WO2016076370A1 - 蓄電デバイス用バインダー組成物、蓄電デバイス用電極合剤、蓄電デバイス用電極、及び二次電池 - Google Patents
蓄電デバイス用バインダー組成物、蓄電デバイス用電極合剤、蓄電デバイス用電極、及び二次電池 Download PDFInfo
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- WO2016076370A1 WO2016076370A1 PCT/JP2015/081779 JP2015081779W WO2016076370A1 WO 2016076370 A1 WO2016076370 A1 WO 2016076370A1 JP 2015081779 W JP2015081779 W JP 2015081779W WO 2016076370 A1 WO2016076370 A1 WO 2016076370A1
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- electricity storage
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Classifications
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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
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- 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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/24—Trifluorochloroethene
- C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
- C08F214/247—Trifluorochloroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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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- H01M4/06—Electrodes for primary cells
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a binder composition for an electricity storage device, an electrode mixture for an electricity storage device, an electrode for an electricity storage device, and a secondary battery.
- Patent Document 1 discloses a battery comprising a fluorine-containing copolymer having a hydrophilic group in a side chain and having a specific molecular weight range, and an aqueous dispersion containing polytetrafluoroethylene (PTFE). It has been shown to be excellent in properties.
- the binder described in Examples (Table 1) of Patent Document 1 is an aqueous dispersion (A) of a fluorinated copolymer having units (a), (b), and (c) in the present invention. This is a mixture of (B) and an aqueous dispersion of polytetrafluoroethylene (PTFE) (G), and the mixture, the electrode active material and the conductive additive are uniformly stirred to prepare an electrode mixture.
- Patent Document 2 describes an aqueous dispersion of a fluorine-containing polymer as a binder to be contained in an aqueous paste for battery formation.
- the stability of the aqueous paste for battery formation and the electrode active material layer, current collector In order to improve the adhesion, a method of mixing an aqueous dispersion of a crystalline fluorine-containing polymer such as PTFE and an aqueous dispersion of an amorphous fluorine-containing polymer is described.
- amorphous fluorine-containing polymer a copolymer of ethyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether and chlorotrifluoroethylene is described (paragraph [0045]).
- Patent Documents 1 and 2 describe aqueous dispersions of fluorine-containing copolymers having units (a), (b), and (c) in the present invention.
- the dispersion stability of the aqueous dispersion is not always sufficient.
- Patent Documents 1 and 2 describe that an aqueous dispersion of a fluorine-containing copolymer and an aqueous dispersion of PTFE are mixed to form a binder.
- PTFE when PTFE is subjected to shearing, the viscosity is likely to increase. Therefore, it is difficult to obtain good coatability in an electrode mixture using such a binder. There are challenges.
- the present invention has good dispersion stability, good adhesion, good coating properties in an electrode mixture for power storage devices, and can realize good charge / discharge characteristics in a secondary battery. It aims at providing the binder composition for devices, the electrode mixture for electrical storage devices using the binder composition, the electrode for electrical storage devices, and a secondary battery.
- the gist of the present invention is the following [1] to [6].
- Unit (a) based on the following monomer (A), unit (b) based on the following monomer (B), unit (c) based on the following monomer (C), and monomer below The binder composition for electrical storage devices containing the fluorine-containing copolymer containing the unit (d) based on (D), and a liquid medium.
- n is 0 or 1
- R represents a saturated hydrocarbon group having 1 to 20 carbon atoms.
- n and R may be the same or different.
- Monomer (C) from the group consisting of a compound having an ethylenically unsaturated bond and a hydroxy group, a compound having an ethylenically unsaturated bond and an epoxy group, and a compound having an ethylenically unsaturated bond and a carboxy group A compound having at least one selected and having a molecular weight of less than 300.
- the content of the unit (a) is 20 to 80 mol%, the content of the unit (b) is 1 to 70 mol%, and the unit (c) with respect to the total of all the units of the fluorine-containing copolymer.
- the content of 0.1 to 40 mol%, the content of unit (d) is 0.1 to 25 mol%, and the total of units (a) to (d) is 70 to 100 mol%
- the binder composition for an electricity storage device according to the above [1].
- the monomer (C) includes one or more compounds selected from the group consisting of compounds represented by the following formulas (III) to (VI): Binder composition for electricity storage device.
- n is 0 or 1
- m is an integer of 0 to 2
- R 1 is a (m + 2) -valent saturated hydrocarbon group having 1 to 10 carbon atoms, or a carbon number having an etheric oxygen atom.
- R 2 is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms or a divalent saturated hydrocarbon having 2 to 8 carbon atoms having an etheric oxygen atom
- R 3 represents a hydrocarbon group, and R 3 represents an alkylene group having 1 to 8 carbon atoms or an alkylene group having 2 to 8 carbon atoms having an etheric oxygen atom.
- a plurality of m, n, R 1 , R 2 , and R 3 may be the same or different.
- the ethylenically unsaturated bond and — (CH 2 CH 2 O) p H (p is 1 to 50) are a linking group containing a 1,4-cyclohexylene group.
- a method for producing a binder composition for an electricity storage device according to the above [1] to [8], wherein the monomer component comprises monomers (A), (B), (C) and (D) Is a method of emulsion polymerization in the liquid medium.
- An electrode mixture for an electricity storage device comprising the binder composition for an electricity storage device according to any one of [1] to [8] above and a battery active material.
- the electrode for an electricity storage device according to [11] wherein a peel strength between the electrode active material layer and the current collector is 3N or more.
- a secondary battery comprising the electricity storage device electrode according to any one of [11] to [13] and an electrolytic solution.
- the binder composition for an electricity storage device of the present invention has good dispersion stability, good adhesion, good coating properties in an electrode mixture for an electricity storage device, and good chargeability in a secondary battery. Discharge characteristics can be realized. Moreover, the reactivity in an electrode is restrained lower, the thermal runaway in a secondary battery is less likely to occur, and higher safety is obtained.
- an electrode for an electricity storage device using the electrode mixture, and a secondary battery comprising the electrode, the adhesion between the electrode active materials and the electrode active material and the current collector Adhesiveness is excellent, good charge / discharge characteristics are obtained, and further, the reactivity of the electrodes is suppressed to a lower level, so that thermal runaway of the secondary battery is less likely to occur and higher safety is obtained.
- the “monomer” is a compound having a polymerizable carbon-carbon double bond (ethylenically unsaturated bond).
- a “unit based on a monomer” is a structural unit composed of monomer molecules formed by polymerization of monomers, in which part of the monomer molecules have disappeared due to decomposition. Also good.
- a monomer and a unit based on the monomer are represented using the same alphabet. For example, “unit (a)” represents “unit based on monomer (A)”.
- the number average molecular weight of the fluorinated copolymer is a value obtained as a polystyrene-converted value measured by gel permeation chromatography (GPC) using a solvent soluble in the fluorinated copolymer.
- examples of the electricity storage device include a lithium ion primary battery, a lithium ion secondary battery, a lithium polymer battery, an electric double layer capacitor, and a lithium ion capacitor.
- a lithium ion primary battery As an electricity storage device, it is particularly preferable to use it for a lithium ion secondary battery because it can more effectively express adhesiveness, electrolytic solution resistance, charge / discharge characteristics, and the like.
- the binder composition for an electricity storage device of the present invention (hereinafter sometimes simply referred to as a binder composition) includes a unit (a) based on the monomer (A) and a unit (b) based on the monomer (B). And a fluorine-containing copolymer having a unit (c) based on the monomer (C) and a unit (d) based on the monomer (D).
- the monomer (A) is one or more compounds selected from the group consisting of tetrafluoroethylene (TFE) and chlorotrifluoroethylene (CTFE). CTFE is preferable.
- the monomer (B) is at least one compound selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following (II).
- CH 2 ⁇ CH— (CH 2 ) n —O—R (I) CH 2 ⁇ CH— (CH 2 ) n —OCO—R (II)
- n is 0 or 1
- R represents a saturated hydrocarbon group having 1 to 20 carbon atoms. When two or more kinds of compounds are used, a plurality of n and R may be the same or different.
- the saturated hydrocarbon group as R may contain a linear, branched or ring structure. R does not have a fluorine atom.
- the saturated hydrocarbon group as R has 1 to 20 carbon atoms, and is preferably 2 to 15 and more preferably 2 to 10 in that good adhesion can be easily obtained.
- Specific examples of the monomer (B) include vinyl ethers such as ethyl vinyl ether (EVE), propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether (CHVE); ethyl allyl ether, propyl allyl ether, butyl allyl ether, And allyl ethers such as cyclohexyl allyl ether; vinyl esters such as butanoic acid vinyl ester and octanoic acid vinyl ester; and allyl esters such as butanoic acid allyl ester and octanoic acid allyl ester. Vinyl ethers and allyl ethers are preferred.
- the monomer (C) is a group consisting of a compound having an ethylenically unsaturated bond and a hydroxy group, a compound having an ethylenically unsaturated bond and an epoxy group, and a compound having an ethylenically unsaturated bond and a carboxy group. It is a compound having at least one selected from those and having a molecular weight of less than 300.
- the monomer (C) has at least one of a hydroxy group, an epoxy group, or a carboxy group, and may have two or more of these. Units based on the monomer (C) contribute to the improvement of adhesion.
- Examples of the compound having an ethylenically unsaturated bond and a hydroxy group include a vinyl ether having a hydroxy group, a vinyl ester having a hydroxy group, an allyl ether having a hydroxy group, and One or more compounds selected from the group consisting of allyl esters having a hydroxy group are preferred.
- the compound represented by the following formula (III) or (IV) is mentioned.
- Examples of the compound having an ethylenically unsaturated bond and an epoxy group include a vinyl ether having an epoxy group, a vinyl ester having an epoxy group, an allyl ether having an epoxy group, and One or more compounds selected from the group consisting of allyl esters having an epoxy group are preferred.
- the compound represented by the following formula (V) or (VI) is mentioned.
- n is 0 or 1.
- m is an integer of 0-2.
- a plurality of m, n, R 1 , R 2 , and R 3 may be the same or different.
- Hydrocarbon group (however, the number of etheric oxygen atoms contained when the saturated hydrocarbon group has 2 carbon atoms is 1 and the etheric oxygen atom contained when the saturated hydrocarbon group has 3 carbon atoms) Is 1 or 2.).
- Specific examples include an alkylene group, a cycloalkylene group, and an alkylene group containing a cycloalkylene group.
- the alkylene group may be linear or branched.
- a cycloalkylene group having 5 to 8 carbon atoms is preferable, and a cyclohexylene group is particularly preferable.
- Examples of the alkylene group including a cycloalkylene group include —CH 2 —C 6 H 10 —CH 2 —.
- R 3 represents an alkylene group having 1 to 8 carbon atoms or an alkylene group having 2 to 8 carbon atoms having an etheric oxygen atom. It may be linear or branched. R 3 is preferably an alkylene group having 1 to 4 carbon atoms.
- the monomer (Ci) examples include 2-hydroxyethyl vinyl ether (HEVE), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether (HBVE), 4-hydroxy-2-methylbutyl vinyl ether, Hydroxyalkyl vinyl ethers such as 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; Monovinyl ethers of alicyclic diols such as cyclohexanedimethanol monovinyl ether (CHMVE); Polyethylene glycol monovinyl ethers such as diethylene glycol monovinyl ether (DEGV), triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether; Hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether, hydroxybutyl allyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl ally
- the monomer (C-ii) examples include allyl glycidyl ether, glycidyl vinyl ether, allyl-3,4-epoxybutyl ether, allyl-5,6-epoxyhexyl ether, and the like.
- Examples of the compound having an ethylenically unsaturated bond and a carboxy group include 3-butenoic acid, 4-pentenoic acid, 2-hexenoic acid, and 3-hexenoic acid.
- the monomer (C) preferably contains at least one compound selected from the group consisting of the monomer (Ci) and the monomer (C-ii).
- the total amount of the monomer (Ci) and the monomer (C-ii) is preferably 50% by mass or more, more preferably 70% by mass or more based on the total amount of the monomer (C). It may be 100% by mass.
- the monomer (D) is one or more kinds of macromonomers having a hydrophilic portion and a compound having a molecular weight of 300 or more.
- the “macromonomer” means a low molecular weight polymer or oligomer having an ethylenically unsaturated bond in the molecule.
- the molecular weight or average molecular weight of the macromonomer is preferably 300 to 10,000, and more preferably 400 to 5000.
