WO2022114044A1 - フッ化ビニリデン共重合体組成物およびその製造方法、ポリマー分散液、非水電解質二次電池用電極、非水電解質二次電池用電解質層、ならびに非水電解質二次電池 - Google Patents
フッ化ビニリデン共重合体組成物およびその製造方法、ポリマー分散液、非水電解質二次電池用電極、非水電解質二次電池用電解質層、ならびに非水電解質二次電池 Download PDFInfo
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- WO2022114044A1 WO2022114044A1 PCT/JP2021/043133 JP2021043133W WO2022114044A1 WO 2022114044 A1 WO2022114044 A1 WO 2022114044A1 JP 2021043133 W JP2021043133 W JP 2021043133W WO 2022114044 A1 WO2022114044 A1 WO 2022114044A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinylidene fluoride
- fluoride copolymer
- copolymer composition
- emulsion
- mass
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 434
- 239000000203 mixture Substances 0.000 title claims abstract description 323
- 239000003792 electrolyte Substances 0.000 title claims description 59
- 239000004815 dispersion polymer Substances 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 29
- 238000002844 melting Methods 0.000 claims abstract description 53
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 230000008018 melting Effects 0.000 claims abstract description 52
- 239000006185 dispersion Substances 0.000 claims abstract description 45
- 239000002612 dispersion medium Substances 0.000 claims abstract description 45
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims description 205
- 239000004094 surface-active agent Substances 0.000 claims description 100
- 238000010438 heat treatment Methods 0.000 claims description 69
- -1 alkyl vinyl compound Chemical class 0.000 claims description 59
- 239000012736 aqueous medium Substances 0.000 claims description 35
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- 238000010521 absorption reaction Methods 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 21
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
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- 239000002563 ionic surfactant Substances 0.000 claims description 11
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 8
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- 238000000034 method Methods 0.000 description 73
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- 239000011149 active material Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 19
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 14
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
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- 230000000694 effects Effects 0.000 description 9
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
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- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 101100223811 Caenorhabditis elegans dsc-1 gene Proteins 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
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- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000000957 temperature-modulated differential scanning calorimetry Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C08F214/22—Vinylidene fluoride
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F214/28—Hexyfluoropropene
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
-
- 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
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- 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
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a vinylidene fluoride copolymer composition and a method for producing the same, a polymer dispersion, an electrode for a non-aqueous electrolyte secondary battery, an electrolyte layer for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery.
- a vinylidene fluoride polymer containing vinylidene fluoride has been widely used as a binder for each layer of a non-aqueous electrolyte secondary battery.
- a copolymer of vinylidene fluoride and a fluoroalkyl vinyl compound (hereinafter, also referred to as “vinylidene fluoride copolymer”) is widely known as a binder for binding a current collector to an electrode active material or the like. has been done.
- Patent Document 1 describes an example in which a vinylidene fluoride copolymer is used as a binder for an electrode layer and an electrolyte layer of an all-solid-state battery, which is a kind of non-aqueous electrolyte secondary battery.
- it is common to mix the vinylidene fluoride copolymer with an electrode active material, a solid electrolyte, a solvent, a dispersion medium, or the like to form the above layer.
- Patent Document 2 a solvent having a small dielectric constant is used in order to suppress the elution of lithium from the solid electrolyte.
- Patent Document 3 describes that when a binder is mixed in the solid electrolyte layer, the ionic conductivity is lowered.
- Patent Document 4 and Patent Document 5 describe a slurry in which a vinylidene fluoride-hexafluoropropylene copolymer is dispersed in butyl butyrate or the like.
- Patent Document 6 describes that if the particulate binder polymer is uniformly dispersed in the dispersion medium, the solid electrolyte can be fixed without being locally or completely covered.
- a binder dispersion By using such a binder dispersion, the increase in interfacial resistance between the solid electrolyte particles and between the solid electrolyte particles and the current collector can be suppressed, and the binder dispersion and the solid electrolyte particles can be mixed and applied. It is shown that it becomes.
- Patent Document 3 since the vinylidene fluoride copolymer is an insulator, the ionic conductivity may be lowered when it is used as a binder for an electrode layer or an electrolyte layer. Therefore, as in Patent Documents 4 to 6, it has been studied to disperse the vinylidene fluoride copolymer without dissolving it to form an electrode layer or a solid electrolyte layer.
- an object of the present invention is to provide a vinylidene fluoride copolymer composition having stable dispersibility over a dispersion medium having a low relative permittivity for a long period of time, and to provide a method for producing the same.
- Another object of the present invention is to provide a polymer dispersion containing the vinylidene fluoride copolymer composition, an electrode for a non-aqueous electrolyte secondary battery, an electrolyte layer for a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery, and the like.
- the present invention provides the following vinylidene fluoride copolymer compositions. That is, the present invention is a fluorovinylidene copolymer composition containing a fluorovinylidene copolymer, wherein the fluorovinylidene copolymer is derived from a constituent unit derived from vinylidene fluoride and a fluoroalkyl vinyl compound.
- the melting point of the vinylidene fluoride copolymer composition is 140 ° C. or lower, and the vinylidene fluoride copolymer composition is the reversing heat flow of the vinylidene fluoride copolymer composition.
- the absolute value of the difference from the melting point of the vinylidene copolymer composition is 10 ° C. or less, the butyl butyrate and the vinylidene fluoride copolymer composition are contained, and the vinylidene fluoride copolymer composition is contained.
- the content of the vinylidene fluoride copolymer composition in the upper 20% by volume of the dispersion after stirring the dispersion having a ratio of 10% by mass at 25 ° C. for 30 minutes and allowing it to stand for 20 hours is determined.
- a vinylidene fluoride copolymer composition having a content of 4.0% by mass or more and 10% by mass or less.
- the present invention also provides a polymer dispersion liquid containing the above-mentioned vinylidene fluoride copolymer composition and a dispersion medium having a relative permittivity of 15 or less.
- the present invention also provides an electrode for a non-aqueous electrolyte secondary battery containing the above-mentioned vinylidene fluoride copolymer composition. Further, an electrolyte layer for a non-aqueous electrolyte secondary battery containing the above-mentioned vinylidene fluoride copolymer composition is provided. Also provided is a non-aqueous electrolyte secondary battery containing the above-mentioned vinylidene fluoride copolymer composition.
- the present invention also provides the following method for producing a vinylidene fluoride copolymer composition.
- a method for producing a vinylidene fluoride copolymer composition which comprises, and has a melting point of the vinylidene fluoride copolymer composition having a melting point of 140 ° C. or lower.
- a method for producing a vinylidene fluoride copolymer composition containing a vinylidene fluoride copolymer containing a structural unit derived from vinylidene fluoride and a structural unit derived from a fluoroalkyl vinyl compound, which is contained in an aqueous medium When the step of preparing an emulsion in which the untreated vinylidene fluoride copolymer is dispersed and the heat flow of the untreated vinylidene fluoride copolymer are measured with a differential scanning calorimeter, the heat absorption peak observed at 185 ° C. or lower. The emulsion is heated at a temperature lower than the end set of the hottest peak and at a temperature of 40 ° C. or higher, and the melting point of the vinylidene fluoride copolymer composition is 140 ° C. or lower. Also provided is a method for producing a vinylidene fluoride copolymer composition.
- the vinylidene fluoride copolymer composition of the present invention has excellent dispersibility in a dispersion medium having a low relative permittivity. Therefore, according to the vinylidene fluoride copolymer composition, it is possible to form an electrode layer and an electrolyte layer uniformly containing the vinylidene fluoride copolymer composition.
- FIG. 1 is a graph for explaining a method for identifying an endothermic peak endpoint of a vinylidene fluoride copolymer.
- the vinylidene fluoride copolymer composition of the present invention is a composition containing a vinylidene fluoride copolymer having predetermined physical properties.
- the vinylidene fluoride copolymer composition may be composed only of the vinylidene fluoride copolymer, or may contain the vinylidene fluoride copolymer and other components such as a surfactant.
- the vinylidene fluoride copolymer composition of the present invention may have a melting point of 140 ° C. or lower, and is usually in a solid state at 25 ° C.
- the fact that the composition is solid at 25 ° C means that the main constituents of the composition are solid at 25 ° C, and the range does not impair the object and effect of the present invention.
- a liquid component may be contained in a part thereof.
- the vinylidene fluoride copolymer when forming the electrode layer and the electrolyte layer of the non-aqueous electrolyte secondary battery, the vinylidene fluoride copolymer is preferably dispersed in a dispersion medium (dispersion medium having a low relative permittivity), and has a long length. It is preferable that the dispersibility is maintained over a period of time.
- a dispersion medium dispersion medium having a low relative permittivity
- the fluorovinylidene copolymer composition when the fluorovinylidene copolymer composition has specific physical properties, it is easy to disperse in a dispersion medium having a low relative permittivity, and further, the fluorovinylidene copolymer composition. It was clarified that the dispersion stability when the dispersion was allowed to stand was very high.
- the melting point of the vinylidene fluoride copolymer composition is 140 ° C. or lower, and the vinylidene fluoride copolymer composition temperature-modulates the reversing heat flow of the vinylidene fluoride copolymer composition.
- the vinylidene fluoride copolymer composition temperature-modulates the reversing heat flow of the vinylidene fluoride copolymer composition.
- ⁇ Hm melting enthalpy amount
- the melting point of the vinylidene fluoride copolymer composition is 140 ° C. or lower means that the vinylidene fluoride copolymer contains a certain or more structural units derived from the fluoroalkyl vinyl compound.
- the vinylidene fluoride copolymer composition contains a structural unit derived from a fluorine-containing alkyl vinyl compound, it is considered that the affinity with a dispersion medium having a low relative permittivity tends to be good.
- a vinylidene fluoride copolymer composition containing a vinylidene fluoride copolymer having a certain composition ratio of a structural unit derived from vinylidene fluoride and a structural unit derived from a fluoroalkyl vinyl compound, the reversing heat thereof.
- the peak top temperature of the largest heat absorption peak in the flow varies depending on the state of the crystalline region of the vinylidene fluoride copolymer in the vinylidene fluoride copolymer composition.
- the peak top temperature is a value that reflects the production history. ..
- the melting point measured by the method described later is not easily affected by the state of the crystalline region formed during production.
- the peak top temperature and the melting point of the vinylidene fluoride copolymer composition are obtained.
