利用
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US12051782B2 (en) 2019-03-29 2024-07-30 Asahi Kasei Kabushiki Kaisha Method for producing non-aqueous alkali metal electricity storage element

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JP6431621B2 (ja) * 2015-11-19 2018-11-28 旭化成株式会社 蓄電デバイス用セパレータ並びにそれを用いた電極体及び蓄電デバイス
FR3044012B1 (fr) * 2015-11-24 2019-04-05 Arkema France Liant permettant de fixer un materiau contenant du poly fluorure de vinylidene sur un metal - electrode pour batterie lithium-ion associee
JP6720550B2 (ja) * 2016-01-21 2020-07-08 東洋インキＳｃホールディングス株式会社 顔料分散体、および積層体
CN105576284A (zh) * 2016-02-18 2016-05-11 福建蓝海黑石科技有限公司 一种锂离子电池负极水性粘合剂及其制备方法
EP3480876B1 (en) * 2016-06-29 2024-02-07 Zeon Corporation Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery
CN109565017B (zh) 2016-08-17 2023-03-24 日本瑞翁株式会社 非水系二次电池功能层用组合物、非水系二次电池用功能层及非水系二次电池
US20190379053A1 (en) * 2016-12-20 2019-12-12 Solvay Specialty Polymers Italy S.P.A. Aqueous electrode binders for lithium ion batteries
CN106833448B (zh) * 2017-02-08 2019-02-15 北京蓝海黑石科技有限公司 一种锂离子电池正极水性粘合剂及其制备方法
US20180254464A1 (en) * 2017-03-03 2018-09-06 Teijin Limited Separator for a non-aqueous secondary battery and non-aqueous secondary battery
CN106905475B (zh) * 2017-03-10 2020-09-25 湖南高瑞电源材料有限公司 一种锂电池陶瓷隔膜用含氟粘合剂的制备方法及使用该粘合剂制备的陶瓷隔膜
JP7031658B2 (ja) * 2017-03-17 2022-03-08 日本ゼオン株式会社 非水系二次電池機能層用組成物、非水系二次電池用機能層並びに非水系二次電池およびその製造方法
WO2018194101A1 (ja) * 2017-04-19 2018-10-25 日本エイアンドエル株式会社 電極用バインダー、電極用組成物及び電極
JP7122858B2 (ja) * 2017-05-24 2022-08-22 昭和電工株式会社 水系バインダー樹脂組成物、非水系電池用スラリー、非水系電池電極、非水系電池セパレータ、及び非水系電池
JP7090076B2 (ja) * 2017-05-29 2022-06-23 株式会社Ｅｎｅｏｓマテリアル 蓄電デバイス活物質層用バインダー組成物、蓄電デバイス電極用スラリー、蓄電デバイス電極及び蓄電デバイス
WO2019124122A1 (ja) 2017-12-21 2019-06-27 パナソニック株式会社 非水電解質二次電池用負極及び非水電解質二次電池
WO2019226641A1 (en) * 2018-05-21 2019-11-28 Kaneka Americas Holding, Inc. Varnish of polyimide having high heat resistance and excellent mechanical strength
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JP7234941B2 (ja) * 2018-11-22 2023-03-08 東レ株式会社 多孔性フィルム、二次電池用セパレータおよび二次電池
CN113272395B (zh) 2019-03-29 2022-11-22 三井化学株式会社 二次电池隔膜用涂覆材料
CN115768944B (zh) * 2020-07-10 2024-10-29 巴川集团股份有限公司 阻燃性片材
EP4391116A4 (en) * 2021-08-18 2025-12-03 Eneos Mat Corporation Composition of energy storage device binder, energy storage device electrode suspension, energy storage device electrode, and energy storage device
US20250118758A1 (en) * 2021-12-27 2025-04-10 Kureha Corporation Binder for non-aqueous electrolyte secondary battery, electrode mixture, electrode, and battery
KR20240160097A (ko) * 2022-03-09 2024-11-08 아란세오 도이치란드 게엠베하 애노드 제조용 고점도 가공을 위한 분말상 중합체 바인더