- the molecular weight of the macromonomer means a formula weight obtained based on the chemical formula.
- “Hydrophilic part” means a part having a hydrophilic group, a part having a hydrophilic bond, or a part composed of a combination thereof. Those corresponding to any of the monomers (A) to (C) are not included in the monomer (D).
- the macromonomer preferably has an ethylenically unsaturated bond in the molecule and a polyether chain or a polyester chain.
- the group having an ethylenically unsaturated bond include vinyl group, vinyl ether group, vinyl ester group, allyl group, allyl ether group, allyl ester group, acryloyl group, and methacryloyl group.
- a vinyl group or a vinyl ether group is preferable because the synthesis of the fluorine-containing copolymer is easy.
- hydrophilic group examples include an ionic (anionic or cationic) hydrophilic group, a nonionic hydrophilic group, an amphoteric hydrophilic group, and a combination thereof.
- the anionic hydrophilic group -SO 3 - NH + 4, -SO 3 - Na + and the like.
- cationic hydrophilic group examples include —NH 3 + CH 3 COO — .
- nonionic hydrophilic groups include — (CH 2 CH 2 O) p H (p is 1 to 50).
- amphoteric hydrophilic group examples include —N + (CH 3 ) 2 CH 2 COO — and the like.
- a portion having a nonionic or amphoteric hydrophilic group and a portion having another hydrophilic group are combined, or a portion having a hydrophilic group and a hydrophilic bond It is preferable to combine with the site
- Examples of the preferred structure of the macromonomer having a hydrophilic site as the monomer (D) include the following (1) to (7).
- (2) CH 2 CHCH 2 O (CH 2 ) d [O (CH 2 ) e ] f OR 2 (d is an integer of 1 to 10, e is an integer of 1 to 4, f is an integer of 2 to 20, R 2 is a hydrogen atom or a lower alkyl group).
- the lower alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
- the monomer (D) one having a vinyl ether type structure in the molecule is preferable because of excellent copolymerizability with the fluoroolefin.
- the polyether chain portion is composed of oxyethylene units or oxyethylene units and oxypropylene units because of excellent hydrophilicity.
- various properties such as stability are improved.
- the solvent resistance with respect to electrolyte solution will worsen.
- the number of oxyalkylene units in one molecule is preferably 2 or more and 100 or less, and more preferably 2 or more and 75 or less.
- Such a macromonomer having a hydrophilic moiety can be produced by a method such as polymerizing formaldehyde or diol with a vinyl ether or allyl ether having a hydroxyl group, or ring-opening polymerization of a compound having an alkylene oxide or a lactone ring.
- Macromonomers having such a hydrophilic moiety are described by Yamashita et al. In Polym. Bull. , 5.335 (1981).
- Methyl) alkyl ether ammonium sulfate Aqualon HS-10 (polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate), Aqualon RN-20 (polyoxyethylene nonylpropenyl phenyl ether); Antox MS-60 (2-sodium manufactured by Nippon Emulsifier Co., Ltd.) Sulfoethyl methacrylate), Antox SAD (alkyl allyl succinate sulfonate Na salt), Antox MS-2N (2-sodium sulfoethyl methacrylate) antox MA-10 (alkoxy polyethylene glycol methacrylate), Ann Krytox EMH-20 (alkoxy polyethylene glycol maleate); manufactured by Sanyo Chemical Industries, Ltd. of ELEMINOL JS-20, a ELEMINOL RS-3000 and the like.
- p is 1 to 50
- the group having an ethylenically unsaturated bond is preferably a vinyl ether group.
- the fluorine-containing copolymer is not a unit (a) to (d), and does not fall under any of the monomers (A) to (D), and can be copolymerized with other monomers. You may have a unit (other units (e)) based on a body (E).
- Examples of other monomers (E) include olefins such as ethylene and propylene, vinyl compounds such as aromatic vinyl compounds such as styrene and vinyltoluene, acryloyl compounds such as butyl acrylate, and ethyl methacrylate. And methacryloyl compounds.
- olefins are preferred.
- the total of the units (a) to (d) is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and further 90 to 100 mol% with respect to all units constituting the fluorinated copolymer. preferable.
- the content of the unit (a) is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, based on the total of all units.
- the total content thereof is the “content of the unit (a)”.
- the content of the unit (b) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, still more preferably 10 to 50 mol%, based on the total of all units.
- the unit (b) contains two or more types of units, the total content thereof is “content of unit (b)”.
- the content of the unit (c) is preferably from 0.1 to 40 mol%, more preferably from 1 to 20 mol%, based on the total of all units. It is excellent in the chemical stability of an aqueous dispersion as it is more than the lower limit of the said range. Good adhesiveness is easy to be obtained if it is below the upper limit.
- the content of the unit (d) is preferably from 0.1 to 25 mol%, more preferably from 0.3 to 20 mol%, based on the total of all units.
- it is at least the lower limit of the above range, good dispersion stability is easily obtained. That is, the formation of precipitates in the mechanical stability test described later is suppressed. Good adhesiveness is easy to be obtained if it is below the upper limit.
- the number average molecular weight of the fluorine-containing copolymer is preferably 20,000 to 1,000,000, more preferably 20,000 to 800,000, still more preferably 20,000 to 700,000, and particularly preferably 20,000 to 500,000.
- the lower limit of the above range good adhesion is easily obtained, and when it is at most the upper limit, good dispersion stability is easily obtained.
- the fluorine-containing copolymer can be produced by copolymerizing the monomers (A), (B), (C), (D), and any monomer (E) by an emulsion polymerization method. According to the emulsion polymerization method, a fluorine-containing copolymer having a high molecular weight (for example, a number average molecular weight of 20,000 or more) is easily obtained.
- a known method can be appropriately used in the production of the fluorinated copolymer.
- the latex obtained in the emulsion polymerization step can be used as it is as the binder composition of the present invention.
- the binder composition for an electricity storage device of the present invention includes a fluorine-containing copolymer and a liquid medium.
- the binder composition is preferably a latex in which a fluorine-containing copolymer is dispersed in a liquid medium.
- Latex is a dispersion of a fluorinated copolymer, but a part of the fluorinated copolymer may be dissolved in a liquid medium.
- the liquid medium is preferably an aqueous medium.
- the aqueous medium is water alone or a mixture of water and a water-soluble organic solvent. It is preferable to use ion-exchanged water.
- water-soluble organic solvent a known compound that can be dissolved in water at an arbitrary ratio can be appropriately used.
- alcohols are preferable, and examples thereof include tert-butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol. Of these, tert-butanol, propylene glycol, dipropylene glycol or dipropylene glycol monomethyl ether is preferred.
- the content (solid content concentration) of the fluorinated copolymer in the binder composition is more preferably 5 to 70% by mass, further preferably 10 to 60% by mass, and more preferably 15 to 55% by mass with respect to the total amount of the binder composition. % Is particularly preferred.
- % Is particularly preferred.
- the electrode mixture is prepared using the binder composition as being above the lower limit of the above range, a good viscosity of the electrode mixture is easily obtained, and a thick coating is performed on the current collector. Can do.
- it is below the upper limit of the above range when preparing an electrode mixture by dispersing an electrode active material or the like in the binder composition, it is easy to obtain good dispersion stability, and good coating properties of the electrode mixture Is easy to obtain.
- the content of the liquid medium in the binder composition for an electricity storage device of the present invention is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and particularly preferably 45 to 85% by mass with respect to the total amount of the binder composition. preferable.
- the content of the liquid medium in the binder composition is not more than the upper limit of the above range, when an electrode mixture is prepared using the binder composition, a good viscosity of the electrode mixture is easily obtained, and the current collector is collected. A thick coating can be applied on the body.
- the electrode mixture is prepared by dispersing an electrode active material or the like in the binder composition as being above the lower limit of the above range, good dispersion stability is easily obtained, and good uniform coating of the electrode mixture It is easy to get sex.
- the binder composition may contain components other than the fluorine-containing copolymer and the liquid medium.
- other components include emulsifiers and initiators used during the production of the fluorine-containing copolymer.
- the total content of components other than the fluorine-containing copolymer and the liquid medium is preferably 10% by mass or less, and more preferably 1% by mass or less, based on the total amount of the binder composition.
- the binder composition of the present invention is excellent in latex dispersion stability because the fluorine-containing copolymer has the unit (d). Specifically, a binder composition having a precipitate production amount of 1% by mass or less by a mechanical stability test is obtained. A small amount of precipitate generated indicates that precipitation hardly occurs even when an external force such as stirring is applied, and that the mechanical stability is excellent.
- the amount of precipitate produced is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less. The lower limit is ideally 0% by mass.
- the latex of the fluorinated copolymer is stirred at 25 ° C.
- the mass ratio (%) with respect to the solid content in the fluorine-containing copolymer latex with respect to the mass after drying the filtration residue at 140 ° C. for 1 hour is defined as the amount of precipitate produced.
- the electrode mixture for an electricity storage device of the present invention contains the binder composition of the present invention and an electrode active material.
- a conductive material may be contained as necessary, and other components other than these may be contained.
- the electrode active material used by this invention is not specifically limited, A well-known thing can be used suitably.
- the positive electrode active material metal oxides such as MnO 2 , V 2 O 5 , V 6 O 13 ; metal sulfides such as TiS 2 , MoS 2 , FeS; LiCoO 2 , LiNiO 2 , LiMn 2 O 4, etc.
- Examples include lithium composite metal oxides containing transition metals such as Co, Ni, Mn, Fe, and Ti; compounds in which a part of transition metal elements in these compounds is substituted with other metal elements; and the like. Further, a conductive polymer material such as polyacetylene or poly-p-phenylene can be used. Moreover, what coat
- the negative electrode active material examples include carbides of high molecular compounds such as coke, graphite, mesophase pitch spherules, phenol resin, polyparaphenylene, and carbonaceous materials such as vapor-generated carbon fiber and carbon fiber.
- metals such as Si, Sn, Sb, Al, Zn, and W that can be alloyed with lithium are also included.
- a silicon oxide represented by a general formula SiOx (x is preferably 0.5 to 1.5) represented by silicon monoxide can be given.
- the electrode active material a material in which a conductive material is attached to the surface by a mechanical modification method or the like can also be used. In the case of an electrode mixture for a lithium ion secondary battery, any electrode active material may be used as long as it can reversibly insert and release lithium ions by applying a potential in the electrolyte. be able to.
- the electrode mixture used for the production of the positive electrode preferably contains a conductive material.
- a conductive material By including a conductive material, the electrical contact between the electrode active materials can be improved, the electrical resistance in the active material layer can be lowered, and the discharge rate characteristics of the non-aqueous secondary battery can be improved.
- the conductive material include conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor grown carbon fiber, and carbon nanotube.
- the electrode mixture contains a conductive material, the effect of reducing electrical resistance is increased by adding a small amount of the conductive material, which is preferable.
- the electrode mixture can be used as other components. Specific examples include water-soluble polymers such as carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid, and polymethacrylic acid.
- the ratio of the fluorinated copolymer in the electrode mixture of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, with respect to 100 parts by mass of the electrode active material. 8 parts by mass is particularly preferable.
- the proportion of the conductive material in the electrode mixture is more than 0 parts by mass with respect to 100 parts by mass of the electrode active material, preferably 20 parts by mass or less, 1 to 10 parts by mass is more preferable, and 3 to 8 parts by mass is particularly preferable.
- the solid content concentration in the electrode mixture is preferably 30 to 95% by mass, more preferably 40 to 85% by mass, and particularly preferably 45 to 80% by mass with respect to 100% by mass of the electrode mixture.
- the electrode for an electricity storage device of the present invention has a current collector and an electrode active material layer containing the binder for an energy storage device of the present invention and an electrode active material on the current collector.
- the current collector is not particularly limited as long as it is made of a conductive material.
- metal foils such as aluminum, nickel, stainless steel, and copper, metal nets, and metal porous bodies are exemplified.
- Aluminum is preferably used as the positive electrode current collector, and copper is preferably used as the negative electrode current collector.
- the thickness of the current collector is preferably 1 to 100 ⁇ m.
- the electrode mixture of the present invention is applied to at least one side, preferably both sides, of a current collector, and the liquid medium in the electrode mixture is removed by drying to obtain an electrode active material. It is obtained by forming a layer. If necessary, the electrode active material layer after drying may be pressed to have a desired thickness.