- the absolute value of the difference from and is 10 ° C. or less. That is, when the absolute value is 10 ° C. or lower, it can be said that the vinylidene fluoride copolymer composition is likely to be dispersed in a solvent having a low relative permittivity.
- the dispersion liquid when a dispersion liquid containing butyl butyrate and the vinylidene fluoride copolymer composition and having a content of the vinylidene fluoride copolymer composition of 10% by mass is prepared, the dispersion liquid is prepared.
- the content of the vinylidene fluoride copolymer composition in the upper 20% by volume of the dispersion after stirring at 25 ° C. for 30 minutes and allowing to stand for 20 hours is 4.0% by volume or more and 10% by volume or less. ..
- the vinylidene fluoride copolymer composition in the dispersion liquid is within the above range, the vinylidene fluoride copolymer composition is less likely to settle in the dispersion medium having a low relative permittivity, and for a long period of time. Good dispersibility is maintained.
- the vinylidene fluoride copolymer contained in the vinylidene fluoride copolymer composition of the present invention contains a structural unit derived from vinylidene fluoride and a structural unit derived from a fluoroalkyl vinyl compound.
- the amount of the constituent unit derived from vinylidene fluoride in the vinylidene fluoride copolymer is preferably 30% by mass or more and 85% by mass or less, preferably 40% by mass or more, based on 100% by mass of the constituent unit of the vinylidene fluoride copolymer. More preferably, it is 80% by mass or less.
- the melting point of the vinylidene fluoride copolymer composition tends to be within a desired range.
- the mass fraction of the structural unit derived from vinylidene fluoride can be specified by analyzing the vinylidene fluoride copolymer by 19 F-NMR.
- the fluorine-containing alkyl vinyl compound has a compound having one vinyl group and an alkyl group in which one or more hydrogens of the alkyl groups are substituted with fluorine, or one vinyl group and the vinyl.
- Any compound having fluorine bonded to the group may be used, and examples thereof include vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and hexa.
- Fluoroethylene, fluoroalkylvinyl ether, perfluoromethylvinyl ether and the like are included.
- the fluorovinylidene copolymer may contain only one type of structural unit derived from the fluorine-containing alkyl vinyl compound, or may contain two or more types.
- the amount of the constituent unit derived from the fluorine-containing alkyl vinyl compound in the vinylidene fluoride copolymer is not particularly limited as long as the melting point of the vinylidene fluoride copolymer composition described later can be set to 140 ° C. or lower. Although it depends on the type of the fluorine-containing alkyl vinyl compound, the amount of the constituent unit derived from the fluorine-containing alkyl vinyl compound is 15% by mass or more and 70% by mass or less with respect to 100% by mass of the constituent unit of the vinylidene fluoride copolymer. It is preferably 20% by mass or more and 60% by mass or less, more preferably.
- the melting point of the vinylidene fluoride copolymer composition tends to be within a desired range.
- the mass fraction of the structural unit derived from the fluorine-containing alkyl vinyl compound can be specified by analyzing the vinylidene fluoride copolymer by 19 F-NMR.
- the vinylidene fluoride copolymer contains some of the structural units derived from vinylidene fluoride and other monomers copolymerizable with the fluoroalkyl vinyl compound, as long as the object and effect of the present invention are not impaired. It may be included.
- Examples of other monomers copolymerizable with vinylidene fluoride and the like include crosslinkable alkylvinyl compounds having one vinyl group and a crosslinkable group.
- Examples of crosslinkable groups also include vinyl groups. That is, the crosslinkable alkyl vinyl compound may be a compound having two or more vinyl groups or the like. Further, the crosslinkable alkyl vinyl compound may contain a fluorine atom. Examples of the crosslinkable alkyl vinyl compound include perfluorodivinyl ether and perfluoroalkylene divinyl ether.
- two vinyl ether groups in which all hydrogen atoms are substituted with fluorine atoms are linear or branched divalent perfluoroalkylenes having 1 or more and 6 or less carbon atoms. Includes compounds having a group-bonded structure.
- Examples of other monomers also include unsaturated dibasic acid or unsaturated dibasic acid monoester.
- the unsaturated dibasic acid is an unsaturated dicarboxylic acid or a derivative thereof, in which example, two carboxyl groups are bonded by a linear or branched unsaturated alkylene group having 1 or more and 6 or less carbon atoms. Contains compounds. More specific examples of the unsaturated dibasic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid and the like.
- the unsaturated dibasic acid monoester is a monoester compound derived from the above-mentioned unsaturated dibasic acid. Examples of the unsaturated dibasic acid monoester include maleic acid monomethyl ester, maleic acid monoethyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester and the like.
- examples of other monomers include compounds containing vinyl groups and polar groups (hereinafter, also referred to as “polar group-containing compounds”).
- polar group-containing compounds include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, (meth) acryloyloxyethyl succinic acid, (meth) acryloyloxypropyl succinic acid, and glycidyl (meth) acrylate. Etc. are included.
- the mass fraction of the structural unit derived from the crosslinkable alkyl vinyl compound, unsaturated dibasic acid, unsaturated dibasic acid monoester, or polar group-containing compound in the vinylidene fluoride copolymer is an object of the present invention and It can be set arbitrarily as long as the effect is not impaired.
- the amount of structural units derived from unsaturated dibasic acid, unsaturated dibasic acid monoester, or polar group-containing compound can be specified by FT-IR analysis of vinylidene fluoride copolymer. ..
- the weight average molecular weight of the vinylidene fluoride copolymer is preferably 100,000 to 10 million, more preferably 200,000 to 5 million, and even more preferably 300,000 to 2 million.
- the weight average molecular weight of the vinylidene fluoride copolymer is in the above range, the dispersibility of the vinylidene fluoride copolymer composition with respect to the dispersion medium tends to be good.
- the vinylidene fluoride copolymer composition is used as a binder for the electrode layer and the electrolyte layer of the all-solid-state battery, it becomes easy to bind the active material and the solid electrolyte.
- the weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).
- the vinylidene fluoride copolymer composition may further contain a surfactant as well as the vinylidene fluoride copolymer.
- the surfactant contained in the vinylidene fluoride copolymer composition may be an ionic surfactant having an anionic group or a cationic group, and may be a nonionic surfactant. May be. Further, the surfactant may be a non-fluorinated surfactant containing no fluorine, or a fluorinated surfactant containing fluorine (perfluorinated surfactant, partially fluorinated surfactant, etc.). good.
- the anionic surfactant that can be used is not particularly limited, and conventionally known ones can be used.
- the hydrophilic group of the anionic surfactant preferably contains a carboxylate, a sulfate, a sulfonate, a phosphate and the like, and may further contain an ester bond, an acid amide bond, an ether bond and the like.
- the hydrophobic group preferably contains an alkyl chain, an alkyl ether chain, a perfluoroalkyl chain, a perfluoroalkyl ether chain, a fluorocarbon chain or a fluoropolyether chain, and these have a branched structure even if they have a linear structure. You may be doing it.
- the cationic surfactant that can be used is not particularly limited, and conventionally known ones can be used.
- the hydrophilic group of the cationic surfactant preferably contains an aliphatic quaternary ammonium salt, an aliphatic amine salt, a cyclic quaternary ammonium salt, and an amine acetate.
- the hydrophobic group preferably contains an alkyl chain, an alkyl ether chain, a perfluoroalkyl chain, a perfluoroalkyl ether chain, a fluorocarbon chain or a fluoropolyether chain, and these have a branched structure even if they have a linear structure. You may be doing it.
- nonionic surfactant that can be used is not particularly limited, and conventionally known ones can be used.
- the hydrophilic group of the nonionic surfactant preferably has a hydroxy group, an ether bond, an acid amide bond, an ester bond or the like in the molecule.
- the hydrophobic group preferably contains an alkyl chain, an alkyl ether chain, a perfluoroalkyl chain, a perfluoroalkyl ether chain, a fluorocarbon chain or a fluoropolyether chain, and these have a branched structure even if they have a linear structure. You may be doing it.
- the surfactant is preferably one that is dissolved or miscible in an aqueous medium in an emulsion prepared in the method for producing a vinylidene fluoride copolymer composition described later.
- the amount of the surfactant contained in the vinylidene fluoride copolymer composition is preferably 0.01% by mass or more and 20% by mass or less with respect to the total amount of the vinylidene fluoride copolymer and the surfactant. More preferably, it is 02% by mass or more and 15% by mass or less.
- the amount of the surfactant is excessively large, when the obtained vinylidene fluoride copolymer composition is used as a binder for the electrode layer or the electrolyte layer, the vinylidene fluoride copolymer composition and the active material, the electrolyte, etc. are used. However, if it is 20% by mass or less, the adhesiveness is unlikely to decrease.
- the amount of the surfactant is 0.01% by mass or more with respect to the total amount of the vinylidene fluoride copolymer composition
- the vinylidene fluoride copolymer composition is dispersed in the dispersion medium, Dispersion stability is improved.
- the vinylidene fluoride copolymer composition of the present invention may have a melting point of 140 ° C. or lower, but is preferably 135 ° C. or lower, more preferably 130 ° C. or lower.
- the melting point of the vinylidene fluoride copolymer composition can be adjusted by adjusting the amount of the constituent units derived from the fluoroalkyl vinyl compound in the vinylidene fluoride copolymer described above and the like. Further, in the present specification, the melting point of the vinylidene fluoride copolymer composition is measured by the following method.
- the powdery vinylidene fluoride copolymer composition is pressed at 200 ° C. to form a film having a thickness of 150 ⁇ m.
- the melting point of the pressed film-like vinylidene fluoride copolymer composition is measured according to ASTM D3418.
- the melting point of the vinylidene fluoride copolymer composition measured by the method is a value measured after melting the vinylidene fluoride copolymer composition once. Therefore, it is not easily affected by the production history in the polymerization reaction process of the vinylidene fluoride copolymer described later and the production method of the vinylidene fluoride copolymer composition.
- the vinylidene fluoride copolymer composition of the present invention has a melting enthalpy amount ( ⁇ Hm) of 2 J / when the reversing heat flow of the vinylidene fluoride copolymer composition is measured by a temperature-modulated differential scanning calorimeter. It has a heat absorption peak of g or more. Since the standard melting enthalpy amount ( ⁇ Hm 0 ) of the vinylidene fluoride polymer is 104.5 J / g, the literature value (value described in M Neidhofer: Polymer volume 45, Issue 5, 2004, 1679-1688) is 104.5 J / g.