CN114920873B (zh) * 2022-05-09 2024-08-13 瑞固新能(上海)材料科技有限公司 一种锂离子电池隔膜用聚合物微球及其制备方法
US20260112636A1 (en) 2023-04-20 2026-04-23 Arlanxeo Deutschland Gmbh Functionalized pre-crosslinked hydrogenated nitrile rubbers as aqueous based cathode binders for li-ion battery applications
CN121464504A (zh) * 2023-05-05 2026-02-03 世索科特殊聚合物意大利有限公司 用于锂离子电池的正电极粘合剂

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004084245A1 (ja) * 2003-03-18 2004-09-30 Zeon Corporation 電気二重層キャパシタ電極用バインダー組成物
WO2005041225A1 (ja) * 2003-10-24 2005-05-06 Zeon Corporation 電気二重層キャパシタ電極用バインダー
WO2011068215A1 (ja) * 2009-12-03 2011-06-09 日本ゼオン株式会社 電気化学素子用バインダー粒子
WO2012169094A1 (ja) * 2011-06-06 2012-12-13 Jsr株式会社 蓄電デバイス用正極
WO2014041983A1 (ja) * 2012-09-11 2014-03-20 Jsr株式会社 保護膜を作製するための組成物および保護膜、ならびに蓄電デバイス

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04370661A (ja) * 1991-06-20 1992-12-24 Toshiba Battery Co Ltd 非水溶媒二次電池
JP3539448B2 (ja) 1995-04-19 2004-07-07 日本ゼオン株式会社 非水二次電池
GB0014464D0 (en) * 2000-06-15 2000-08-09 Aea Technology Plc A cell incorporating a porous membrane
EP1313158A3 (en) 2001-11-20 2004-09-08 Canon Kabushiki Kaisha Electrode material for rechargeable lithium battery, electrode comprising said electrode material, rechargeable lithium battery having said electrode , and process for the production thereof
JP4199703B2 (ja) * 2004-06-30 2008-12-17 東邦チタニウム株式会社 溶融塩電解による金属の製造方法
JP4748439B2 (ja) 2004-07-30 2011-08-17 日立化成工業株式会社 リチウム電池電極用バインダ樹脂組成物、電極および電池
KR101245064B1 (ko) 2004-10-06 2013-03-18 니폰 제온 가부시키가이샤 전극 조성물, 전극 및 전지
TW200740913A (en) * 2006-02-02 2007-11-01 Jsr Corp Polymer composition, paste for secondary battery electrode, and secondary battery electrode
JP4661843B2 (ja) 2007-08-28 2011-03-30 ソニー株式会社 非水電解質二次電池
JP5062526B2 (ja) 2007-09-27 2012-10-31 三洋電機株式会社 非水電解質電池用セパレータ及び非水電解質電池
US20100255380A1 (en) 2007-09-27 2010-10-07 Sanyo Electric Co., Ltd. Separator for nonaqueous electrolyte battery and nonaqueous electrolyte battery
WO2009123168A1 (ja) * 2008-03-31 2009-10-08 日本ゼオン株式会社 多孔膜および二次電池電極
JP5359074B2 (ja) * 2008-07-11 2013-12-04 東洋インキＳｃホールディングス株式会社 水系炭素材料組成物及びそれを用いた電池用組成物
JP5449327B2 (ja) * 2009-04-03 2014-03-19 東洋インキＳｃホールディングス株式会社 非水系二次電池電極用バインダー組成物
JP2011009116A (ja) * 2009-06-26 2011-01-13 Jsr Corp 電気化学デバイス電極用バインダー組成物、電気化学デバイス電極用スラリー、及び電気化学デバイス電極
JP5796279B2 (ja) * 2009-07-10 2015-10-21 シンフォニアテクノロジー株式会社 ロードポート装置、並びにその蓋体着脱装置及びマッピング装置の各昇降機構の制御方法
CN102714317B (zh) * 2010-01-15 2015-02-25 Jsr株式会社 全固体型电池用粘合剂组合物以及全固体型电池电极用浆料
JPWO2011099344A1 (ja) * 2010-02-15 2013-06-13 Jsr株式会社 電極バインダー用組成物、電極用組成物、電極および電気化学デバイス
JP5570393B2 (ja) 2010-11-11 2014-08-13 東洋化学株式会社 電極用バインダー
JP4849286B1 (ja) 2011-06-06 2012-01-11 Ｊｓｒ株式会社 正極用バインダー組成物