- Various application methods can be used as a method of applying the electrode mixture to the current collector. Examples thereof include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
- the coating temperature is not particularly limited, but usually a temperature around room temperature is preferable.
- Drying can be performed using various drying methods, for example, drying by warm air, hot air, low-humidity air, etc., vacuum drying, drying by irradiation with (far) infrared rays, electron beams, or the like.
- the drying temperature is not particularly limited, but is usually preferably room temperature to 200 ° C. in a heating vacuum dryer or the like.
- a pressing method a mold press, a roll press or the like can be used.
- the electrode adhesion that is, the peel strength between the electrode active material layer and the current collector, is preferably high, and is determined as follows.
- the press peel resistance strength between the electrode active material layer and the current collector is also high. That is, when an electrode manufactured by adjusting the thickness of the electrode active material layer after drying to 120 ⁇ m was cut into a rectangle 25 mm wide ⁇ 40 mm long and roll-pressed at a feed rate of 0.8 m / min
- the maximum pressure at which no peeling occurs was defined as the press peeling resistance strength. It shows that peeling is hard to occur at the time of press, so that this value is large.
- the press peel resistance strength is preferably 0.7 kN / cm or more, and more preferably 1.0 kN / cm or more. Although there is no upper limit in particular, it is 10 kN / cm, for example.
- a lithium ion secondary battery as an electricity storage device includes the electrode for an electricity storage device of the present invention as at least one of a positive electrode and a negative electrode, and an electrolyte. Furthermore, it is preferable to provide a separator.
- the electrolytic solution includes an electrolyte and a solvent.
- the solvent include aprotic organic solvents such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), and methyl ethyl carbonate (MEC).
- Alkyl carbonates such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfur-containing compounds such as sulfolane and dimethyl sulfoxide;
- dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, or methyl ethyl carbonate is preferable because high ion conductivity is easily obtained and the use temperature range is wide.
- the electrolyte include lithium salts such as LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 5 , CF 3 SO 3 Li, and (CF 3 SO 2 ) 2 NLi.
- composition of fluorine-containing copolymer The content of units based on each monomer (composition of the copolymer) relative to the total of all units of the fluorinated copolymer is measured by 19 F-NMR analysis, infrared absorption spectrum analysis, fluorine content analysis, etc. did.
- a latex of a fluorine-containing copolymer was dried in an oven at 140 ° C. for 1 hour and then dried in a vacuum dryer (internal pressure 10 Torr, 50 ° C.) for 24 hours.
- Evaluation of the charge / discharge characteristics of the secondary battery was performed by the following method.
- [Evaluation of positive electrode] (1) Manufacture of secondary batteries (positive electrode half cell) The manufactured positive electrode was cut into a circle having a diameter of 18 mm, and a lithium metal foil having the same area and a polyethylene separator were laminated in a 2032 type coin cell in the order of the lithium metal foil, the separator, and the positive electrode to prepare a battery element. A non-aqueous electrolyte solution was added thereto, and then sealed, thereby producing a coin-type non-aqueous electrolyte secondary battery.
- Discharge capacity ratio (%) (3C discharge capacity / 0.2C discharge capacity) ⁇ 100
- 3C discharge was performed as described above, and the discharge capacity ratio after 100 cycles was calculated.
- a high discharge capacity ratio after 100 cycles indicates that an increase in resistance in the electrode is suppressed even after the charge / discharge cycle.
- the obtained secondary battery in a charged state was decomposed in an argon atmosphere to obtain a charged positive electrode.
- the obtained positive electrode was washed three times with dimethyl carbonate (2 mL), vacuum-dried, then punched out to a diameter of 5 mm, placed in a sealed container made of SUS, and further sealed with 2 ⁇ L of the non-aqueous electrolyte of each example. And it was set as the evaluation sample.
- Each of the obtained evaluation samples was measured with a differential scanning calorimeter (DSC-6000 manufactured by SII Nano Technology) at a temperature range of 50 to 350 ° C. and a heating rate of 5 ° C./min.
- the positive electrode reactivity was evaluated by “exothermic peak temperature” and “exothermic amount at the exothermic peak temperature”.
- the “exothermic peak temperature” is the temperature showing the highest calorific value in the measured temperature range, and the calorific value at that temperature (a value obtained by correcting the calorific value at 60 ° C. to 0) is “the calorific value at the exothermic peak temperature”. ( ⁇ W) ”.
- a high initial discharge capacity ratio indicates that the resistance in the electrode is small and excellent.
- Discharge capacity ratio (%) (3C discharge capacity / 0.2C discharge capacity) ⁇ 100
- 3C discharge was performed in the same manner as described above using a battery that had been subjected to 100 charge / discharge cycles, and the discharge capacity ratio after 100 cycles was calculated.
- a high discharge capacity ratio after 100 cycles indicates that an increase in resistance in the electrode is suppressed even after the charge / discharge cycle.
- the positive electrode used for the evaluation was prepared by mixing 100 parts by mass of LiCoO 2 having an average particle diameter of 10 ⁇ m as a positive electrode active material and 7 parts by mass of acetylene black as a conductive material, and kneading by adding 8 parts by mass of NMP.
- the positive electrode mixture obtained by adding NMP (solid content concentration 12% by mass) in which PVDF is dissolved as a binder to 3 parts by mass of PVDF with respect to a total of 100 parts by mass of the positive electrode active material, It was applied to a 15 ⁇ m aluminum foil (current collector) with a doctor blade so that the thickness after drying was 80 ⁇ m, pressed to 60 ⁇ m, dried in a vacuum dryer at 120 ° C., and manufactured.
- a high initial discharge capacity ratio indicates that the resistance in the electrode is small and excellent.
- Discharge capacity ratio (%) (2C discharge capacity / 0.1C discharge capacity) ⁇ 100
- 2C discharge was performed in the same manner as described above using a battery that had been subjected to 100 charge / discharge cycles, and the discharge capacity ratio after 100 cycles was calculated.
- a high discharge capacity ratio after 100 cycles indicates that an increase in resistance in the electrode is suppressed even after the charge / discharge cycle.
- the main raw materials used in the production examples are as follows. ⁇ Monomer (A)> (A1): Chlorotrifluoroethylene (CTFE) ⁇ Monomer (B)> (B1): 2-ethylhexyl vinyl ether (B2): ethyl vinyl ether (EVE) (B3): cyclohexyl vinyl ether (CHVE) ⁇ Monomer (C)> (C1): cyclohexanedimethanol monovinyl ether (CHMVE), CH 2 ⁇ CHOCH 2 —cycloC 6 H 10 —CH 2 OH. “CycloC 6 H 10 ” represents “1,4-cyclohexylene” (hereinafter the same).
- C2 4-hydroxybutyl vinyl ether (HBVE)
- C3 10-Undecenoic acid ⁇ Monomer (D)>
- D1 CH 2 ⁇ CHOCH 2 —cycloC 6 H 10 —CH 2 O (C 2 H 4 O) 15 H, average molecular weight 570, manufactured by Nippon Emulsifier Co., Ltd.
- Nonionic emulsifier (1) DKS NL-100 (product name), manufactured by Daiichi Kogyo Seiyaku Co., Ltd., compound name: polyoxyethylene lauryl ether.
- Anionic emulsifier (2) sodium lauryl sulfate.
- Initiator (2) tert-butyl peroxypivalate
- ⁇ Production Example 2 Production of fluorinated copolymer (F2)>
- the monomer (D) is not used, and the amount of the monomer (D1) used is zero. Others were the same as in Production Example 1 to obtain a fluorinated copolymer (F2) latex.
- the content of the fluorinated copolymer (F2) in the latex was 50% by mass.
- KYOWARD 500SH is an acid adsorbent (hydrotalcite composed of a double salt of magnesium and aluminum) manufactured by Kyowa Chemical Industry Co., Ltd.
- Example 1 Preparation of negative electrode mixture 1 and production of negative electrode 1>
- a negative electrode mixture 1 was prepared using the fluorine-containing copolymer (F1) latex obtained in Production Example 1 as a binder composition. Furthermore, the negative electrode 1 was produced using the negative electrode mixture 1. That is, after adding and kneading 40 parts by mass of a carboxymethylcellulose aqueous solution having a concentration of 1% by mass as a viscosity modifier to 100 parts by mass of artificial graphite as a negative electrode active material, the fluorinated copolymer (F1) latex is added to the negative electrode active material.
- a negative electrode mixture 1 was prepared by adding the fluorine-containing copolymer (F1) to 5 parts by mass with respect to 100 parts by mass of the substance.
- the obtained negative electrode mixture 1 is applied to a copper foil (current collector) having a thickness of 20 ⁇ m with a doctor blade so that the thickness after drying becomes 70 ⁇ m, and then dried in a vacuum dryer at 120 ° C. (Internal pressure: 10 Torr, 3 hours) to manufacture the negative electrode 1.
- the coatability and adhesion (peel strength) were evaluated by the above methods.
- Charge / discharge characteristics charge / discharge cycle characteristics, discharge rate characteristics
- ⁇ Comparative Example 1 Preparation of negative electrode mixture 2 and production of negative electrode 2> A negative electrode mixture 2 and a negative electrode 2 were produced in the same manner as in Example 1 except that the fluorine-containing copolymer (F2) latex obtained in Production Example 2 was used as a binder composition, and evaluated in the same manner.
- F2 fluorine-containing copolymer
- ⁇ Comparative Example 3 Preparation of negative electrode mixture 4 and production of negative electrode 4> A negative electrode mixture 4 and a negative electrode 4 were produced in the same manner as in Example 1 except that a styrene-butadiene copolymer (SBR) latex (solid content concentration 50% by mass) was used as the binder composition, and evaluation was performed in the same manner. did.
- SBR styrene-butadiene copolymer
- the negative electrode mixture 5 was prepared by adding the fluorine-containing copolymer (F1) latex so that the fluorine-containing copolymer (F1) was 5 parts by mass with respect to a total of 100 parts by mass of the negative electrode active material. .
- the obtained negative electrode mixture 5 was applied to a copper foil (current collector) having a thickness of 20 ⁇ m with a doctor blade so that the thickness after drying would be 70 ⁇ m, and then dried in a 120 ° C. vacuum dryer. (Internal pressure: 10 Torr, 3 hours) to manufacture the negative electrode 5. About this, evaluation similar to Example 1 was performed.
- Example 1 using a latex of a fluorine-containing copolymer (F1) having units (a) to (d) as a binder composition was a fluorine-containing material having no unit (d).
- an electrode active material Between the electrode active material and the current collector, and a secondary battery using the same was excellent in charge / discharge characteristics.
- Comparative Example 3 using an SBR latex as the binder composition had good adhesion, but the electrode resistance was large, so the discharge rate characteristics were inferior.
- Example 2 and Comparative Example 4 which mixed silicon monoxide with graphite as a negative electrode active material are compared, Example 2 is more excellent in adhesiveness and charging / discharging characteristics.
- Example 4 Preparation of negative electrode mixture 7 and production of negative electrode 7> A negative electrode mixture 7 in the same manner as in Example 1 except that the fluorine-containing copolymer (F1) latex obtained in Production Example 1 was used as a binder composition, the thickness after drying was 120 ⁇ m, and the thickness was pressed to 80 ⁇ m. And the negative electrode 7 was manufactured and adhesiveness (press-resistant strength) was evaluated. The evaluation results are shown in Table 3. Charge / discharge characteristics (charge / discharge cycle characteristics, discharge rate characteristics) were evaluated by the methods described in (8) to (10) above. The evaluation results are shown in Table 4 (hereinafter the same).
- Example 5 Preparation of negative electrode mixture 8 and production of negative electrode 8> A negative electrode mixture 8 was prepared in the same manner as in Example 1, except that the fluorine-containing copolymer (F4) latex obtained in Production Example 4 was used as a binder composition, the thickness after drying was 120 ⁇ m, and the thickness was pressed to 80 ⁇ m. And the negative electrode 8 was manufactured and evaluated similarly.
- F4 fluorine-containing copolymer
- Example 6 Preparation of negative electrode mixture 9 and production of negative electrode 9> A negative electrode mixture 9 was prepared in the same manner as in Example 1, except that the fluorine-containing copolymer (F5) latex obtained in Production Example 5 was used as a binder composition, the thickness after drying was 120 ⁇ m, and the thickness was pressed to 80 ⁇ m. And the negative electrode 9 was manufactured and evaluated similarly.