- the upper limit of the melt enthalpy amount ( ⁇ Hm) of the vinylidene compound polymer is 104.5 J / g.
- the amount of melting enthalpy ( ⁇ Hm) of the vinylidene fluoride copolymer composition, the number of peak tops of heat absorption peaks, and the peak top temperature are determined by the vinylidene fluoride copolymer composition (particularly the vinylidene fluoride copolymer). ), That is, it changes depending on the state of the crystalline region, that is, the production method described later.
- the heat absorption peak of the vinylidene fluoride copolymer is obtained.
- the endothermic peak having a melting enthalpy amount ( ⁇ Hm) of 2 J / g or more is a peak observed at a temperature of 0 ° C. or higher, and the endothermic peak is observed in a temperature range of less than 0 ° C. The peak to be done is not included.
- the reversing heat flow of the vinylidene fluoride copolymer composition is specified by a temperature-modulated differential scanning calorimeter. Specifically, a powdery vinylidene fluoride copolymer composition obtained by freeze-drying an emulsion containing the vinylidene fluoride copolymer composition is used as a measurement sample. Then, heating is performed at an average heating rate of 5 ° C./min, a modulation cycle of 40 seconds, and a modulation amplitude of ⁇ 0.531 ° C. so as to be in a heat-only condition, and a rebirthing heat flow having a downwardly convex endothermic peak is generated. obtain.
- a baseline is drawn linearly so as to overlap the linear heat flow on the high temperature side of the end set. Then, among the endothermic peaks that are convex below the rebirthing heat flow, the point where the distance from the baseline to the rebirthing heat flow is the longest when a line is drawn vertically from the baseline to the rebirthing heat flow. Is the peak top of the largest endothermic peak, and the temperature at which the peak top is specified is specified.
- the number of minimum values in the endothermic peaks convex below the rebirthing heat flow is defined as the number of peak tops of the endothermic peaks.
- the region surrounded by the baseline and the reversing heat flow is defined as the melting enthalpy amount ( ⁇ Hm).
- the peak top temperature of the largest heat absorption peak is the endothermic peak having a melting enthalpy amount ( ⁇ Hm) of 2 J / g or more, from the baseline drawn by the above method toward the reversing heat flow.
- the absolute value is more preferably 9.5 ° C or lower, and even more preferably 9 ° C or lower.
- the absolute value is in the range, as described above, a vinylidene fluoride copolymer composition having both affinity and dispersibility for a dispersion medium having a low relative permittivity is obtained. If the absolute value exceeds 10 ° C., the crystallinity of the vinylidene fluoride copolymer composition tends to be too high, and the dispersibility tends to decrease.
- the absolute value can be adjusted by the method for producing a vinylidene fluoride copolymer composition described later. For example, if the vinylidene fluoride copolymer is made into a solid state (powder form) and then heated, the absolute value tends to exceed 10 ° C.
- the vinylidene fluoride copolymer composition of the present invention contains butyl butyrate and the vinylidene fluoride copolymer composition, and the content of the vinylidene fluoride copolymer composition is 10% by mass.
- the content of the vinylidene fluoride copolymer composition in the upper 20% by volume of the dispersion after standing for 20 hours is 4.0% by mass or more and 10% by mass or less.
- the content of the vinylidene fluoride copolymer composition in the upper 20% by volume is more preferably 7.0% by mass or more and 10% by mass or less.
- the vinylidene fluoride copolymer composition When the vinylidene fluoride copolymer composition has such dispersion stability with respect to butyl butyrate, the vinylidene fluoride copolymer composition is used in a polymer dispersion liquid for forming an electrode layer, an electrolyte layer, or the like. Is hard to settle, and it becomes easy to obtain an electrode layer and an electrolyte layer having desired performance.
- the content of the vinylidene fluoride copolymer composition in the dispersion liquid after standing can be adjusted by the method for producing the vinylidene fluoride copolymer composition described later. For example, it can be adjusted by adjusting the amount and type of the surfactant to be mixed with the vinylidene fluoride copolymer, the presence or absence of heating of the emulsion, and the like.
- the content rate of the vinylidene fluoride copolymer composition after the above-mentioned standing is measured as follows.
- a dispersion (10% by mass of the vinylidene fluoride copolymer composition) prepared by adding the vinylidene fluoride copolymer composition to butyl butyrate is prepared. Put 20 mL of the dispersion in a 20 mL graduated cylinder, cover with parafilm, and let stand for 20 hours. Then, 4 mL is collected from the supernatant of the measuring cylinder, dried at 135 ° C. for 1 hour, and allowed to cool in a desiccator for 1 hour. Then, by measuring the weight before and after drying, the content of the vinylidene fluoride copolymer composition in the upper 20% by volume of the dispersion is calculated.
- the turbidity of the dispersion is preferably 5% or more.
- the vinylidene fluoride copolymer composition is dissolved in the dispersion medium, and when it is 5% or more, at least the vinylidene fluoride copolymer composition is used. Part of it is dispersed without being dissolved in the dispersion medium.
- the turbidity can be adjusted by the type of surfactant used when preparing the vinylidene fluoride copolymer composition, the presence or absence of heating, and the like. The turbidity of the dispersion is measured by the following method.
- a butyl butyrate dispersion of a vinylidene fluoride copolymer composition (10% by mass of the vinylidene fluoride copolymer composition) is prepared, allowed to stand for 20 hours, and then stirred.
- the turbidity of the dispersion immediately after stirring is measured according to JIS K7136.
- the shape of the vinylidene fluoride copolymer composition of the present invention is not particularly limited, but it is usually preferably in the form of particles (powder).
- the average secondary particle size of the vinylidene fluoride copolymer composition is not particularly limited, but is preferably 1 ⁇ m or more and 5000 ⁇ m or less, and more preferably 2 ⁇ m or more and 3000 ⁇ m or less. When the average secondary particle size of the vinylidene fluoride copolymer composition is in the above range, the vinylidene fluoride copolymer can be easily handled.
- the average secondary particle diameter is the cumulative average diameter (D50) of the particle size distribution measured by the laser diffraction / scattering method on a volume basis.
- the vinylidene fluoride copolymer composition satisfying the above-mentioned physical characteristics can be produced, for example, by the following three methods.
- the method for producing the above-mentioned vinylidene fluoride copolymer composition is not limited to the following three methods.
- emulsion preparation step a step of preparing an emulsion in which an untreated vinylidene fluoride copolymer is dispersed in an aqueous medium.
- emulsion preparation step a step of adding an ionic surfactant to the emulsion and stirring it to obtain a surfactant-containing emulsion having a surface tension of 40 mN / m or less at 25 ° C.
- surfactant addition step also referred to as
- the surfactant-containing emulsion is dried to take out the vinylidene fluoride copolymer (hereinafter, also referred to as “drying step”), whereby the above-mentioned vinylidene fluoride copolymer weight is performed.
- the combined composition is obtained in solid form.
- heating at a temperature higher than the melting point of the vinylidene fluoride copolymer composition is not performed.
- an emulsion in which an untreated vinylidene fluoride copolymer is dispersed in an aqueous medium is prepared.
- the emulsion may be a commercially available product.
- the untreated fluorovinylidene copolymer refers to a copolymer of vinylidene fluoride and a fluoroalkyl vinyl compound prepared by a general method, after the polymerization of the vinylidene fluoride copolymer.
- the untreated vinylidene fluoride copolymer has substantially the same composition as the above-mentioned vinylidene fluoride copolymer.
- the specific dielectric constant of the untreated fluorovinylidene copolymer is 15 or less by performing the surfactant addition step described later on the emulsion in which the untreated vinylidene fluoride copolymer is dispersed in the aqueous medium. Dispersibility with respect to the dispersion medium changes.
- the emulsion in which the untreated vinylidene fluoride copolymer is dispersed in an aqueous medium may be prepared by a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a microsuspension polymerization method or the like. Further, a commercially available product of an emulsion in which an untreated vinylidene fluoride copolymer is dispersed in an aqueous medium may be used. Above all, a method of obtaining an emulsion in which an untreated vinylidene fluoride copolymer is dispersed in water by an emulsion polymerization method is preferable.
- vinylidene fluoride, a fluorine-containing alkyl vinyl compound, other monomers if necessary, an aqueous medium, and an emulsifier are mixed in an autoclave. Then, a polymerization initiator soluble in an aqueous medium is added to the mixed solution, and vinylidene fluoride, a fluorine-containing alkyl vinyl compound, and other monomers are polymerized, if necessary.
- the pressure in the autoclave during polymerization is preferably 0 to 20 MPa, more preferably 0.5 to 15 MPa, and even more preferably 1 to 10 MPa.
- the aqueous medium used for the emulsifying polymerization is not particularly limited as long as it is a liquid in which the above-mentioned vinylidene fluoride and the fluorine-containing alkyl vinyl compound are sparingly soluble, and if the liquid whose main component is water, a solvent miscible with water other than water is used. May include.
- the aqueous medium is preferably water.
- the emulsifier is not particularly limited as long as it can form micelles in an aqueous medium and can stably disperse the synthesized untreated vinylidene fluoride copolymer in the aqueous medium.
- it can be a known surfactant.
- the emulsifier may be any of nonionic surfactant, cationic surfactant, anionic surfactant, and amphoteric surfactant, and these may be used in combination.
- examples of emulsifiers include perfluorinated surfactants, partially fluorinated surfactants, non-fluorinated surfactants and the like conventionally used for the polymerization of polyvinylidene fluoride.
- a fluorinated surfactant having a perfluoroalkyl sulfonic acid and a salt thereof, a perfluoroalkyl carboxylic acid and a salt thereof, and a fluorocarbon chain or a fluoropolyether chain is preferable.
- the emulsifier one type alone or two or more types selected from the above can be used.
- the amount of the emulsifier added is preferably 0.0001 to 22 parts by mass, where 100 parts by mass is the total amount of all the monomers used in the polymerization.
- the polymerization initiator is not particularly limited as long as it is a compound that can be dissolved in an aqueous medium and can polymerize a monomer.
- the polymerization initiator include known water-soluble peroxides, water-soluble azo compounds, redox-based initiators and the like.
- water-soluble peroxides include ammonium persulfate, potassium persulfate and the like.
- water-soluble azo compounds include 2,2'-azobis-isobutyronitrile (AIBN) and 2,2'-azobis-2-methylbutyronitrile (AMBN).