JP5782861B2 (ja) * 2011-06-23 2015-09-24 日本ゼオン株式会社 二次電池用正極及び二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004084245A1 (ja) * 2003-03-18 2004-09-30 Zeon Corporation 電気二重層キャパシタ電極用バインダー組成物
WO2005041225A1 (ja) * 2003-10-24 2005-05-06 Zeon Corporation 電気二重層キャパシタ電極用バインダー
WO2011068215A1 (ja) * 2009-12-03 2011-06-09 日本ゼオン株式会社 電気化学素子用バインダー粒子
WO2012169094A1 (ja) * 2011-06-06 2012-12-13 Jsr株式会社 蓄電デバイス用正極
WO2014041983A1 (ja) * 2012-09-11 2014-03-20 Jsr株式会社 保護膜を作製するための組成物および保護膜、ならびに蓄電デバイス

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015103482A (ja) * 2013-11-27 2015-06-04 旭化成イーマテリアルズ株式会社 蓄電デバイス用セパレータ、蓄電デバイス、リチウムイオン二次電池及び共重合体
JP2015128059A (ja) * 2013-11-27 2015-07-09 旭化成イーマテリアルズ株式会社 蓄電デバイス用セパレータ、蓄電デバイス、リチウムイオン二次電池及び共重合体
JP2016033921A (ja) * 2013-11-27 2016-03-10 旭化成イーマテリアルズ株式会社 蓄電デバイス用セパレータ、蓄電デバイス及びリチウムイオン二次電池
JP2016201367A (ja) * 2013-11-27 2016-12-01 旭化成株式会社 蓄電デバイス用セパレータ、蓄電デバイス、リチウムイオン二次電池及び共重合体
JP2015141840A (ja) * 2014-01-29 2015-08-03 旭化成イーマテリアルズ株式会社 蓄電デバイス用セパレータ、蓄電デバイス及びリチウムイオン二次電池
JP2016126856A (ja) * 2014-12-26 2016-07-11 三星エスディアイ株式会社Samsung SDI Co., Ltd. 二次電池用バインダ、二次電池用セパレータ、及び二次電池
WO2016111185A1 (ja) * 2015-01-05 2016-07-14 Ｎｅｃエナジーデバイス株式会社 電極およびそれを用いたリチウムイオン二次電池
JP2016213019A (ja) * 2015-05-01 2016-12-15 旭化成株式会社 蓄電デバイス用セパレータ、蓄電デバイス、及びリチウムイオン二次電池
EP3379623A4 (en) * 2015-11-19 2018-10-31 Asahi Kasei Kabushiki Kaisha Binder for electricity storage device and binder composition for electricity storage device
US10770706B2 (en) 2015-11-19 2020-09-08 Asahi Kasei Kabushiki Kaisha Binder for electricity storage device and binder composition for electricity storage device
JP7020416B2 (ja) 2016-08-25 2022-02-16 日本ゼオン株式会社 非水系二次電池機能層用組成物、非水系二次電池用機能層、非水系二次電池、および非水系二次電池用電極の製造方法
JPWO2018037867A1 (ja) * 2016-08-25 2019-06-20 日本ゼオン株式会社 非水系二次電池機能層用組成物、非水系二次電池用機能層、非水系二次電池、および非水系二次電池用電極の製造方法
WO2018037867A1 (ja) * 2016-08-25 2018-03-01 日本ゼオン株式会社 非水系二次電池機能層用組成物、非水系二次電池用機能層、非水系二次電池、および非水系二次電池用電極の製造方法
US10930912B2 (en) 2016-08-25 2021-02-23 Zeon Corporation Composition for non-aqueous secondary battery functional layer, functional layer for non-aqueous secondary battery, non-aqueous secondary battery, and method of producing electrode for non-aqueous secondary battery
JP2018163872A (ja) * 2017-03-03 2018-10-18 帝人株式会社 非水系二次電池用セパレータ及び非水系二次電池
JP2018200838A (ja) * 2017-05-29 2018-12-20 三星エスディアイ株式会社Samsung SDI Co., Ltd. 正極活物質層、およびリチウムイオン二次電池
JP7105544B2 (ja) 2017-05-29 2022-07-25 三星エスディアイ株式会社 正極活物質層、およびリチウムイオン二次電池
WO2019082660A1 (ja) 2017-10-27 2019-05-02 日本ゼオン株式会社 蓄電デバイス用接着剤組成物、蓄電デバイス用機能層、蓄電デバイス、及び蓄電デバイスの製造方法
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WO2020017418A1 (ja) * 2018-07-20 2020-01-23 東亞合成株式会社 二次電池電極用バインダー及びその利用
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