- F5 fluorine-containing copolymer
- ⁇ Comparative Example 6 Preparation of negative electrode mixture 10 and production of negative electrode 10>
- a negative electrode mixture 10 was prepared in the same manner as in Example 1 except that the fluorine-containing copolymer (F3) latex obtained in Production Example 3 was used as a binder composition, the thickness after drying was 120 ⁇ m, and the thickness was pressed to 80 ⁇ m.
- the negative electrode 10 was manufactured and evaluated in the same manner. Manufactured and evaluated similarly.
- ⁇ Comparative Example 7 Preparation of negative electrode mixture 11 and production of negative electrode 11> Except for using a styrene-butadiene copolymer (SBR) latex (solid content concentration of 50%) as the binder composition and setting the thickness after drying to 120 ⁇ m and pressing to 80 ⁇ m, the negative electrode composite was performed in the same manner as in Example 1. Agent 11 and negative electrode 11 were produced and evaluated in the same manner.
- SBR styrene-butadiene copolymer
- Examples 4 to 6 using latexes of fluorine-containing copolymers (F1, F4, F5) having units (a) to (d) as the binder composition were prepared using units (d) Compared with Comparative Example 6 using a latex of a fluorine-containing copolymer (F3) having a small number average molecular weight, the adhesion between the electrode active materials and the adhesion between the electrode active material and the current collector are excellent. .
- Examples 4 to 6 using latexes of fluorine-containing copolymers (F1, F4, F5) having units (a) to (d) of the present invention as binder compositions The full cell charge / discharge cycle characteristics were excellent.
- Comparative Example 7 using SBR latex as the binder composition had good adhesion, but had high electrode resistance and poor cycle characteristics.
- a positive electrode mixture 1 was prepared using the fluorine-containing copolymer (F1) latex obtained in Production Example 1 as a binder composition. That is, 100 parts by mass of LiNi 0.5 Mn 0.2 Co 0.3 O 2 having an average particle diameter of 10 ⁇ m as a positive electrode active material and 7 parts by mass of acetylene black as a conductive material are mixed, and the concentration is 1 mass as a viscosity modifier.
- a positive electrode mixture 1 was prepared.
- the obtained positive electrode mixture 1 was applied to an aluminum foil (current collector) having a thickness of 15 ⁇ m so that the thickness after drying was 60 ⁇ m with a doctor blade, and was dried in a 120 ° C. vacuum dryer ( Internal pressure: 10 Torr, 3 hours), the positive electrode 1 was manufactured.
- the coatability and adhesion (peel strength) were evaluated by the above methods.
- Charge / discharge characteristics charge / discharge cycle characteristics, discharge rate characteristics
- ⁇ Reference Example 1 Example of mixing PTFE aqueous dispersion>
- a latex of polytetrafluoroethylene (PTFE) was produced, and the fluorine-containing copolymer obtained in Production Example 3 was produced.
- a polymer (F3) latex was mixed to prepare a binder composition. Specifically, 736 g of paraffin wax, 59 L of ultrapure water, and 15 g of ammonium perfluorooctanoate (APFO) as an emulsifier were charged in a 100 L pressure-resistant polymerization tank.
- APFO ammonium perfluorooctanoate
- TFE tetrafluoroethylene
- aqueous dispersion 0.2 kg of a nonionic surfactant mainly composed of polyoxyethylene (average degree of polymerization 9) lauryl ether was added and dissolved, and 0.3 kg of anion exchange resin (Diaion manufactured by Mitsubishi Chemical Corporation) was dissolved. WA-30) was dispersed and stirred for 24 hours. Thereafter, the anion exchange resin was removed by filtration. Subsequently, 0.04 kg of 28 mass% ammonia water was added to the filtrate, and it concentrated at 80 degreeC by the phase-separation method for 10 hours, and removed the supernatant liquid.
- a nonionic surfactant mainly composed of polyoxyethylene (average degree of polymerization 9) lauryl ether was added and dissolved, and 0.3 kg of anion exchange resin (Diaion manufactured by Mitsubishi Chemical Corporation) was dissolved. WA-30) was dispersed and stirred for 24 hours. Thereafter, the anion exchange resin was removed by filtration. Subsequently, 0.04 kg of 28 mass% ammonia
- Example 3 instead of the fluorine-containing copolymer (F1) latex used in Example 3, the PTFE aqueous dispersion obtained above (PTFE content 50%) and the fluorine-containing copolymer (F3) obtained in Production Example 3 were used. ) Example 3 except that latex was used so that PTFE was 1.5 parts by mass and fluorine-containing copolymer (F3) was 1.5 parts by mass with respect to a total of 100 parts by mass of the positive electrode active material. In the same manner as above, a positive electrode mixture 3 was prepared. The positive electrode mixture 3 rapidly increased in viscosity at the time of stirring and mixing, and became a high viscosity. A positive electrode 3 was produced and evaluated in the same manner as in Example 3.
- Example 3 The positive electrode reactivity of Example 3 and Reference Example 2 was evaluated by the method described in (4) above. The evaluation results are shown in Table 6.
- the secondary battery using was excellent in charge / discharge characteristics.
- the positive electrode of Example 2 in which the latex of the fluorinated copolymer (F1) having units (a) to (d) was used as the binder composition, the positive electrode of Reference Example 2 However, the calorific value was low, the reactivity of the positive electrode was kept low, thermal runaway was less likely to occur, and a secondary battery with higher safety was obtained.
- An electrode using the electrode mixture for an electricity storage device containing the binder composition for an electricity storage device of the present invention is an electricity storage device such as a lithium primary battery, a lithium ion secondary battery, a lithium polymer battery, an electric double layer capacitor, or a lithium ion capacitor. In particular, it can be widely used as an electrode of a lithium ion secondary battery.
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Abstract
Description
蓄電デバイス用バインダーは、通常、バインダーとなるポリマーを水や有機溶媒に溶解又は分散させたバインダー組成物として用いられ、該バインダー組成物に電極活物質、導電材を分散させて、電極合剤が調製される。