- AIBN 2,2'-azobis-isobutyronitrile
- AMBN 2,2'-azobis-2-methylbutyronitrile
- redox-based initiators include ascorbic acid-hydrogen peroxide and the like.
- water-soluble peroxides are preferable from the viewpoint of reactivity and the like.
- These polymerization initiators can be used alone or in combination of two or more.
- the amount of the polymerization initiator added is preferably 0.01 to 5 parts by mass, where 100 parts by mass is the total amount of all the monomers used in the polymerization.
- the emulsification polymerization method may be a soap-free emulsification polymerization method, a miniemulsion polymerization method, a seed emulsification polymerization method, or the like.
- the soap-free emulsion polymerization method is a method of emulsion polymerization without using an ordinary emulsifier as described above. Further, in the soap-free emulsification polymerization method, a reactive emulsifier having a polymerizable double bond in the molecule can also be used as the emulsifier.
- the reactive emulsifier forms micelles in the system at the initial stage of polymerization, but as the polymerization progresses, it is used and consumed as a monomer in the polymerization reaction. Therefore, it hardly exists in the free state in the finally obtained reaction system. Therefore, there is an advantage that the reactive emulsifier is unlikely to bleed out to the particle surface of the obtained untreated vinylidene fluoride copolymer.
- reactive emulsifiers include polyoxyalkylene alkenyl ether, sodium alkylallyl sulfosuccinate, sodium methacryloyloxypolyoxypropylene sulfate, alkoxypolyethylene glycol methacrylate and the like.
- a strong shearing force is applied using an ultrasonic oscillator or the like to atomize oil droplets of monomers such as vinylidene fluoride and a fluorine-containing alkyl vinyl compound to a submicron size for polymerization. How to do it. At this time, a known hydrohove is added to the mixed solution in order to stabilize the oil droplets of the finely divided monomer.
- the miniemulsion polymerization method ideally, the polymerization reaction occurs only in each monomer oil droplet, and each oil droplet becomes an untreated fluorovinylidene copolymer (fine particles). Therefore, it is easy to control the particle size and particle size distribution of the obtained untreated vinylidene fluoride copolymer.
- Seed emulsion polymerization is a polymerization in which fine particles obtained by the above-mentioned polymerization method are coated with a polymer composed of other monomers.
- a monomer, an aqueous medium, a surfactant, a polymerization initiator and the like, if necessary, are further added to the fine particle emulsion to polymerize.
- a chain transfer agent may be used in order to adjust the degree of polymerization of the obtained untreated vinylidene fluoride copolymer.
- chain transfer agents include ethyl acetate, methyl acetate, diethyl carbonate, acetone, ethanol, n-propanol, acetaldehyde, propylaldehyde, ethyl propionate, carbon tetrachloride and the like.
- a pH adjuster may be used if necessary.
- an electrolyte substance having a buffering ability such as sodium dihydrogen phosphate, disodium hydrogen phosphate and potassium dihydrogen phosphate, as well as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and ammonia.
- sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and ammonia Such as basic substances can be mentioned.
- a sedimentation inhibitor such as a dispersion stabilizer, a corrosion inhibitor, an antifungal agent, and a wetting agent
- the amount of these optional components added is preferably 5 ppm or more and 10 parts by mass or less, more preferably 10 ppm or more and 7 parts by mass or less, based on 100 parts by mass of the total amount of all the monomers used in the polymerization.
- the polymerization temperature may be appropriately selected depending on the type of the polymerization initiator and the like, and is, for example, 0 to 120 ° C, preferably 20 to 110 ° C, more preferably 40 to 40. It may be set to 100 ° C.
- the polymerization time is not particularly limited, but is preferably 1 to 24 hours in consideration of productivity and the like.
- an emulsion in which untreated vinylidene fluoride copolymer particles are uniformly dispersed can be obtained.
- the commercially available emulsion and the emulsion thus obtained may be used as they are or diluted with an aqueous medium to any concentration before use.
- the emulsion is pulverized by at least one method selected from salting out, freeze-grinding, spray-drying, freeze-drying and the like, and then physically or chemically redispersed in a desired aqueous medium, which will be described later.
- a surfactant addition step may be performed.
- the untreated vinylidene fluoride copolymer may be pulverized by freeze pulverization, classification or the like, mixed with an aqueous medium, and subjected to the surfactant addition step described later.
- the method for dispersing the untreated vinylidene fluoride copolymer in an aqueous medium is not particularly limited, and a known dispersion method can be applied.
- the content of the untreated vinylidene fluoride copolymer in the emulsion is preferably 5% by mass or more and 70% by mass or less, and more preferably 10% by mass or more and 60% by mass or less.
- the emulsion prepared or purchased by the above method may be used as it is, or may be diluted with an aqueous medium before use.
- the content of the untreated vinylidene fluoride copolymer is 5% by mass or more, the vinylidene fluoride copolymer composition can be efficiently prepared.
- it is 70% by mass or less the dispersibility of the emulsion tends to be stable.
- the average primary particle size determined by the dynamic light scattering method of the untreated vinylidene fluoride copolymer in the emulsion is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, still more preferably 1 ⁇ m or less.
- the average primary particle size is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more.
- the average primary particle size of the untreated vinylidene fluoride copolymer in the emulsion is calculated by a regularized analysis of the dynamic light scattering method. For example, using DECKMAN COULTER's DelsaMaxCORE, the measurement medium can be water and the measurement temperature can be set to 25 ° C. in accordance with JIS Z8828. In addition, the largest peak obtained by regularization analysis is defined as the average primary particle size.
- an ionic surfactant is added to the emulsion prepared in the above-mentioned emulsion preparation step and stirred to obtain a surfactant-containing emulsion having a surface tension of 40 mN / m or less at 25 ° C.
- the ionic surfactant added in this step is not particularly limited as long as the surface tension of the added emulsion (surfactant-containing emulsion) can be 40 mN / m or less.
- the surface tension of the emulsion (surfactant-containing emulsion) after the addition of the ionic surfactant at 25 ° C. is preferably 5 mN / m or more and 40 mN / m or less, and more preferably 10 mN / m or more and 40 mN / m or less.
- the surface tension of the surfactant-containing emulsion is measured by a surface tension meter (Sigma701 / 700, manufactured by KSV instruments) using the Wilhelmy method. A platinum plate is used for the measurement, and the average value when the surface tension at 25 ° C. is measured three times is taken as the value of the surface tension.
- the ionic surfactant added in this step is selected to be soluble or miscible in the aqueous medium contained in the emulsion, and may be either an anionic surfactant or a cationic surfactant, and is anionic. Surfactants are particularly preferred. Only one kind of these may be added, or two or more kinds thereof may be added in combination. By adding an ionic surfactant, it can be adsorbed on the surface of the untreated vinylidene fluoride copolymer contained in the above emulsion, and its dispersibility in a dispersion medium having a relative permittivity of 15 or less can be obtained. improves.
- anionic surfactant and the cationic surfactant that can be used are the same as those exemplified for the surfactant contained in the above-mentioned vinylidene fluoride copolymer composition.
- the amount of the ionic surfactant added is appropriately selected according to the surface tension of the surfactant-containing emulsion, but is usually 0.01 part by mass with respect to the total amount of the untreated vinylidene fluoride copolymer in the emulsion. 20 parts by mass or more is preferable, and 0.02 parts by mass or more and 15 parts by mass or less is more preferable.
- the amount of the ionic surfactant becomes excessively large, when the obtained vinylidene fluoride copolymer composition is used as a binder for the electrode layer or the electrolyte layer, the vinylidene fluoride copolymer composition and the active material or the electrolyte are used. Adhesion to etc. may decrease.
- the fluorovinylidene copolymer composition was dispersed in the dispersion medium. Increased dispersion stability at times.
- the surfactant added in this step the surplus component may be removed by a dialysis membrane, an ion exchange resin or the like, if necessary.
- the aqueous medium is removed from the surfactant-containing emulsion.
- the method for removing the aqueous medium is not particularly limited, but it is preferable to dry at a temperature that does not affect the physical properties of the vinylidene fluoride copolymer composition in the surfactant-containing emulsion.
- the drying step may be carried out under atmospheric pressure or under reduced pressure.
- the drying gives the above-mentioned solid (powdered) vinylidene fluoride copolymer composition.
- the device for removing the aqueous medium is not particularly limited, and a shelf-type dryer, a conical dryer, a fluidized bed dryer, an air flow dryer, a spray dryer, a freeze dryer and the like can be used.
- emulsion preparation step a step of preparing an emulsion in which an untreated vinylidene fluoride copolymer is dispersed in an aqueous medium.
- At least the step of heating the emulsion at a temperature lower than the end set of the high temperature peak (hereinafter, also referred to as “heating step”) is performed.
- the emulsion is dried to take out the vinylidene fluoride copolymer (hereinafter, also referred to as “drying step”), whereby the above-mentioned solid (powder) fluoride is subjected to the step of drying.
- drying step the vinylidene fluoride copolymer
- a vinylidene copolymer composition is obtained.
- heating at a temperature higher than the melting point of the vinylidene fluoride copolymer composition shall not be performed.
- Emmulsion preparation process In the emulsion preparation step, an emulsion in which an untreated vinylidene fluoride copolymer is dispersed in an aqueous medium is prepared.
- the emulsion preparation step can be the same as the emulsion preparation step of the first method described above. As mentioned above, a commercially available emulsion may be used.
- the emulsion is heated after the emulsion preparation step.
- the heating step may be continuously carried out as it is after the polymerization, or the polymerization and the heating step may be carried out separately.
- the emulsion obtained by the polymerization it is preferable to remove at least the unreacted vinylidene fluoride and the fluoroalkyl vinyl compound by purging the system out of the system after the polymerization and before the heating step.
- the polymerization reaction for forming the vinylidene fluoride copolymer does not start again during the heating step.
- the state of the crystalline region of the untreated vinylidene fluoride copolymer can be easily adjusted in the heating step.
- the temperature at which the emulsion is heated is determined as follows. First, a part of the above-mentioned untreated vinylidene fluoride copolymer is pulverized and then formed into a film. The heat flow of the untreated vinylidene fluoride copolymer in the form of a film is measured by a method according to ASTM D3418 using a differential scanning calorimeter. Then, among the endothermic peaks of the vinylidene fluoride copolymer observed at 185 ° C. or lower, the temperature lower than the endothermic peak of the highest temperature peak is defined as the heating temperature. By performing the heating step, the dispersibility in a dispersion medium having a relative permittivity of 15 or less is improved.