それとともに、電極活物質が蓄電デバイス用バインダーで覆われても、電極の抵抗を低く抑えて、良好な充放電特性を実現できることが要求される。
また、特許文献1、2には、含フッ素共重合体の水分散液と、PTFEの水分散液とを混合して結着剤とすることが記載されている。しかし、本発明者等の知見によれば、PTFEがせん断を受けると粘度が上昇しやすいため、かかる結着剤を用いた電極合剤にあっては、良好な塗工性が得られ難いという課題がある。
[1]下記単量体(A)に基づく単位(a)、下記単量体(B)に基づく単位(b)、下記単量体(C)に基づく単位(c)、及び下記単量体(D)に基づく単位(d)を含有する含フッ素共重合体と、液状媒体とを含む蓄電デバイス用バインダー組成物。
単量体(A):テトラフルオロエチレン、及びクロロトリフルオロエチレンからなる群より選ばれる1種以上の化合物。
単量体(B):下式(I)で表わされる化合物、及び下記(II)で表わされる化合物からなる群より選ばれる1種以上の化合物。
CH2=CH-(CH2)n-O-R・・・(I)
CH2=CH-(CH2)n-OCO-R・・・(II)
[式中、nは0又は1であり、Rは炭素数1~20の飽和炭化水素基を表す。2種以上の化合物を用いる場合は、複数のn及びRは同一であっても異なっていてもよい。]
単量体(C):エチレン性不飽和結合とヒドロキシ基とを有する化合物、エチレン性不飽和結合とエポキシ基とを有する化合物、及びエチレン性不飽和結合とカルボキシ基とを有する化合物からなる群より選ばれる1種以上であり、かつ、分子量が300未満である化合物。
単量体(D):親水性部位を有するマクロモノマーの1種以上であり、かつ、分子量が300以上である化合物。
[3]前記単量体(C)が、下式(III)~(VI)で表される化合物からなる群より選ばれる1種以上の化合物を含む、上記[1]又は[2]に記載の蓄電デバイス用バインダー組成物。
[5]前記含フッ素重合体が5~70質量%含有され、前記液状媒体が30~95質量%含有される、上記[1]~[4]のいずれかに記載の蓄電デバイス用バインダー組成物。
[6]前記液状媒体が、水単独、または水と水溶性有機溶剤との混合物である、上記[1]~[5]のいずれかに記載の蓄電デバイス用バインダー組成物。
[7]前記含フッ素共重合体の数平均分子量が2万~100万である、上記[1]~[6]のいずれかに記載の蓄電デバイス用バインダー組成物。
[8]ホモジナイザーを用いた機械的安定性試験における沈殿物生成量が1質量%以下である、上記[1]~[7]のいずれかに記載の蓄電デバイス用バインダー組成物。
[9]上記[1]~[8]に記載の蓄電デバイス用バインダー組成物の製造方法であり、単量体(A)、(B)、(C)及び(D)を含む単量体成分を、前記液状媒体中で乳化重合させる製造方法。
[10]上記[1]~[8]のいずれかに記載の蓄電デバイス用バインダー組成物と電池活物質とを含有する蓄電デバイス用電極合剤。
[11]集電体と、該集電体上に、上記[10]に記載の蓄電デバイス用電極合剤を用いて形成された電極活物質層を有する、蓄電デバイス用電極。
[12]前記電極活物質層と前記集電体との剥離強度が、3N以上である、上記[11]に記載の蓄電デバイス用電極。
[13]前記電極活物質層と前記集電体とのプレス剥離耐性強度が、0.7kN/cm以上である、上記[11]又は[12]に記載の蓄電デバイス用電極。
[14]上記[11]~[13]のいずれかに記載の蓄電デバイス用電極及び電解液を備える二次電池。
本発明の蓄電デバイス用電極合剤、該電極合剤を用いた蓄電デバイス用電極、及び該電極を備える二次電池においては、電極活物質間の密着性及び電極活物質と集電体との密着性が優れ、良好な充放電特性が得られ、さらに、電極における反応性がより低く抑えられることにより、二次電池の熱暴走がより生じ難く、より高い安全性が得られる。
「単量体に基づく単位」とは、単量体が重合することによって形成された、単量体分子から構成される構成単位であり、単量体分子の一部が分解によって消失していてもよい。
本発明において、特に断りの無い限り、単量体と該単量体に基づく単位を同じアルファベットを用いて表す。例えば、「単位(a)」は「単量体(A)に基づく単位」であることを表す。
含フッ素共重合体の数平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)により、含フッ素共重合体に可溶な溶媒を用いて測定し、ポリスチレン換算値として得られる値である。
本発明の蓄電デバイス用バインダー組成物(以下、単にバインダー組成物ということがある。)は、単量体(A)に基づく単位(a)と、単量体(B)に基づく単位(b)と、単量体(C)に基づく単位(c)と、単量体(D)に基づく単位(d)を有する含フッ素共重合体を含む。
[単量体(A)]
単量体(A)は、テトラフルオロエチレン(TFE)、及びクロロトリフルオロエチレン(CTFE)からなる群より選ばれる1種以上の化合物である。好ましくは、CTFEである。
単量体(B)は、下式(I)で表わされる化合物、及び下記(II)で表わされる化合物からなる群より選ばれる1種以上の化合物である。
CH2=CH-(CH2)n-O-R・・・(I)
CH2=CH-(CH2)n-OCO-R・・・(II)
式(I)、(II)において、nは0又は1であり、Rは炭素数1~20の飽和炭化水素基を表す。2種以上の化合物を用いる場合は、複数のn及びRは同一であっても異なっていてもよい。
Rとしての飽和炭化水素基は、直鎖状、分岐状又は環構造を含んでもよい。Rはフッ素原子を有しない。
単量体(B)の具体例として、エチルビニルエーテル(EVE)、プロピルビニルエーテル、ブチルビニルエーテル、2‐エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル(CHVE)等のビニルエーテル類;エチルアリルエーテル、プロピルアリルエーテル、ブチルアリルエーテル、シクロヘキシルアリルエーテル等のアリルエーテル類;ブタン酸ビニルエステル、オクタン酸ビニルエステルなどのビニルエステル類;ブタン酸アリルエステル、オクタン酸アリルエステル等のアリルエステル類;が挙げられる。好ましくはビニルエーテル類やアリルエーテル類である。
単量体(C)は、エチレン性不飽和結合とヒドロキシ基とを有する化合物、エチレン性不飽和結合とエポキシ基とを有する化合物、及びエチレン性不飽和結合とカルボキシ基とを有する化合物からなる群より選ばれる1種以上であり、かつ、分子量が300未満である化合物である。単量体(C)は、少なくともヒドロキシ基、エポキシ基又はカルボキシ基のいずれかを有しており、これらのうちの2以上を有していてもよい。単量体(C)に基づく単位は密着性の向上に寄与する。
エチレン性不飽和結合とヒドロキシ基を有する化合物(以下、単量体(C-i)ともいう。)としては、ヒドロキシ基を有するビニルエーテル、ヒドロキシ基を有するビニルエステル、ヒドロキシ基を有するアリルエーテル、及びヒドロキシ基を有するアリルエステルからなる群より選ばれる1種以上の化合物が好ましい。例えば、下式(III)又は(IV)で表される化合物が挙げられる。
エチレン性不飽和結合とエポキシ基を有する化合物(以下、単量体(C-ii)ともいう。)としては、エポキシ基を有するビニルエーテル、エポキシ基を有するビニルエステル、エポキシ基を有するアリルエーテル、及びエポキシ基を有するアリルエステルからなる群より選ばれる1種以上の化合物が好ましい。例えば、下式(V)又は(VI)で表される化合物が挙げられる。
2価(m=0)のR1としての飽和炭化水素基は、例えば、炭素数1又は2の直鎖のアルキレン基、又はエーテル性酸素原子1~3個を有する炭素数2~6の飽和炭化水素基(ただし、飽和炭化水素基の炭素数が2の場合に含まれるエーテル性酸素原子の数は1個であり、飽和炭化水素基の炭素数が3の場合に含まれるエーテル性酸素原子の数は1個又は2個である。)が挙げられる。
具体的には、アルキレン基、シクロアルキレン基、シクロアルキレン基を含むアルキレン基等が挙げられる。アルキレン基は直鎖でも分岐でもよい。シクロアルキレン基としては、炭素数5~8のシクロアルキレン基が好ましく、シクロヘキシレン基が特に好ましい。シクロアルキレン基を含むアルキレン基としては、例えば-CH2-C6H10-CH2-等が挙げられる。
3価(m=1)又は4価(m=2)のR1としての飽和炭化水素基は、前記2価の飽和炭化水素基からm個の水素原子を除いた基が挙げられる。
特に式(III)において、R1が炭素数1又は2の直鎖のアルキレン基、又はエーテル性酸素原子1~3個を有する炭素数2~6のアルキレン基(ただし、エーテル性酸素原子の数は3個以下である。)であることが好ましい。
特に、式(IV)において、R2R3が炭素数1~4のアルキレン基であることが好ましい。
2-ヒドロキシエチルビニルエーテル(HEVE)、3-ヒドロキシプロピルビニルエーテル、2-ヒドロキシプロピルビニルエーテル、2-ヒドロキシ-2-メチルプロピルビニルエーテル、4-ヒドロキシブチルビニルエーテル(HBVE)、4-ヒドロキシ-2-メチルブチルビニルエーテル、5-ヒドロキシペンチルビニルエーテル、6-ヒドロキシヘキシルビニルエーテル等のヒドロキシアルキルビニルエーテル類;
シクロヘキサンジメタノールモノビニルエーテル(CHMVE)等の脂環族ジオールのモノビニルエーテル類;
ジエチレングリコールモノビニルエーテル(DEGV)、トリエチレングリコールモノビニルエーテル、テトラエチレングリコールモノビニルエーテル等のポリエチレングリコールモノビニルエーテル類;
ヒドロキシエチルアリルエーテル、ヒドロキシブチルアリルエーテル、2-ヒドロキシエチルアリルエーテル、4-ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテル等のヒドロキシアルキルアリルエーテル類;
ヒドロキシエチルビニルエステル、ヒドロキシブチルビニルエステル等のヒドロキシアルキルビニルエステル類;
ヒドロキシエチルアリルエステル、ヒドロキシブチルアリルエステル等のヒドロキシアルキルアリルエステル類;
ヒドロキシエチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキルエステル類等が挙げられる。
単量体(C-ii)の具体例としては、アリルグリシジルエーテル、グリシジルビニルエーテル、アリル-3,4-エポキシブチルエーテル、アリル-5,6-エポキヘキシルエーテル等が挙げられる。
上記単量体(C-iii)の例示のうち、他のフッ素系単量体との共重合性や、入手の容易性の点で、クロトン酸、イタコン酸、マレイン酸、マレイン酸モノエステル、フマル酸、フマル酸モノエステル、3-アリルオキシプロピオン酸、又は10-ウンデシレン(ウンデセン)酸が好ましい。
これらのうち、HEVE、HBVE、CHMVE、DEGV、アリルグリシジルエーテル、3-アリルオキシ-1,2-プロパンジオール、5-(2-プロペニルオキシ)-1-ペンタノール、6-(2-プロペニルオキシ)-1-ヘキサノール、2-(2-プロペニルオキシ)-1,4-ブタンジオール、4-(2-プロペニルオキシ)-1,2-ブタンジオール、2-[2-(3-ブテニル)エチル]オキシラン、2-[3-(2-ブテニル)プロピル]オキシラン、及び2-[4-(2-ブテニル)ブチル]オキシランからなる群より選ばれる少なくとも1種が好ましく、HBVE、CHMVE、アリルグリシジルエーテル、及び3-アリルオキシ-1,2-プロパンジオールからなる群より選ばれる少なくとも1種がより好ましく、HBVE又はCHMVEが最も好ましい。
単量体(C)の分子量は300未満であり、80~200が好ましい。
単量体(D)は、親水性部位を有するマクロモノマーの1種以上であり、かつ、分子量が300以上である化合物である。
本発明において、「マクロモノマー」とは、分子内にエチレン性不飽和結合を有する低分子量のポリマー又はオリゴマーを意味する。マクロモノマーの分子量又は平均分子量は300~10,000が好ましく、400~5000がより好ましい。
本明細書において、マクロモノマーの分子量とは、化学式に基づいて得られる式量を意味する。エーテル鎖長が異なる分子の混合物等、分子量が異なる分子の混合物である場合は、分子量(式量)の平均値である平均分子量で表す。
「親水性部位」とは、親水性基を有する部位、親水性の結合を有する部位、又はこれらの組み合わせからなる部位を意味する。
単量体(A)~(C)のいずれかに該当するものは、単量体(D)に含まれないものとする。
陰イオン性の親水性基としては、-SO3 -NH+ 4、-SO3 -Na+等が挙げられる。
陽イオン性の親水性基としては、-NH3 +CH3COO-等が挙げられる。
ノニオン性の親水性基としては、-(CH2CH2O)pH(pは1~50)等が挙げられる。
両性の親水性基としては、-N+(CH3)2CH2COO-等が挙げられる。
バインダー組成物の分散安定性の点からは、ノニオン性又は両性の親水性基を有する部位と他の親水性基を有する部位とを組合せるか、又は親水性基を有する部位と親水性の結合を有する部位とを組合せるのが好ましい。
(1)CH2=CHO(CH2)a[O(CH2)b]cOR11(aは1~10の整数、bは1~4の整数、cは2~20の整数、R11は水素原子又は低級アルキル基である。);
(2)CH2=CHCH2O(CH2)d[O(CH2)e]fOR2(dは1~10の整数、eは1~4の整数、fは2~20の整数、R2は水素原子又は低級アルキル基である。);
(3)CH2=CHO(CH2)g(OCH2CH2)h(OCH2CH(CH3))kOR3(gは1~10の整数、hは2~20の整数、kは0~20の整数、R3は水素原子又は低級アルキル基であり、オキシエチレン単位及びオキシプロピレン単位は、ブロック、ランダムのいずれの型で配列されていてもよい。);
(4)CH2=CHCH2O(CH2)m1(OCH2CH2)n1OCH2CH(CH3))pOR4((m1)は1~10の整数、(n1)は2~20の整数、pは0~20の整数、R4は水素原子又は低級アルキル基であり、オキシエチレン単位とオキシプロピレン単位は、ブロック、ランダムのいずれの型で配列されていてもよい。);
(5)CH2=CHO(CH2)qO(CO(CH2)rO)sH(qは1~10の整数、rは1~10の整数、sは1~30の整数);が挙げられる。