- the method for determining the temperature at which the emulsion is heated is as follows. First, the emulsion is freeze-dried to make the untreated vinylidene fluoride copolymer into a powder. Then, a mold having a length of 5 cm, a width of 5 cm, and a thickness of 150 ⁇ m and a powdery untreated vinylidene fluoride copolymer (about 1 g) are sandwiched between two aluminum foils sprayed with a release agent and pressed at 200 ° C. And make it into a film.
- a heat flow of the untreated vinylidene fluoride copolymer in the form of a film is obtained by a method according to ASTM D3418 using a differential scanning calorimeter (“DSC-1” manufactured by METTLER). Then, the endothermic peak of the endothermic peak of the untreated vinylidene fluoride copolymer observed at 185 ° C. or lower in the heat flow is specified, and the temperature lower than the endpoint set is set to the temperature at which the emulsion is heated. And.
- the end set is specified as follows. Draw a linear baseline so that it overlaps the linear heat flow on the high temperature side of the endothermic peak (eg, above 185 ° C). Among the endothermic peaks of the vinylidene fluoride copolymer observed at 185 ° C. or lower of the heat flow, the temperature range is on the high temperature side of the peak top of the highest temperature, and the temperature is lower than the lowest temperature at which the heat flow and the baseline overlap. In the temperature range of, as shown in FIG. 1, a tangent line is drawn on the heat flow. Then, the intersection of the tangent line and the baseline is used as an end set of the vinylidene fluoride copolymer.
- the temperature at which the emulsion is heated is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of appropriately changing the crystal structure of the untreated vinylidene fluoride copolymer in the emulsion. It is more preferably 80 ° C. or higher.
- the heating step can be continuously carried out as it is after the polymerization.
- at least unreacted vinylidene fluoride and the fluoroalkyl vinyl compound are purged out of the system, removed, and then heated at the above temperature.
- the polymerization and the heating step can be carried out separately.
- the cooling method at this time is not particularly limited. By cooling to the temperature, it becomes easy to obtain a heating effect (change in the state of the crystalline region of the untreated vinylidene fluoride copolymer), and a vinylidene fluoride copolymer composition having desired physical properties can be obtained. It will be easier.
- the polymerization when the polymerization is not performed in the above-mentioned emulsion preparation step, for example, when a commercially available emulsion is used, it may be heated to the above-mentioned temperature as it is.
- heating at a heating temperature means holding the emulsion at the above heating temperature for a certain period of time. Since the heating time is not intended to remove the initiator remaining in the emulsion by the heating step, the heating time is not particularly limited as long as the state of the crystalline region of the untreated vinylidene fluoride copolymer changes, but as an example. It is preferably 10 seconds or more and 24 hours or less, preferably 20 seconds or more and 12 hours or less, and more preferably 30 seconds or more and 6 hours or less.
- the untreated vinylidene fluoride copolymer By holding the untreated vinylidene fluoride copolymer for the above time at the heating temperature, the state of the crystalline region formed in the polymerization process of the untreated vinylidene fluoride copolymer is likely to change, and the vinylidene fluoride copolymer composition having desired physical properties is obtained. Is easy to obtain.
- the heating method is not particularly limited, and the emulsion may be carried out without stirring or may be carried out with stirring, but it is preferable to carry out with stirring from the viewpoint of dispersion stability of the emulsion.
- the heating device is also not particularly limited.
- the above emulsion may be heated under pressure, saturated steam pressure or atmospheric pressure using an autoclave or the like.
- the aqueous medium is removed from the emulsion.
- the method for removing the aqueous medium is not particularly limited, but it is preferable to dry at a temperature that does not affect the physical properties of the vinylidene fluoride copolymer composition in the emulsion.
- the drying step may be carried out under atmospheric pressure or under reduced pressure. The drying gives the above-mentioned solid (powdered) vinylidene fluoride copolymer composition.
- the drying method can be the same as the drying step in the first method.
- a surfactant is added to the emulsion after the emulsion preparation step in the second method and before the heating step (hereinafter, surfactant).
- surfactant addition step At least a step (hereinafter, also referred to as a “surfactant addition step”) of adding the agent to the emulsion (also referred to as a “surfactant-containing emulsion”) is performed. That is, the emulsion preparation step, the surfactant addition step, and the heating step are performed in this order.
- the emulsion is dried to take out the vinylidene fluoride copolymer (hereinafter, also referred to as “drying step”), whereby the solid vinylidene fluoride copolymer composition described above is obtained. Is obtained. Also in this method, after obtaining the solid vinylidene fluoride copolymer composition, heating at a temperature higher than the melting point of the vinylidene fluoride copolymer composition shall not be performed. Hereinafter, each step will be described.
- Emmulsion preparation process In the emulsion preparation step, an emulsion in which an untreated vinylidene fluoride copolymer is dispersed in an aqueous medium is prepared.
- the emulsion preparation step can be the same as the emulsion preparation step of the first method described above.
- the surfactant addition step the surfactant is added to the emulsion prepared in the above-mentioned emulsion preparation step to prepare a surfactant-containing emulsion.
- the emulsion or the surfactant-containing emulsion
- the emulsion may be cooled before, after, or during the addition of the surfactant.
- the emulsion or the surfactant-containing emulsion after adding the surfactant to a temperature lower than the polymerization temperature in the emulsion preparation step. Specifically, it is preferable to cool to a temperature 5 ° C. or higher lower than the polymerization temperature.
- the cooling method at this time is not particularly limited. By cooling, the effect of performing the heating step (change in the state of the crystalline region of the untreated fluorovinylidene copolymer) can be easily obtained, and the fluorovinylidene copolymer composition having desired physical properties can be obtained. It will be easier to obtain.
- surfactant-containing emulsion it is preferable to add a surfactant to the emulsion in this step because the stability of the emulsion is improved in the heating step. Since it is sufficient that the emulsion in the heating step is stable by the surfactant addition step, the surface tension and the addition amount of the emulsion after addition (surfactant-containing emulsion) are not limited in the surfactant addition step. It can be the same as the above-mentioned first method of adding a surfactant.
- the surfactant is added to the emulsion prepared in the above-mentioned emulsion preparation step and stirred.
- the surface tension of the emulsion (surfactant-containing emulsion) after addition is not particularly limited, but the surface tension at 25 ° C. is preferably 40 mN / m or less, and more preferably 35 mN / m or less.
- the surfactant added in this step is not particularly limited as long as it is soluble or miscible in the aqueous medium contained in the above-mentioned emulsion, and for example, in addition to the above-mentioned surfactant added by the first method, the surfactant is added.
- Nonionic surfactants can also be used.
- the nonionic surfactant that can be used is the same as the surfactant contained in the above-mentioned vinylidene fluoride copolymer composition.
- the surplus component may be removed by dialysis, ion exchange resin or the like, if necessary.
- Heating process In the heating step, the surfactant-containing emulsion obtained in the above-mentioned surfactant addition step is heated.
- the heating step can be the same as the heating step of the second method described above.
- the excess surfactant contained in the surfactant-containing emulsion may be removed by dialysis, an ion exchange resin or the like.
- dialysis is performed by injecting a heat-treated surfactant-containing emulsion into a cellulose dialysis membrane, immersing it in a water tank filled with pure water together with the dialysis membrane, and exchanging the pure water in the water tank at regular intervals. be able to.
- drying process In the drying step, the aqueous medium is removed from the surfactant-containing emulsion.
- the drying method can be the same as the drying step in the first method.
- the above-mentioned vinylidene fluoride copolymer composition is in the form of a polymer dispersion in which the above-mentioned vinylidene fluoride copolymer composition and a dispersion medium are mixed to form an electrode layer described later. It can be used as an electrode mixture or an electrolyte mixture for forming an electrolyte layer.
- the vinylidene fluoride copolymer composition has very good dispersibility in a dispersion medium having a low relative permittivity, and can maintain a stable state for a long period of time.
- the dispersion medium that can be used is preferably a medium that can be removed by drying and has a relative permittivity of 15 or less.
- the dispersion medium having a relative permittivity of 15 or less is not particularly limited, and includes, for example, a non-polar solvent and a low-polarity solvent. Specific examples thereof include a hydrocarbon compound, an ether compound having an ether bond, a ketone compound having a ketone group, and an ester compound having an ester bond. Ester compounds are preferred from the viewpoint of easy dehydration treatment.
- the hydrocarbon compound may be any compound composed of carbon atoms and hydrogen atoms, and may have a chain structure, a branched structure, or a cyclic structure.
- the number of carbon atoms is not particularly limited, and it may have a multiple bond such as a double bond or a triple bond, or an aromatic structure.
- Specific examples include pentane, hexane, heptane, octane, nonane, decane, dodecane, hexene, heptene, cyclohexane, cycloheptane, toluene, xylene, mesitylene, tetraline, and the like.
- the ether compound examples include alkylene glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, etc.
- alkylene glycol alkyl ethers ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, etc.
- ketone compound examples include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diisopropyl ketone, cyclohexanone, holon, acetophenone, isophorone and the like.
- ester compound examples include ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, isopentyl acetate, benzyl acetate, ethyl butyrate, propyl butyrate, butyl butyrate, isopentyl butyrate, ethyl propionate, butyl pentanate, methyl lactate, and lactic acid.
- Examples thereof include ethyl, butyl lactate, ethylene glycol monoalkyl ether acetate and the like. Butyl butyrate is preferred from the viewpoint of easy dehydration treatment.
- the amount of the dispersion medium in the polymer dispersion is appropriately selected depending on the use of the polymer dispersion, the type of vinylidene fluoride copolymer composition, and the like, but with respect to 100% by mass of the polymer dispersion. It is preferably 50% by mass or more and 99.9% by mass or less, and more preferably 75% by mass or more and 99.9% by mass or less. When the amount of the dispersion medium is in the above range, the dispersibility of the vinylidene fluoride copolymer composition in the polymer dispersion tends to be good.
- the polymer dispersion may contain a solvent in addition to the dispersion medium and the vinylidene fluoride copolymer composition.
- the type of solvent is preferably a medium that can be removed by drying, and includes polar solvents and ionic liquids in addition to non-polar solvents and low-polar solvents.
- solvents examples include amide compounds such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; methanol, ethanol, isopropyl alcohol, 2-ethyl-1-hexanol, 1-nonanol, lauryl alcohol, tripropylene glycol.
- Alcohols such as; amine compounds such as o-toluidine, m-toluidine, p-toluidine; 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide; lactones such as ⁇ -butyrolactone, ⁇ -butyrolactone; dimethyl Sulfoxide-sulfone compounds such as sulfoxide and sulfolane; ionic liquids such as ethylmethylimidazolium salt and butylmethylimidazolium salt can be mentioned.
- the amount of the solvent in the polymer dispersion is not particularly limited as long as the dispersibility of the vinylidene fluoride copolymer composition in the polymer dispersion is maintained, but in one example, it is preferably 10% by mass or less.
- Electrodes for non-aqueous electrolyte secondary batteries The above-mentioned polymer dispersion can be used to form an electrode layer for electrodes of various non-aqueous electrolyte secondary batteries and the like.
- the electrodes of the non-aqueous electrolyte secondary battery include, for example, a current collector and an electrode layer arranged on the current collector. At this time, the above-mentioned polymer dispersion can be used to form the electrode layer.
- the electrode may be for a positive electrode or a negative electrode.
- the current collector for the negative electrode and the positive electrode is a terminal for extracting electricity.
- the material of the current collector is not particularly limited, and metal foils such as aluminum, copper, iron, stainless steel, steel, nickel, and titanium, metal nets, and the like can be used. Further, the surface of another medium may be coated with the above metal foil, metal net, or the like.
- Electrode layer is prepared by mixing the above-mentioned vinylidene fluoride copolymer composition or polymer dispersion, an active material, and if necessary, a dispersion medium to prepare an electrode mixture.
- the electrode mixture can be applied onto the current collector to form a dried layer.
- the electrode layer may be formed on only one surface of the current collector, or may be arranged on both surfaces.
- the dispersion medium in the electrode mixture is the same as that described in the above-mentioned polymer dispersion.
- the components in the electrode layer are appropriately selected according to the type of the non-aqueous electrolyte secondary battery.
- it can be a layer containing the above-mentioned vinylidene fluoride copolymer composition and an active substance.
- the electrode layer of the electrode for the all-solid-state battery is preferably a layer containing the above-mentioned vinylidene fluoride copolymer composition, an active material, and a solid electrolyte.
- the electrode layer may contain components other than these, if necessary. Examples of other components include various additives such as conductive aids, pigment dispersants, adhesive aids, and thickeners.
- the amount of the vinylidene fluoride copolymer composition with respect to the total amount of the electrode layer is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.2% by mass or more and 40% by mass or less, and more preferably 0.3% by mass. More preferably, it is 30% by mass or less.
- the amount of the vinylidene fluoride copolymer composition is in the above range, the adhesiveness between the active material, the solid electrolyte and other components in the electrode layer and the current collector tends to be good.
- the active material contained in the electrode layer is not particularly limited, and for example, a conventionally known active material for a negative electrode (negative electrode active material) or an active material for a positive electrode (positive electrode active material) can be used.
- the negative electrode active material examples include artificial graphite, natural graphite, non-graphitized carbon, easily graphitized carbon, activated carbon, or carbon materials such as phenolic resin and calcined by firing; Cu, Li, Mg, B. , Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Cd, Ag, Zn, Hf, Zr and Y and other metal / alloy materials; and GeO, GeO 2 , SnO, SnO 2 , PbO, Metal oxides such as PbO 2 are included. In addition, those having a coating on the surface of these active materials are also included.
- the negative electrode active material may be a commercially available product.
- examples of the positive electrode active material include a lithium-based positive electrode active material containing lithium.
- lithium-based positive electrode active materials include the general formula LiMY 2 (M is Co, Ni, Fe, Mn, Cr, and V) such as LiCoO 2 , LiNi x Co 1-x O 2 (0 ⁇ x ⁇ 1).
- transition metals such as, Y is a composite metal chalcogen compound represented by a chalcogen element such as O and S; a composite metal oxide having a spinel structure such as LiMn 2 O 4 ; and LiFePO 4 Oribin-type lithium compounds such as; etc. are included.
- Y is a composite metal chalcogen compound represented by a chalcogen element such as O and S; a composite metal oxide having a spinel structure such as LiMn 2 O 4 ; and LiFePO 4 Oribin-type lithium compounds such as; etc.
- the positive electrode active material may be a commercially available product.
- the amount of the active material contained in the electrode layer is appropriately selected according to the type, the function of the electrode, the type of the battery, and the like, and is not particularly limited.
- the active material and the vinylidene fluoride copolymer composition It is preferably 50% by mass or more and 99.9% by mass or less with respect to the total amount of the substance and the conductive auxiliary agent.
- the amount of the active material is within the above range, for example, a sufficient charge / discharge capacity can be obtained, and the battery performance tends to be good.
- the conductive auxiliary agent is not particularly limited as long as it is a compound capable of further enhancing the conductivity between the active materials or between the active materials and the current collector.
- the electrode layer contains a solid electrolyte as another component, in addition to the above, the conductivity between the active material and the solid electrolyte, between the solid electrolyte and the current collector, or between the solid electrolytes is further enhanced.
- the compound is not particularly limited as long as it can be used. Examples of conductive aids include acetylene black, ketjen black, carbon black, graphite powder, carbon nanofibers, carbon nanotubes, carbon fibers and the like.
- the amount of the conductive auxiliary agent contained in the electrode layer is appropriately selected according to the type, the function of the electrode, the type of the battery, etc., and is not particularly limited, but is arbitrarily set according to the type and the type of the battery. can. From the viewpoint of improving both the conductivity and the dispersibility of the conductive auxiliary agent, in one example, 0.1% by mass and 15% by mass with respect to the total amount of the active material, the vinylidene fluoride copolymer composition, and the conductive auxiliary agent. % Or less is preferable, 0.1% by mass or more and 7% by mass or less is more preferable, and 0.1% by mass or more and 5% by mass or less is further preferable.
- the solid electrolyte contained in the electrode mixture layer is not particularly limited as long as it is a solid compound having ionic conductivity, and conventionally known inorganic solid electrolytes and polymer solid electrolytes can be used.
- the inorganic solid electrolyte include an oxide-based solid electrolyte, a sulfide-based solid electrolyte, a nitride-based solid electrolyte, a complex hydride-based solid electrolyte, and the like.
- the polymer solid electrolyte includes, for example, a gel-based electrolyte, an intrinsic polymer electrolyte, and the like.
- the oxide-based solid electrolyte is not limited to this, but is limited to perovskite type LLTO, garnet type LLZ, NASICON type compound, LISION type compound, LIPON type compound, ⁇ -alumina type compound and the like. Can be mentioned. Specific examples include Li 3 PO 4 , Li 0.34 La 0.51 TiO 3 , Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 , Li 6 .
- BaLa 2 Ta 2 O 12 Li 2.9 PO 3.3 N 0.46 , Li 4.3 Al 0.3 Si 0.7 O 4 , 50Li 4 SiO 4-50Li 3 BO 3 , Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 -TiO 2 , Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3-0.05 Li 2 O and the like are included.
- the sulfide-based solid electrolyte includes a solid electrolyte containing Li, A (A is at least one of P, Si, Ge, Al and B), and S, and the sulfide-based solid electrolyte is a halogen. It may further contain an element. Further, LGPS (Li-Ge-PS) type compounds, algyrodite-type compounds, amorphous compounds, Li-PS-based compounds and the like can also be mentioned. Specific examples of the sulfide-based solid electrolyte include Li 2 SP 2 S 5, Li 2 SP 2 S 3, Li 2 SP 2 S 3-P 2 S 5 , Li 2 S - SiS 2 , and Li 2 S-SiS 2.
- LiI-Li 2 S-SiS 2 LiI-Li 2 SP 2 S 5, LiI-Li 2 SP 2 O 5, LiI-Li 3 PO 4-P 2 S 5 , LiI - Li 2 S - SiS 2 -P 2 S 5 , Li 2 S-SiS 2 -Li 4 SiO 4 , Li 2 S-SiS 2 -Li 3 PO 4 , Li 3 PS 4 -Li 4 GeS 4 , Li 3.4 P 0.6 Si 0.4 S 4 , Li 3.25 P 0.25 Ge 0.76 S 4 , Li 3.25 P 0.75 Ge 0.25 S 4 , Li 10 GeP 2 S 12 , Li 4-x Ge 1- x P x S 4 , Li 6 PS 5 Cl, Li 6 PS 5 Br, Li 6 PS 5 I and the like are included.
- the nitride-based solid electrolyte is not limited to this, and specific examples thereof include LiN 3 .
- the complex hydride solid electrolyte is not limited to this, and specific examples thereof include LiBH 4 .
- the gel-based electrolyte is not limited to this, and specific examples thereof include Poly (ethylene oxide) 8 -LiClO 4 (ethylene carbonate (EC) + propylene carbonate (PC)) and Poly (ethylene oxide) 8- .
- LiClO 4 (PC) Poly (vinylidene fluororide) -LiN (CF 3 SO 2 ) 2 (EC + PC), Poly (vinylidene fluororide-co-hexafluoropolylone) -LiPF 6 (EC + diethyl carbonate (DEC)) , Poly (ethylene glycoclylate) -LiClO 4 (PC), Poly (acrylonylene) -LiClO 4 (EC + PC), Poly (methyl methyllate) -LiClO 4 (PC) and the like.
- the intrinsic polymer electrolyte include, but are not limited to, Poly (etherylene oxide) 8 -LiClO 4 , Poly (oxymethylene) -LiClO 4 , Poly (polyline oxide) 8 -LiClO 4 , Poly (poly). dimethyl siloxane) -LiClo 4 , Poly (vinylideene fluororide-co-hexafluoropolylone) -LiTFSI, Poly (2,2- dimethium perchlorate) -Lithium perchlorate, etc.
- the electrode layer may contain only one type of the above solid electrolyte, or may contain two or more types.
- the amount of the solid electrolyte is appropriately selected according to the type, the function of the electrode, the type of the battery, and the like, and is not particularly limited. It is preferably 1% by mass or more and 99.9% by mass or less with respect to the total amount of the vinylidene copolymer composition and the solid electrolyte. When the amount of the solid electrolyte is in the above range, sufficient ionic conductivity can be obtained and the battery performance tends to be good.
- the electrode layer may contain a pigment dispersant, an adhesion auxiliary agent, a thickener, and the like, and known compounds can be used as these. These amounts are not particularly limited as long as they do not impair the object and effect of the present invention, but in one example, they are 15% by mass based on the active material, the vinylidene fluoride copolymer composition, and the total amount thereof. The following is preferable.