上記(1)~(5)における低級アルキル基の炭素数は1~30が好ましく、1~20がより好ましい。
具体例として以下のものが挙げられる。(n2)はオキシエチレン基の付加モル数を表し、2~40の整数である。
CH2=CHOCH2-cycloC6H10-CH2O(CH2CH2O)n2H、
CH2=CHCH2OCH2-cycloC6H10-CH2O(CH2CH2O)n2H、
CH2=CHO-cycloC6H10-C(CH3)2-cycloC6H10-O(CH2CH2O)n2H、
CH2=CHCH2O-cycloC6H10-C(CH3)2-cycloC6H10-O(CH2CH2O)n2H、
CH2=CHO-cycloC6H10-CH2O-(CH2CH2O)n2-H、
CH2=CHCH2O-cycloC6H10-CH2O-(CH2CH2O)n2-H。
また、オキシエチレン単位を2個以上有すれば、安定性等の諸性質が良好になる。また、オキシアルキレン単位の数が多すぎると、電解液に対する耐溶剤性が悪くなる。1分子中のオキシアルキレン単位は、2個以上100個以下が好ましく、2個以上75個以下がより好ましい。
このような親水性部位を有するマクロモノマーは、水酸基を有するビニルエーテル若しくはアリルエーテルに、ホルムアルデヒド若しくはジオールを重合させるか、又はアルキレンオキシド若しくはラクトン環を有する化合物を開環重合させる等の方法により製造できる。
このような親水性部位を有するマクロモノマーは、山下らがPolym.Bull.,5.335(1981)に記載の方法等により製造できる。
花王社製のラムテルPD-104(ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム)、ラムテルPD-420(ポリオキシアルキレンアルケニルエーテル);第一工業製薬社製のアクアロンKH-10(ポリオキシエチレン-1-(アリルオキシメチル)アルキルエーテル硫酸アンモニウムアクアロンHS-10(ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸アンモニウム)、アクアロンRN-20(ポリオキシエチレンノニルプロペニルフェニルエーテル);日本乳化剤社製のアントックスMS-60(2-ソジウムスルホエチルメタクリレート)、アントックスSAD(アルキル・アリルサクシネートスルホン酸Na塩)、アントックスMS-2N(2-ソジウムスルホエチルメタクリレート)アントックスLMA-10(アルコキシポリエチレングリコールメタクリレート)、アントックスEMH-20(アルコキシポリエチレングリコールマレイン酸エステル);三洋化成社製のエレミノールJS‐20、エレミノールRS‐3000等である。
含フッ素共重合体は、単位(a)~(d)のほかに、単量体(A)~(D)のいずれにも該当せず、かつ、これらと共重合可能な、その他の単量体(E)に基づく単位(その他の単位(e))を有してもよい。
その他の単量体(E)の例としては、エチレン、プロピレンなどのオレフィン類、スチレン、ビニルトルエンなどの芳香族ビニル化合物類などのビニル系化合物、アクリル酸ブチルなどのアクリロイル化合物類、メタクリル酸エチルなどのメタクリロイル化合物類などが挙げられる。特に、オレフィン類が好ましい。
含フッ素共重合体を構成する全単位に対して、単位(a)~(d)の合計は、70~100モル%が好ましく、80~100モル%がより好ましく、90~100モル%がさらに好ましい。
含フッ素共重合体において、単位(a)の含有量は、全単位の合計に対して、20~80モル%であることが好ましく、30~70モル%がより好ましい。上記範囲の下限値以上であると良好な分散安定性が得られやすい。上限値以下であると良好な密着性が得られやすい。単位(a)として2種の単位を含む場合、それらの合計の含有量が「単位(a)の含有量」である。他の単位についても同様である。
単位(b)の含有量は、全単位の合計に対して1~70モル%であることが好ましく、5~60モル%がより好ましく、10~50モル%がさらに好ましい。上記範囲の下限値以上であると良好な密着性が得られやすい。上限値以下であると柔軟性が良好な塗膜が得られやすい。単位(b)として2種以上の単位を含む場合、それらの合計の含有量が「単位(b)の含有量」である。
単位(c)の含有量は、全単位の合計に対して0.1~40モル%であることが好ましく、1~20モル%がより好ましい。上記範囲の下限値以上であると水性分散液の化学的安定性に優れる。上限値以下であると良好な密着性が得られやすい。
単位(d)の含有量は、全単位の合計に対して0.1~25モル%であることが好ましく、0.3~20モル%がより好ましい。上記範囲の下限値以上であると良好な分散安定性が得られやすい。すなわち、後述の機械的安定性試験における沈殿物生成が抑えられる。上限値以下であると良好な密着性が得られやすい。
含フッ素共重合体は、単量体(A)、(B)、(C)、(D)、及び任意の単量体(E)を、乳化重合法により共重合させることにより製造できる。乳化重合法によれば、高分子量(例えば数平均分子量が2万以上)の含フッ素共重合体が得られやすい。
乳化重合法では、水性媒体、及びラジカル重合開始剤、さらに好ましくは、乳化剤の存在下に、単量体(A)~(D)を含む単量体成分を重合(乳化重合)する工程(以下、乳化重合工程とも記す。)を経て、含フッ素共重合体のラテックスを得る。
乳化重合法は、含フッ素共重合体の製造において公知の手法を適宜用いることができる
乳化重合工程で得られるラテックスは、そのまま本発明のバインダー組成物として用いることができる。
本発明の蓄電デバイス用バインダー組成物は、含フッ素共重合体と液状媒体を含む。該バインダー組成物は、含フッ素共重合体が液状媒体に分散したラテックスであることが好ましい。ラテックスは含フッ素共重合体の分散液であるが、含フッ素共重合体の一部が液状媒体に溶解していてもよい。液状媒体は水性媒体が好ましい。
水性媒体とは、水単独、又は水と水溶性有機溶剤との混合物である。水はイオン交換水を用いることが好ましい。
水溶性有機溶剤としては、水と任意の割合で溶解できる公知の化合物を適宜用いることができる。水溶性有機溶剤としては、アルコール類が好ましく、tert-ブタノール、プロピレングリコール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコール等が挙げられる。これらのうち、tert-ブタノール、プロピレングリコール、ジプロピレングリコール又はジプロピレングリコールモノメチルエーテルが好ましい。
機械的安定性試験は、含フッ素共重合体のラテックスを、ホモジナイザーを用いて、25℃、5000rpmで5分攪拌し、100メッシュのステンレス製金網でろ過する。ろ過残渣を140℃、1時間乾燥した後の質量に対する、上記含フッ素共重合体ラテックス中の固形分に対する質量割合(%)を沈殿物生成量とする。
本発明の蓄電デバイス用電極合剤(本明細書において、単に電極合剤ということもある。)は、本発明のバインダー組成物を含有するほか、電極活物質を含有する。必要に応じて導電材を含有してもよく、これら以外のその他の成分を含有してもよい。
本発明で用いられる電極活物質は特に限定されず、公知のものを適宜使用できる。
正極活物質としては、MnO2、V2O5、V6O13等の金属酸化物;TiS2、MoS2、FeS等の金属硫化物;LiCoO2、LiNiO2、LiMn2O4等の、Co、Ni、Mn、Fe、Ti等の遷移金属を含むリチウム複合金属酸化物等;これらの化合物中の遷移金属元素の一部を他の金属元素で置換した化合物;等が例示される。さらに、ポリアセチレン、ポリ‐p‐フェニレン等の導電性高分子材料を用いることもできる。また、これらの表面の一部又は全面に、炭素材料や無機化合物を被覆させたものも用いることができる。
電極活物質は、機械的改質法などにより表面に導電材を付着させたものも使用できる。
リチウムイオン二次電池用の電極合剤の場合、用いる電極活物質は、電解質中で電位をかけることにより、可逆的にリチウムイオンを挿入放出できるものであればよく、無機化合物でも有機化合物でも用いることができる。
導電材としては、アセチレンブラック、ケッチェンブラック、カーボンブラック、グラファイト、気相成長カーボン繊維、カーボンナノチューブ等の導電性カーボンが挙げられる。
電極合剤が、導電材を含有すると、少量の導電材の添加で電気抵抗の低減効果が大きくなり好ましい。
本発明の電極合剤中の含フッ素共重合体の割合は、電極活物質100質量部に対して、0.1~20質量部が好ましく、0.5~10質量部がより好ましく、1~8質量部が特に好ましい。
また、電極合剤が導電材を含有する場合には、電極合剤中の導電材の割合は、電極活物質100質量部に対して、0質量部超であり、20質量部以下が好ましく、1~10質量部がより好ましく、3~8質量部が特に好ましい。
電極合剤中の固形分濃度は、電極合剤の100質量%に対して、30~95質量%が好ましく、40~85質量%がより好ましく、45~80質量%が特に好ましい。
本発明の蓄電デバイス用電極は、集電体と、該集電体上に、本発明の蓄電デバイス用バインダー及び電極活物質を含有する電極活物質層を有する。
集電体としては、導電性材料からなるものであれば特に限定されない。一般的には、アルミニウム、ニッケル、ステンレススチール、銅等の金属箔、金属網状物、金属多孔体等が挙げられる。正極集電体としては、好適にはアルミニウムが、負極集電体としては銅が好適に用いられる。集電体の厚さは1~100μmであることが好ましい。
電極合剤を集電体に塗布する方法としては、種々の塗布方法が挙げられる。例えば、ドクターブレード法、ディップ法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、ハケ塗り法等が挙げられる。塗布温度は、特に制限ないが、通常は常温付近の温度が好ましい。乾燥は、種々の乾燥法を用いて行うことができ、例えば、温風、熱風、低湿風等による乾燥、真空乾燥、(遠)赤外線や電子線等の照射による乾燥法が挙げられる。乾燥温度は、特に制限ないが、加熱式真空乾燥機等では、通常、室温~200℃が好ましい。プレス方法としては、金型プレスやロールプレス等を用いて行うことができる。
電極の密着性、すなわち、電極活物質層と集電体との剥離強度は、高いことが好ましく、下記により求められる。すなわち、製造した電極を幅2cm×長さ10cmの短冊状に切り、電極合剤の塗膜面を上にして固定し、電極合剤の塗膜面にセロハンテープを貼り付け、テープを10mm/minの速度で90度方向に剥離したときの強度(N)を5回測定し、その平均値を剥離強度とした。この値が大きいほどバインダーによる密着性(結着性)に優れていることを示す。すなわち、バインダーにより結着されている電極活物質間の密着性及び電極活物質と集電体との密着性に優れていることを示す。当該剥離強度は、3N以上が好ましく、5以上がより好ましく10N以上が特に好ましい。上限値は特に無いが、例えば、100Nである。
また、電極活物質層と集電体とのプレス剥離耐性強度も、高いことが好ましい。すなわち、乾燥後の電極活物質層の厚みが120μmになるように調整して製造した電極を、幅25mm×長さ40mmの長方形に切り、送り速度0.8m/minでロールプレスをかけた際に、剥離が起きない最大の圧力をプレス剥離耐性強度とした。この値が大きいほど、プレス時に剥離が起きにくいことを示す。当該プレス剥離耐性強度は、0.7kN/cm以上が好ましく、1.0kN/cm以上がより好ましい。上限値は特に無いが、例えば、10kN/cmである。
蓄電デバイスとしてのリチウムイオン二次電池は、本発明の蓄電デバイス用電極を、正極及び負極の少なくとも一方の電極として備えるとともに、電解液を備える。さらに、セパレーターを備えることが好ましい。
電解液は電解質と溶媒を含む。溶媒としては、非プロトン性有機溶媒、例えば、ジメチルカーボネート(DMC)、エチレンカーボネート(EC)、ジエチルカーボネート(DEC)、プロピレンカーボネート(PC)、ブチレンカーボネート(BC)、メチルエチルカーボネート(MEC)等のアルキルカーボネート類;γ-ブチロラクトン、ギ酸メチル等のエステル類、1,2-ジメトキシエタン、テトラヒドロフラン等のエーテル類;スルホラン、ジメチルスルホキシド等の含硫黄化合物類;などが用いられる。特に、高いイオン伝導性が得易く、使用温度範囲が広いため、ジメチルカーボネート、エチレンカーボネート、プロピレンカーボネート、ジエチルカーボネート又はメチルエチルカーボネートが好ましい。これらは、単独、又は2種以上を混合して用いることができる。
電解質としては、LiClO4、LiBF4、LiPF6、LiAsF5、CF3SO3Li、(CF3SO2)2NLi等のリチウム塩が挙げられる。
含フッ素共重合体の全単位の合計に対する、各単量体に基づく単位の含有量(共重合体の組成)は、19F-NMR分析、赤外吸収スペクトル分析、フッ素含有量分析等により測定した。
分析に用いる測定試料は、含フッ素共重合体のラテックスを、140℃のオーブンで1時間乾燥した後、真空乾燥機(内圧10Torr、50℃)で、24時間乾燥させたものを用いた。
含フッ素共重合体のラテックスを、テトラヒドロフランに溶解させ、東ソー社製のGPC(型式 HLC-8320)により測定した。
[含フッ素共重合体ラテックスの機械的安定性(沈殿物生成量)]
前に記載したとおりである。
集電体上に電極合剤をドクターブレードで塗布する方法を用いて製造した電極(大きさ150mm×250mm)から、直径18mmの円状のサンプルを50個切り出した。
各サンプルの厚みを測定して平均値を求めた。次いで、50個のサンプルの厚みの平均値からのずれを、下記の基準により3段階(A~C、Aが最も良い。)で評価し、塗工性の指標とした。塗工性が良いほどサンプルの厚みは均一になる。
A:平均値厚みの±10%の厚みに含まれるサンプル数が、全体の80%以上である。
B:平均値厚みの±10%の厚みに含まれるサンプル数が、全体の60%以上80%未満である。
C:平均値厚みの±10%の厚みに含まれるサンプル数が、全体の60%未満である。
前に記載したとおりである。
[密着性(プレス剥離耐性強度)]
前に記載したとおりである。
二次電池の充放電特性の評価は、以下の方法により行った。
[正極の評価]
(1)二次電池の製造(正極ハーフセル)
製造した正極を直径18mmの円形に切りぬき、これと同面積のリチウム金属箔、及びポリエチレン製のセパレーターを、リチウム金属箔、セパレーター、正極の順に2032型コインセル内に積層して電池要素を作製した。これに非水電解液を添加し、次いで、密封することにより、コイン型非水電解液二次電池を製造した。非水電解液としては、LiPF6が1Mの濃度で溶媒(エチルメチルカーボネート:エチレンカーボネート=1:1(体積比)の混合溶媒)に溶解したものを使用した。
上記(1)で製造したコイン型非水電解液二次電池について、25℃において、0.2Cに相当する定電流で、4.3V(電圧はリチウムに対する電圧を表す)まで充電し、さらに、充電上限電圧において、電流値が0.02Cになるまで充電を行い、その後、0.2Cに相当する定電流で3Vまで放電するサイクルを行った。1サイクル目放電時の放電容量に対する、100サイクル目の放電容量の容量維持率(単位:%)を求め、電池の充放電特性の指標とした。容量維持率の値が高いほど優れていることを示す。
なお、1Cとは、電池の基準容量を1時間で放電する電流値を表し、0.5Cとは、その1/2の電流値を表す。
上記(1)と同様に製造した、コイン型非水電解液二次電池を使用し、25℃において、0.2Cに相当する定電流で4.3V(電圧はリチウムに対する電圧を表す)まで充電し、さらに、充電上限電圧において、電流値が0.02Cになるまで充電を行った。次いで、0.2Cに相当する定電流で3Vまで放電した後、上記と同様に充電を行い、3Cに相当する定電流で3Vまで放電することにより、放電レート特性の評価を行った。0.2C放電後の放電容量を100%としたときの、3C放電後の放電容量の維持率を、下式に基づいて算出し、初期の放電容量比とした。初期の放電容量比が高いと、電極内の抵抗が小さく優れていることを示す。
放電容量比(%)=(3C放電容量/0.2C放電容量)×100
次いで、上記(2)の充放電サイクル特性の試験において、100サイクルの充放電サイクルを行った電池を用いて、上記と同様に、3C放電を行い、100サイクル後の放電容量比を算出した。100サイクル後の放電容量比が高いと、充放電サイクル後も電極内の抵抗増加が抑制されていることを示す。
上記(1)と同様に製造した、コイン型非水電解液二次電池を使用し、以下の充放電サイクルを実施した。サイクル1~4は、0.5Cに相当する電流で、4.2Vまで定電流充電を行い、さらに、充電下限電圧において、電流値が0.02Cに相当する電流となるまで定電圧充電を行った。その後、0.2Cに相当する電流で、3.0Vまで定電流放電を行った。サイクル5は、0.5Cに相当する電流で、4.3Vまで定電流充電を行い、さらに、充電下限電圧において、電流値が0.02Cに相当する電流となるまで定電圧充電を行った。その後、得られた充電状態の二次電池をアルゴン雰囲気下で分解し、充電状態の正極を得た。得られた正極を、ジメチルカーボネート(2mL)で3回洗浄し、真空乾燥した後に、直径5mmに打ち抜き、SUS製の密封容器に入れ、さらに、各例の非水電解液を2μL入れて封止し、評価サンプルとした。得られた各評価サンプルについて、示差走査熱量計(エスアイアイナノテクノロジー社製DSC-6000)によって、温度範囲50~350℃、昇温速度5℃/分で測定を行った。
正極反応性の評価は、「発熱ピーク温度」及び「発熱ピーク温度における発熱量」で行った。
「発熱ピーク温度」は、前記測定温度範囲において、もっとも高い発熱量を示した温度とし、その温度における発熱量(60℃での発熱量を0と補正した値)を「発熱ピーク温度における発熱量(μW)」とした。発熱量は低いほど、発熱ピーク温度は高温にシフトするほど、正極の反応性が抑えられ、二次電池がより熱暴走しにくく、安全性がより高いことを示す。
(5)二次電池の製造(負極ハーフセル)
製造した負極を直径18mmの円形に切りぬき、これと同面積のリチウム金属箔、及びポリエチレン製のセパレーターを、リチウム金属箔、セパレーター、負極の順に2016型コインセル内に積層して電池要素を作製した。これに非水電解液を添加し、次いで、密封することにより、コイン型非水電解液二次電池を製造した。非水電解液としては、LiPF6が1Mの濃度で溶媒(エチルメチルカーボネート:エチレンカーボネート=1:1(体積比)の混合溶媒)に溶解したものを使用した。
上記(5)で製造したコイン型非水電解液二次電池について、25℃において、0.2Cに相当する定電流で、0.02V(電圧はリチウムに対する電圧を表す)まで充電し、さらに、充電上限電圧において、電流値が0.02Cになるまで充電を行い、その後、0.2Cに相当する定電流で、1.5Vまで放電するサイクルを行った。1サイクル目放電時の放電容量に対する、150サイクル目の放電容量の容量維持率(単位:%)を求め、電池の充放電特性の指標とした。容量維持率の値が高いほど優れていることを示す。
上記(5)と同様に製造した、コイン型非水電解液二次電池を使用し、25℃において、0.2Cに相当する定電流で、0.02V(電圧はリチウムに対する電圧を表す)まで充電し、さらに、充電上限電圧において、電流値が0.02Cになるまで充電を行った。次いで、0.2Cに相当する定電流で、1.5Vまで放電後、上記と同様に充電を行い、3Cに相当する定電流で、1.5Vまで放電することにより、放電レート特性の評価を行った。0.2C放電後の放電容量を100%としたときの、3C放電後の放電容量の維持率を、下式に基づいて算出し、初期の放電容量比とした。初期の放電容量比が高いと、電極内の抵抗が小さく優れていることを示す。
放電容量比(%)=(3C放電容量/0.2C放電容量)×100
次いで、上記(6)の充放電サイクル特性の試験において、100サイクルの充放電サイクルを行った電池を用いて、上記と同様に、3C放電を行い、100サイクル後の放電容量比を算出した。100サイクル後の放電容量比が高いと、充放電サイクル後も電極内の抵抗増加が抑制されていることを示す。
製造した負極を直径19mmの円形に打ち抜いた電極と、正極を直径18mmの円形に打ち抜いた電極、及びポリエチレン製のセパレーターを、合剤層が対向する向きに負極、セパレーター、正極の順に2032型コインセル内に積層して電池要素を作製した。
これに非水電解液を添加し、その後、密封することにより、コイン型非水電解液二次電池を製造した。
非水電解液としては、LiPF6が1Mの濃度で溶媒(エチルメチルカーボネート:エチレンカーボネート=1:1(体積比)の混合溶媒)に溶解したものを使用した。
評価に用いた正極は、正極活物質として、平均粒径10μmのLiCoO2の100質量部と、導電材としてアセチレンブラックの7質量部を混合し、NMPの8質量部を加えて混練した後、バインダーとしてPVDFを溶解したNMP(固形分濃度12質量%)を、正極活物質の合計100質量部に対して、PVDFが3質量部となるように加えて得られた正極合剤を、厚さ15μmのアルミニウム箔(集電体)に、ドクターブレードで乾燥後の厚さが80μmとなるように塗布し、60μmまでプレスし、120℃の真空乾燥機に入れて乾燥し、製造した。
上記(8)で製造したコイン型非水電解液二次電池について、25℃において、0.5Cに相当する定電流で、4.35Vまで充電し、さらに、充電上限電圧において、電流値が0.02Cになるまで充電を行った。次いで、0.5Cに相当する定電流で、3Vまで放電するサイクルを行った。1サイクル目放電時の放電容量に対する、100サイクル目の放電容量の容量維持率(単位:%)を求め、電池の充放電特性の指標とした。容量維持率の値が高いほど優れていることを示す。
上記(8)と同様に製造した、コイン型非水電解液二次電池を使用し、25℃において、0.5Cに相当する定電流で4.35Vまで充電し、さらに充電上限電圧において電流値が0.02Cになるまで充電を行った。次いで、0.1Cに相当する定電流で3Vまで放電後、上記と同様に充電を行い、2Cに相当する定電流で3Vまで放電することの意より、放電レート特性の評価を行った。0.1C放電後の放電容量を100%としたときの、2C放電後の放電容量の維持率を下式に基づいて算出し、初期の放電容量比とした。初期の放電容量比が高いと、電極内の抵抗が小さく優れていることを示す。
放電容量比(%)=(2C放電容量/0.1C放電容量)×100
次いで、上記(9)の充放電サイクル特性の試験において、100サイクルの充放電サイクルを行った電池を用いて、上記と同様に、2C放電を行い、100サイクル後の放電容量比を算出した。100サイクル後の放電容量比が高いと、充放電サイクル後も電極内の抵抗増加が抑制されていることを示す。
<単量体(A)>
(A1):クロロトリフルオロエチレン(CTFE)
<単量体(B)>
(B1):2‐エチルヘキシルビニルエーテル
(B2):エチルビニルエーテル(EVE)
(B3):シクロヘキシルビニルエーテル(CHVE)
<単量体(C)>
(C1):シクロヘキサンジメタノールモノビニルエーテル(CHMVE)、CH2=CHOCH2-cycloC6H10-CH2OH。「cycloC6H10」は「1,4-シクロヘキシレン」を表す(以下、同様)。
(C2):4-ヒドロキシブチルビニルエーテル(HBVE)
(C3):10-ウンデセン酸
<単量体(D)>
(D1):CH2=CHOCH2-cycloC6H10-CH2O(C2H4O)15H、平均分子量570、日本乳化剤社製。
ノニオン性乳化剤(1):DKS NL-100(製品名)、第一工業製薬社製、化合物名:ポリオキシエチレンラウリルエーテル。
アニオン性乳化剤(2):ラウリル硫酸ナトリウム。
<重合開始剤>
開始剤(1):過硫酸アンモニウム(APS)
開始剤(2):tert-ブチルペルオキシピバレート
内容積250mLのステンレス製撹拌機付きオートクレーブ中に、単量体(C1)2.8g、単量体(B1)19g、単量体(B3)34g、単量体(D1)1.7g、イオン交換水93g、開始剤(1)0.012g、ノニオン性乳化剤(1)5.2g、及びアニオン性乳化剤(2)0.1gを仕込み、氷で冷却した。次いで、窒素ガスを導入し、オートクレーブ内の圧力が約0.34MPa(3.5kg/cm2)になるように加圧し、脱気した。この加圧脱気を2回繰り返した後、0.001MPa(10mmHg)まで脱気して、溶存空気を除去した後、単量体(A1)47gを仕込み、50℃で24時間反応を行った。
反応後、得られた水性分散液を200メッシュのナイロン布で濾過して、凝集物を取り除き、含フッ素共重合体(F1)ラテックスを得た。ラテックス中の含フッ素共重合体(F1)の含有量は52質量%であった。
得られた含フッ素共重合体の組成(各単位の含有量)、数平均分子量の測定結果、及びラテックスの機械的安定性試験における沈殿物生成量を表1に示す(以下、同様である。)。
製造例1において単量体(D)を用いない例であり、単量体(D1)の使用量をゼロとした。その他は、製造例1と同様にして含フッ素共重合体(F2)ラテックスを得た。ラテックス中の含フッ素共重合体(F2)の含有量は50質量%であった。
単量体(D)を用いず、溶液重合法で含フッ素共重合体を製造した例である。
上記特許文献1の段落[0078]~[0079]に記載されている製造例と同様にして、含フッ素共重合体(F3)ラテックスを製造した。
すなわち、内容積250mLの耐圧重合槽に、単量体(B2)10.3g、単量体(C1)16.7g、単量体(C2)15.4g、その他の単量体として10-ウンデセン酸(C3)4.9g、有機溶媒であるメチルエチルケトン(MEK)67g、開始剤(2)0.6g、及びキョーワード500SHの2gを仕込み、冷却した。キョーワード500SHは協和化学工業社製の酸吸着剤(マグネシウムとアルミニウムの複塩からなるハイドロタルサイト)である。
製造例1と同様にして脱気を行い、溶存空気を除去した後、単量体(A1)52.2gを仕込み、50℃で24時間反応を行った。
反応後、得られたポリマー溶液167gに、トリエチルアミン1.85gを加えて中和し、イオン交換水145gを撹拌しながらゆっくり加えた。次いで、MEKを減圧留去し、含フッ素共重合体(F3)ラテックスを得た。ラテックス中の含フッ素共重合体(F3)の含有量は50質量%であった。
製造例1において、単量体(B1)を用いずに、(B2)を16.3g、及び(B3)を20.5g用いた例である。その他は、製造例1と同様にして含フッ素共重合体(F4)ラテックスを得た。ラテックス中の含フッ素共重合体(F4)の含有量は50質量%であった。
製造例1において、単量体(B1)を用いずに、(B2)を29g、及び(B3)を1.1g用いた例である。その他は、製造例1と同様にして含フッ素共重合体(F5)ラテックスを得た。ラテックス中の含フッ素共重合体(F5)の含有量は50質量%であった。
製造例1で得られた含フッ素共重合体(F1)ラテックスをバインダー組成物として用いて、負極合剤1を調製した。さらに、該負極合剤1を用いて負極1を製造した。
すなわち、負極活物質として人造黒鉛の100質量部に、粘度調整剤として濃度1質量%のカルボキシメチルセルロース水溶液の40質量部を加えて混練した後、含フッ素共重合体(F1)ラテックスを、負極活物質100質量部に対して、含フッ素共重合体(F1)が5質量部となるように加えて負極合剤1を調製した。
得られた負極合剤1を、厚さ20μmの銅箔(集電体)に、ドクターブレードで、乾燥後の厚さが70μmとなるように塗布し、120℃の真空乾燥機に入れて乾燥(内圧;10Torr、3時間)し、負極1を製造した。
上記の方法で、塗工性、密着性(剥離強度)を評価した。上記(5)~(7)に記載の方法で、充放電特性(充放電サイクル特性、放電レート特性)を評価した。評価結果を表2に示す(以下、同様である。)。
製造例2で得られた含フッ素共重合体(F2)ラテックスをバインダー組成物として用いた以外は、実施例1と同様にして負極合剤2および負極2を製造し、同様に評価した。
製造例3で得られた含フッ素共重合体(F3)ラテックスをバインダー組成物として用いた以外は、実施例1と同様にして負極合剤3および負極3を製造し、同様に評価した。
バインダー組成物として、スチレン-ブタジエン共重合体(SBR)ラテックス(固形分濃度50質量%)を用いた以外は、実施例1と同様にして負極合剤4および負極4を製造し、同様に評価した。
本例は、実施例1において、負極活物質に一酸化シリコンを加えた例である。
製造例1で得られた含フッ素共重合体(F1)ラテックスをバインダー組成物として用いて、負極合剤5を調製した。