- the electrode layer is a nitrogen compound such as a phosphorus compound, a sulfur compound, an organic acid, an amine compound, and an ammonium compound; an organic ester, various silane-based, titanium-based and aluminum-based coupling agents; other than the above-mentioned vinylidene fluoride copolymer.
- Additives such as vinylidene fluoride polymer, polytetrafluoroethylene (PTFE), styrene / butadiene rubber (SBR), and resins such as polyacrylonitrile (PAN); may be further contained.
- the thickness of the electrode layer is not particularly limited, but in one example, it is preferably 1 ⁇ m or more and 1000 ⁇ m or less.
- the basis weight of the active material contained in the electrode layer is not particularly limited and may be any amount, but in one example, 50 to 1000 g / m 2 is preferable, and 100 to 500 g / m. 2 is more preferable.
- the electrode layer is an electrode in which the above-mentioned vinylidene fluoride copolymer composition or polymer dispersion liquid, an active material, and if necessary, a solid electrolyte, a dispersion medium, a solvent, a conductive auxiliary agent, various additives, and the like are mixed. It can be formed by performing a step of preparing a mixture, a step of applying the electrode mixture onto a current collector, and a step of drying the mixture.
- the electrode mixture may be prepared by mixing all the components at once, or may be prepared by mixing some components first and then the remaining components. For this reason, it is preferable to mix with a mixer equipped with a temperature control device so that the temperature of the electrode layer mixture does not rise excessively.
- the dispersion medium and solvent in the electrode mixture may be any as long as it is possible to uniformly disperse the vinylidene fluoride copolymer composition, the active material, the solid electrolyte, the conductive auxiliary agent and the like.
- the type of the dispersion medium to be added is not particularly limited, but it is preferably the same as the dispersion medium contained in the above-mentioned polymer dispersion liquid.
- a solvent is added, it is preferably the same as the solvent contained in the above-mentioned polymer dispersion.
- the total amount of the dispersion medium in the polymer dispersion and the dispersion medium added thereto is not particularly limited and may be any amount from the viewpoint of production, but in one example, the amount of the above-mentioned active material. It is preferably 10 parts by mass or more and 20000 parts by mass or less with respect to 100 parts by mass.
- the total amount of the solvent in the polymer dispersion and the solvent added thereto is not particularly limited and may be any amount from the viewpoint of production, but in one example, the amount of the above-mentioned active material is 100% by mass. It is preferably 2000 parts by mass or less with respect to the part.
- the viscosity of the electrode mixture can prevent dripping, uneven coating of the electrode, and delay in drying after coating when the electrode mixture is applied to obtain an electrode, and the workability of electrode production and the coatability of the electrode are improved.
- the viscosity is not particularly limited as long as it has a good viscosity. In one example, 0.1 Pa ⁇ s or more and 100 Pa ⁇ s or less are preferable.
- the viscosity of the electrode mixture is measured by an E-type viscometer or the like.
- the method for applying the electrode mixture is not particularly limited, and a doctor blade method, a reverse roll method, a comma bar method, a gravure method, an air knife method, a die coat method, a dip coat method, etc. can be applied.
- the drying temperature is preferably 30 ° C. or higher and 500 ° C. or lower. Drying may be performed multiple times at different temperatures. At this time, it may be dried under atmospheric pressure, pressurization, or depressurization. Further heat treatment may be performed after drying.
- the electrode density can be improved by performing the pressing process.
- the press pressure is preferably 1 kPa or more and 10 GPa or less.
- Electrolyte layer for non-aqueous electrolyte secondary battery The above-mentioned vinylidene fluoride copolymer composition or polymer dispersion can also be used for producing, for example, an electrolyte layer for non-aqueous electrolyte secondary battery.
- the electrolyte layer for a non-aqueous electrolyte secondary battery (hereinafter, also simply referred to as “electrolyte layer”) may include, for example, only the electrolyte layer.
- the above-mentioned polymer dispersion (vinylidene fluoride copolymer) can be used as a material for the electrolyte layer.
- the electrolyte layer may contain at least the above-mentioned vinylidene fluoride copolymer composition and an electrolyte, and may further contain other components if necessary.
- the electrolyte layer may be a layer for binding the electrode and the electrolyte, may be a layer for conducting various ions, or may be a layer having these functions at the same time.
- the above-mentioned vinylidene fluoride copolymer composition may be in the form of particles, a film (including a porous film), or a gel.
- the all-solid-state battery has, for example, a structure in which an electrolyte layer is sandwiched between a pair of electrodes (both having a current collector and an electrode layer).
- the above-mentioned polymer dispersion can also be used to form an electrolyte layer of such an all-solid-state battery.
- the electrolyte layer is based on an electrolyte mixture containing, for example, a vinylidene fluoride copolymer composition or a polymer dispersion, a solid electrolyte, a dispersion medium if necessary, and optionally other components. It may be a layer applied on the material and dried. At this time, the dried layer may be peeled off from the base material. Further, the layer may be a layer in which the electrolyte mixture is directly applied onto the electrodes and dried.
- an electrolyte mixture containing, for example, a vinylidene fluoride copolymer composition or a polymer dispersion, a solid electrolyte, a dispersion medium if necessary, and optionally other components. It may be a layer applied on the material and dried. At this time, the dried layer may be peeled off from the base material. Further, the layer may be a layer in which the electrolyte mixture is directly applied onto the electrodes and dried.
- the same compounds as those described in the above description of the electrode layer of the electrode can be used.
- the amount of the solid electrolyte with respect to the total amount of the electrolyte layer is appropriately selected according to the type, the function of the electrolyte layer, the type of the battery, etc., and is not particularly limited. It is preferably 10% by mass or more and 99.9% by mass or less.
- the electrolyte layer may contain components other than the above-mentioned vinylidene fluoride copolymer and the above-mentioned solid electrolyte, and examples thereof include pigment dispersants, adhesion aids, thickeners, fillers and various additives. Etc. are included.
- pigment dispersant, the adhesive aid, and the thickener known compounds can be used, and they may be the same as the additives contained in the electrode layer. Further, these amounts are not particularly limited as long as they do not impair the object and effect of the present invention, but in one example, they are preferably 0.1% by mass or more and 90% by mass or less with respect to the total amount of the electrolyte layer.
- the filler contained in the electrolyte layer may be an inorganic filler or an organic filler.
- inorganic fillers include silicon dioxide (SiO 2 ), alumina (Al 2 O 3 ), titanium dioxide (TIO 2 ), calcium oxide (CaO), strontium oxide (SrO), barium oxide (BaO), magnesium oxide (BaO).
- Oxides such as MgO), zinc oxide (ZnO), barium titanate (BaTIO 3 ); magnesium hydroxide (Mg (OH) 2 ), calcium hydroxide (Ca (OH) 2 ), zinc hydroxide (Zn (OH) 2 ) Hydroxides such as aluminum hydroxide (Al (OH) 3 ) and aluminum hydroxide (AlO (OH)); carbonates such as calcium carbonate (CaCO 3 ); sulfates such as barium sulfate; nitrides Includes; clay minerals; and boehmite and the like.
- the filler may contain only one kind, or may contain two or more kinds of fillers. Further, these amounts are not particularly limited as long as they do not impair the object and effect of the present invention, but in one example, they are preferably 0.1% by mass or more and 90% by mass or less with respect to the total amount of the electrolyte layer.
- the thickness of the electrolyte layer is appropriately selected according to the function of the electrolyte layer and is not particularly limited, but in one example, it is preferably 1 ⁇ m or more and 1000 ⁇ m or less.
- the amount of the vinylidene fluoride copolymer composition with respect to the total amount of the electrolyte layer is appropriately selected according to the type, the function of the electrolyte layer, the type of the battery, etc., and is not particularly limited, but in one example, it is 0. .1% by mass or more and 10% by mass or less is preferable.
- the method for forming the electrolyte layer is not particularly limited, and as described above, the electrolyte mixture can be applied and dried to form the electrolyte layer.
- the method of applying the electrolyte mixture and the method of drying are the same as the method of forming the electrode layer.
- the electrolyte mixture the above-mentioned polymer dispersion may be mixed with the solid electrolyte as it is, or a dispersion medium or a solvent may be further added if necessary.
- the dispersion medium used for forming the electrolyte layer is not particularly limited, but is preferably the same as the dispersion medium contained in the above-mentioned polymer dispersion liquid.
- Non-aqueous electrolyte secondary battery As described above, the above-mentioned vinylidene fluoride copolymer composition or polymer dispersion can be used for electrodes of various non-aqueous electrolyte secondary batteries including all-solid-state batteries and for the electrolyte layer. However, it may be used to form other layers of non-aqueous electrolyte secondary batteries.
- Emulsion 1 280 parts by mass of ion-exchanged water was placed in an autoclave, and degassing was performed by nitrogen bubbling for 30 minutes. Next, 0.2 parts by mass of disodium hydrogen phosphate and 1.0 part by mass of perfluorooctanoic acid ammonium salt (PFOA) were charged and pressurized to 4.5 MPa to perform nitrogen substitution three times. Then, 0.1 part by mass of ethyl acetate, 11 parts by mass of vinylidene fluoride (VDF), and 24 parts by mass of hexafluoropropylene (HFP) were added to the autoclave. The temperature was raised to 80 ° C. with stirring.
- PFOA perfluorooctanoic acid ammonium salt
- the solid content concentration (concentration of vinylidene fluoride copolymer) of the emulsion 1 was 21.0% by mass. Further, the untreated vinylidene fluoride copolymer was taken out by freeze-drying, and the endothermic peak endpoint of the vinylidene fluoride copolymer observed at 185 ° C. or lower was measured at 132 ° C. based on the method described later. ..
- the emulsion was freeze-dried to obtain a powdery vinylidene fluoride copolymer.
- a mold measuring 5 cm in length ⁇ 5 cm in width ⁇ 150 ⁇ m in thickness and about 1 g of powdered vinylidene fluoride copolymer were sandwiched between two aluminum foils sprayed with a release agent and pressed at 200 ° C. The film was prepared. Then, the measurement was performed according to ASTM D3418 using a differential scanning calorimeter (“DSC-1” manufactured by METTLER) to obtain a heat flow of the vinylidene fluoride copolymer.
- DSC-1 differential scanning calorimeter
- the baseline is set so as to overlap the linear heat flow in the temperature range on the high temperature side of the peak top of the highest temperature. I drew it in a straight line.