すなわち、負極活物質として、一酸化シリコン(Ardrich社製)10質量部と人造黒鉛の90質量部を混合した後、粘度調整剤として濃度1質量%のカルボキシメチルセルロース水溶液の40質量部を加えて混練した。その後、含フッ素共重合体(F1)ラテックスを、負極活物質の合計100質量部に対して、含フッ素共重合体(F1)が5質量部となるように加えて負極合剤5を調製した。
得られた負極合剤5を、厚さ20μmの銅箔(集電体)に、ドクターブレードで、乾燥後の厚さが70μmとなるように塗布し、120℃の真空乾燥機に入れて乾燥(内圧;10Torr、3時間)し、負極5を製造した。これについて、実施例1と同様の評価を行った。
製造例2で得られた含フッ素共重合体(F2)ラテックスをバインダー組成物として用いた以外は、実施例2と同様にして負極合剤6および負極6を製造し、同様に評価した。
SBRのラテックスをバインダー組成物として用いた比較例3は、密着性は良好であったが、電極抵抗が大きいため、放電レート特性が劣る。
また、負極活物質として、黒鉛に一酸化シリコンを混合した、実施例2と比較例4を比べても、実施例2の方が密着性及び充放電特性に優れる。
製造例1で得られた含フッ素共重合体(F1)ラテックスをバインダー組成物として用い、乾燥後の厚さを120μmとし、80μmまでプレスした以外は、実施例1と同様にして負極合剤7および負極7を製造し、密着性(プレス耐性強度)を評価した。評価結果を表3に示す。
上記(8)~(10)に記載の方法で、充放電特性(充放電サイクル特性、放電レート特性)を評価した。評価結果を表4に示す(以下、同様である。)。
製造例4で得られた含フッ素共重合体(F4)ラテックスをバインダー組成物として用い、乾燥後の厚さを120μmとし、80μmまでプレスした以外は、実施例1と同様にして負極合剤8および負極8を製造し、同様に評価した。
製造例5で得られた含フッ素共重合体(F5)ラテックスをバインダー組成物として用い、乾燥後の厚さを120μmとし、80μmまでプレスした以外は、実施例1と同様にして負極合剤9および負極9を製造し、同様に評価した。
製造例3で得られた含フッ素共重合体(F3)ラテックスをバインダー組成物として用い、乾燥後の厚さを120μmとし、80μmまでプレスした以外は、実施例1と同様にして負極合剤10おおび負極10を製造し、同様に評価した。製造し、同様に評価した。
バインダー組成物として、スチレン-ブタジエン共重合体(SBR)ラテックス(固形分濃度50%)を用い、乾燥後の厚さを120μmとし、80μmまでプレスした以外は、実施例1と同様にして負極合剤11および負極11を製造し、同様に評価した。
製造例1で得られた含フッ素共重合体(F1)ラテックスをバインダー組成物として用いて、正極合剤1を調製した。
すなわち、正極活物質として平均粒子径10μmのLiNi0.5Mn0.2Co0.3O2の100質量部、導電材としてアセチレンブラックの7質量部を混合し、粘度調整剤とし濃度1質量%のカルボキシメチルセルロース水溶液の40質量部を加えて混練した後、含フッ素共重合体(F1)ラテックスを、正極活物質の合計100質量部に対して、含フッ素共重合体(F1)が3質量部となるように加えて正極合剤1を調製した。
得られた正極合剤1を、厚さ15μmのアルミニウム箔(集電体)に、ドクターブレードで乾燥後の厚さが60μmとなるように塗布し、120℃の真空乾燥機に入れて乾燥(内圧;10Torr、3時間)し、正極1を製造した。
上記の方法で塗工性、密着性(剥離強度)を評価した。上記(1)~(3)に記載の方法で、充放電特性(充放電サイクル特性、放電レート特性)を評価した。評価結果を表5に示す(以下、同様である。)。
製造例3で得られた含フッ素共重合体(F3)ラテックスをバインダー組成物として用いた以外は、実施例3と同様にして正極合剤2および正極2を製造し、同様に評価した。
上記特許文献1の段落[0084]~[0085]に記載されている製造例と同様にして、ポリテトラフルオロエチレン(PTFE)のラテックスを製造し、これと製造例3で得られた含フッ素共重合体(F3)ラテックスを混合してバインダー組成物を調製した。
すなわち、100Lの耐圧重合槽に、パラフィンワックス736g、超純水59L、及び乳化剤であるペルフルオロオクタン酸アンモニウム(APFO)15gを仕込んだ。70℃に昇温後、窒素パージしてから脱気し、撹拌しながらテトラフルオロエチレン(TFE)を内圧1.9MPaまで導入した。これに0.5質量%ジコハク酸ペルオキシド水溶液の1Lを圧入して重合を開始した。重合はTFEを供給しながら、重合圧力1.9MPaに保持して45分間行った。その後、90℃まで昇温して、2.5質量%のAPFO水溶液1Lを加え、95分間加熱重合を継続した。その後、常温、常圧に戻し、得られた乳濁液から凝集物やパラフィン等を除去して、ポリテトラフルオロエチレン(PTFE)含有量26.0質量%、APFO含有量0.05質量%の水性分散液25.1kgを得た。
実施例3と同様にして正極3を製造し、評価した。
実施例3で用いた含フッ素共重合体(F1)ラテックスに代えて、上記で得たPTFE水性分散液(PTFE含有量50%)を用い、正極活物質の合計100質量部に対して、PTFEが3質量部となるよう加えた他は、実施例3と同様にして正極合剤4を調製した。正極合剤4は、撹拌混合時に粘度が急上昇し、高粘度となった。
実施例3と同様にして正極4を製造し、同様に評価した。
なお、2014年11月14日に出願された日本特許出願2014-231895号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (14)
- 下記単量体(A)に基づく単位(a)、下記単量体(B)に基づく単位(b)、下記単量体(C)に基づく単位(c)、及び下記単量体(D)に基づく単位(d)を含有する含フッ素共重合体と、液状媒体とを含む蓄電デバイス用バインダー組成物。
単量体(A):テトラフルオロエチレン、及びクロロトリフルオロエチレンからなる群より選ばれる1種以上の化合物。
単量体(B):下式(I)で表わされる化合物、及び下記(II)で表わされる化合物からなる群より選ばれる1種以上の化合物。
CH2=CH-(CH2)n-O-R・・・(I)
CH2=CH-(CH2)n-OCO-R・・・(II)
[式中、nは0又は1であり、Rは炭素数1~20の飽和炭化水素基を表す。2種以上の化合物を用いる場合は、複数のn及びRは同一であっても異なっていてもよい。]
単量体(C):エチレン性不飽和結合とヒドロキシ基とを有する化合物、エチレン性不飽和結合とエポキシ基とを有する化合物、及びエチレン性不飽和結合とカルボキシ基とを有する化合物からなる群より選ばれる1種以上であり、かつ、分子量が300未満である化合物。
単量体(D):親水性部位を有するマクロモノマーの1種以上であり、かつ、分子量が300以上である化合物。 - 前記含フッ素共重合体の全単位の合計に対して、単位(a)の含有量が20~80モル%、単位(b)の含有量が1~70モル%、単位(c)の含有量が0.1~40モル%、及び単位(d)の含有量が0.1~25モル%であり、かつ、単位(a)~(d)の合計が70~100モル%である、請求項1に記載の蓄電デバイス用バインダー組成物。
- 前記単量体(C)が、下式(III)~(VI)で表される化合物からなる群より選ばれる1種以上の化合物を含む、請求項1又は2に記載の蓄電デバイス用バインダー組成物。
- 前記単量体(D)が、エチレン性不飽和結合と-(CH2CH2O)pH(pは1~50)とが、1,4-シクロヘキシレン基を含む連結基を介して結合されているマクロモノマーである、請求項1~3のいずれか一項に記載の蓄電デバイス用バインダー組成物。
- 前記含フッ素重合体が5~70質量%含有され、前記液状媒体が30~95質量%含有される、請求項1~4のいずれか一項に記載の蓄電デバイス用バインダー組成物。
- 前記液状媒体が、水単独、または水と水溶性有機溶剤との混合物である、請求項1~5のいずれか一項に記載の蓄電デバイス用バインダー組成物。
- 前記含フッ素共重合体の数平均分子量が2万~100万である、請求項1~6のいずれか一項に記載の蓄電デバイス用バインダー組成物。
- ホモジナイザーを用いた機械的安定性試験における沈殿物生成量が1質量%以下である、請求項1~7のいずれか一項に記載の蓄電デバイス用バインダー組成物。
- 請求項1~8に記載の蓄電デバイス用バインダー組成物の製造方法であり、単量体(A)、(B)、(C)及び(D)を含む単量体成分を、前記液状媒体中で乳化重合させる製造方法。
- 請求項1~8のいずれか一項に記載の蓄電デバイス用バインダー組成物と電池活物質とを含有する蓄電デバイス用電極合剤。
- 集電体と、該集電体上に、請求項10に記載の蓄電デバイス用電極合剤を用いて形成された電極活物質層を有する、蓄電デバイス用電極。
- 前記電極活物質層と前記集電体との剥離強度が、3N以上である、請求項11に記載の蓄電デバイス用電極。
- 前記電極活物質層と前記集電体とのプレス剥離耐性強度が、0.7kN/cm以上である、請求項11又は12に記載の蓄電デバイス用電極。
- 請求項11~13のいずれか一項に記載の蓄電デバイス用電極及び電解液を備える二次電池。
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WO2016132872A1 (ja) * | 2015-02-20 | 2016-08-25 | 富士フイルム株式会社 | 固体電解質組成物、これを用いた電池用電極シートおよび全固体二次電池、ならびに電池用電極シートおよび全固体二次電池の製造方法 |
WO2021254245A1 (en) * | 2020-06-17 | 2021-12-23 | Guangdong Haozhi Technology Co. Limited | Binder composition for secondary battery |
WO2024092813A1 (zh) * | 2022-11-04 | 2024-05-10 | 宁德时代新能源科技股份有限公司 | 含氟聚合物、导电浆料、正极极片、二次电池、用电装置 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH04106170A (ja) * | 1990-08-28 | 1992-04-08 | Asahi Glass Co Ltd | 水性分散液 |
JPH0797497A (ja) * | 1993-09-29 | 1995-04-11 | Asahi Glass Co Ltd | 含フッ素水性分散液 |
WO2010134465A1 (ja) * | 2009-05-18 | 2010-11-25 | 旭硝子株式会社 | 含フッ素結着剤 |
JP2011086378A (ja) * | 2008-02-08 | 2011-04-28 | Asahi Glass Co Ltd | 蓄電素子電極形成用水性ペースト |
JP2012129104A (ja) * | 2010-12-16 | 2012-07-05 | Daikin Ind Ltd | 非水二次電池などの集電積層体の導電性保護層形成用ペースト |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008105298A1 (ja) * | 2007-02-21 | 2008-09-04 | Asahi Glass Company, Limited | 積層シート |
EP2624341B1 (en) * | 2010-09-30 | 2017-06-14 | Asahi Glass Company, Limited | Positive electrode material mixture for nonaqueous secondary cell, and positive electrode for nonaqueous secondary cell and secondary cell using the same |
-
2015
- 2015-11-11 CN CN201580057340.0A patent/CN107078301A/zh active Pending
- 2015-11-11 WO PCT/JP2015/081779 patent/WO2016076370A1/ja active Application Filing
- 2015-11-11 KR KR1020177006546A patent/KR20170082496A/ko unknown
- 2015-11-11 JP JP2016559094A patent/JPWO2016076370A1/ja not_active Withdrawn
-
2017
- 2017-04-07 US US15/482,176 patent/US20170214049A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04106170A (ja) * | 1990-08-28 | 1992-04-08 | Asahi Glass Co Ltd | 水性分散液 |
JPH0797497A (ja) * | 1993-09-29 | 1995-04-11 | Asahi Glass Co Ltd | 含フッ素水性分散液 |
JP2011086378A (ja) * | 2008-02-08 | 2011-04-28 | Asahi Glass Co Ltd | 蓄電素子電極形成用水性ペースト |
WO2010134465A1 (ja) * | 2009-05-18 | 2010-11-25 | 旭硝子株式会社 | 含フッ素結着剤 |
JP2012129104A (ja) * | 2010-12-16 | 2012-07-05 | Daikin Ind Ltd | 非水二次電池などの集電積層体の導電性保護層形成用ペースト |
Also Published As
Publication number | Publication date |
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US20170214049A1 (en) | 2017-07-27 |
JPWO2016076370A1 (ja) | 2017-08-31 |
CN107078301A (zh) | 2017-08-18 |
KR20170082496A (ko) | 2017-07-14 |
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