- the temperature range is on the high temperature side of the peak top of the highest temperature, and the temperature is lower than the minimum temperature of the temperature at which the heat flow and the baseline overlap. In this temperature range, a tangent line was drawn on the heat flow, and the intersection of the tangent line and the baseline was defined as the end set of the vinylidene fluoride copolymer.
- Emulsion 2 Emulsion except that the amount of VDF collectively added to the autoclave was changed from 11 parts by mass to 15 parts by mass and the amount of HFP was changed from 24 parts by mass to 20 parts by mass before the start of polymerization.
- Polymerization was carried out in the same manner as in the preparation of No. 1 to obtain an emulsion 2 in which the untreated vinylidene fluoride copolymer was dispersed in water.
- the solid content concentration (concentration of vinylidene fluoride copolymer) of the emulsion 2 was 20.8% by mass.
- the endothermic peak of the endothermic peak of the untreated vinylidene fluoride copolymer identified at 185 ° C. or lower in the same manner as in Emulsion 1 is 134 ° C. there were.
- Emulsion 3 Emulsion except that the amount of VDF collectively added to the autoclave was changed from 11 parts by mass to 25 parts by mass and the amount of HFP was changed from 24 parts by mass to 10 parts by mass before the start of polymerization.
- Polymerization was carried out in the same manner as in the preparation of No. 1 to obtain an emulsion 3 in which the untreated vinylidene fluoride copolymer was dispersed in water.
- the solid content concentration (concentration of vinylidene fluoride copolymer) of the emulsion 3 was 21.3% by mass.
- the endothermic peak of the endothermic peak of the untreated vinylidene fluoride copolymer identified by the same method as in Emulsion 1 was 152 ° C.
- Emulsion 1 was placed in an autoclave, and SDS was further added so that the concentration of sodium dodecyl sulfate (SDS) with respect to water in the emulsion was 1% by mass to obtain a surfactant-containing emulsion. At this time, the surface tension of the surfactant-containing emulsion at 25 ° C. was measured. The results are shown in Table 1.
- SDS sodium dodecyl sulfate
- the mixture was heated at 125 ° C., which is a temperature lower than that of the end set, for 1 hour. Then, while continuing stirring, the can was air-cooled at room temperature (24 ° C.) until the temperature inside the can became 40 ° C. or lower. Further, the emulsion was freeze-dried to obtain a powdery vinylidene fluoride copolymer composition. The average secondary particle size of the powdery vinylidene fluoride copolymer composition was 174 ⁇ m. At this time, the freeze-dried product was obtained by freezing the polymerized emulsion with liquid nitrogen and drying it under reduced pressure at room temperature.
- Example 2 Heat treatment and freeze-drying were carried out in the same manner as in Example 1 except that the concentration of SDS with respect to water in Emulsion 1 was changed from 1% by mass to 0.5% by mass to obtain a powdery vinylidene fluoride copolymer composition. Obtained.
- the powdery vinylidene fluoride copolymer composition had an average secondary particle size of 141 ⁇ m.
- Example 3 Heat treatment and freeze-drying were carried out in the same manner as in Example 2 except that the surfactant added to Emulsion 1 was changed from SDS to Emulgen LS-110 (polyoxyalkylene alkyl ether manufactured by Kao Co., Ltd.), and fluorinated in powder form. A vinylidene copolymer composition was obtained. The average secondary particle size of the powdery vinylidene fluoride copolymer composition was 197 ⁇ m.
- Example 4 Heat treatment and freeze-drying were carried out in the same manner as in Example 2 except that the surfactant added to Emulsion 1 was changed from SDS to PFOA (perfluorooctanoic acid) to obtain a powdery vinylidene fluoride copolymer composition. ..
- the average secondary particle size of the powdery vinylidene fluoride copolymer composition was 163 ⁇ m.
- Example 5 Heat treatment and freeze-drying were carried out in the same manner as in Example 2 except that the heating temperature of Emulsion 1 was changed from 125 ° C. to 95 ° C. to obtain a powdery vinylidene fluoride copolymer composition.
- the average secondary particle size of the powdery vinylidene fluoride copolymer composition was 391 ⁇ m.
- Example 6 Heat treatment and freeze-drying were carried out in the same manner as in Example 2 except that the heating temperature of Emulsion 1 was changed from 125 ° C. to 75 ° C. to obtain a powdery vinylidene fluoride copolymer composition.
- the powdery vinylidene fluoride copolymer composition had an average secondary particle size of 364 ⁇ m.
- Example 7 Heat treatment and freeze-drying were carried out in the same manner as in Example 2 except that the concentration of SDS with respect to water in Emulsion 1 was changed from 0.5% by mass to 0% by mass to obtain a powdery vinylidene fluoride copolymer composition. Obtained. The average secondary particle size of the powdery vinylidene fluoride copolymer composition was 173 ⁇ m.
- Example 8 Heat treatment and freeze-drying were carried out in the same manner as in Example 6 except that the concentration of SDS with respect to water in Emulsion 1 was changed from 0.5% by mass to 0% by mass to obtain a powdery vinylidene fluoride copolymer composition. Obtained.
- the powdery vinylidene fluoride copolymer composition had an average secondary particle size of 424 ⁇ m.
- Example 9 The same as in Example 2 except that the emulsion to be put into the autoclave was changed from emulsion 1 to emulsion 2, and the heating temperature of the emulsion (surfactant-containing emulsion) after adding the surfactant was changed from 125 ° C to 130 ° C. Heat treatment and freeze-drying were carried out to obtain a powdery vinylidene fluoride copolymer composition.
- the average secondary particle size of the powdery vinylidene fluoride copolymer composition was 52 ⁇ m.
- Emulsion 1 was placed in an autoclave, and PFOA was further added so that the concentration of PFOA with respect to water in the emulsion was 0.5% by mass. Then, PFOA was dissolved in the emulsion by stirring at room temperature (24 ° C.) at 500 rpm. The emulsion was freeze-dried to obtain a powdery vinylidene fluoride copolymer composition. The average secondary particle size of the powdery vinylidene fluoride copolymer composition was 160 ⁇ m.
- Emulsion 1 was placed in an autoclave, SDS was further added so that the concentration of SDS with respect to water in the emulsion was 1% by mass, and the SDS was dissolved in the emulsion by stirring at room temperature (24 ° C.) at 500 rpm. The emulsion was freeze-dried to obtain a powdery vinylidene fluoride copolymer composition. The average secondary particle size of the powdery vinylidene fluoride copolymer composition was 148 ⁇ m.
- Example 12 Dissolution and freeze-drying were carried out in the same manner as in Example 11 except that the concentration of SDS with respect to water in the emulsion was changed from 1% by mass to 0.5% by mass to obtain a powdery vinylidene fluoride copolymer composition. rice field. The average secondary particle size of the powdery vinylidene fluoride copolymer composition was 126 ⁇ m.
- Example 13 Dissolution and freeze-drying were carried out in the same manner as in Example 10 except that the concentration of PFOA with respect to water in the emulsion was changed from 0.5% by mass to 1% by mass to obtain a powdery vinylidene fluoride copolymer composition. rice field.
- the powdery vinylidene fluoride copolymer composition had an average secondary particle size of 219 ⁇ m.
- Example 14 A powdery vinylidene fluoride copolymer composition was dissolved and freeze-dried in the same manner as in Example 10 except that the concentration of PFOA with respect to water in the emulsion was changed from 0.5% by mass to 0.1% by mass. Got The average secondary particle size of the powdery vinylidene fluoride copolymer composition was 178 ⁇ m.
- Emulsion 1 is placed in an autoclave, and acetamine 86 (stearylamine acetate manufactured by Kao Co., Ltd.) is added so that the concentration of acetamine 86 in the water in the emulsion is 0.05% by mass, and the temperature is 500 rpm at room temperature (24 ° C.). Acetamine 86 was dissolved in the emulsion by stirring. The emulsion was freeze-dried to obtain a powdery vinylidene fluoride copolymer composition. The average secondary particle size of the powdery vinylidene fluoride copolymer composition was 821 ⁇ m.
- Emulsion 1 was freeze-dried to obtain a powdery vinylidene fluoride copolymer composition.
- the average secondary particle size of the powdery vinylidene fluoride copolymer composition was 215 ⁇ m.
- Example 2 The powdery vinylidene fluoride copolymer composition obtained in Example 11 was heat-treated at 125 ° C. for 1 hour to obtain a powdery vinylidene fluoride copolymer composition. Since the vinylidene fluoride copolymer composition aggregates violently, the average secondary particle size cannot be measured.
- Comparative Example 3 The powdery vinylidene fluoride copolymer composition obtained in Comparative Example 1 was heat-treated at 125 ° C. for 1 hour to obtain a powdery vinylidene fluoride copolymer composition. Since the vinylidene fluoride copolymer composition aggregates violently, the average secondary particle size cannot be measured.
- Example 4 Dissolution and freeze-drying were carried out in the same manner as in Example 10 except that the surfactant to be added to the emulsion was changed from PFOA to Emargen LS-110 to obtain a powdery vinylidene fluoride copolymer composition.
- the powdery vinylidene fluoride copolymer composition had an average secondary particle size of 127 ⁇ m.
- ⁇ Comparative Example 5> The emulsion to be put into the autoclave was changed from emulsion 1 to emulsion 3, and heat treatment and freeze-drying were performed in the same manner as in Example 2 except that the heating temperature of the emulsion was changed from 125 ° C to 150 ° C. A polymer composition was obtained. The average secondary particle size of the powdery vinylidene fluoride copolymer composition was 39 ⁇ m.
- the average secondary particle size of vinylidene fluoride copolymer composition is laser diffraction / scattering for powdery vinylidene fluoride copolymer composition.
- the measurement was performed on a volume basis by the method, and the cumulative average diameter (D50) of the particle size distribution was calculated. Specifically, using Microtrac MT3300EXII manufactured by Microtrac Bell, about 0.5 mg of the powdery vinylidene fluoride copolymer composition was dispersed in water by stirring to prepare a sample for measurement.
- the measurement medium is water, the medium refractive index is 1.333, the particle shape is non-spherical, the particle refractive index is 1.42, the measurement time is 30 seconds, and the average value of D50 when measured 5 times in the transmission mode is 2 on average. The next particle size was used.
- the melting point of vinylidene fluoride copolymer composition was measured in the form of a film produced by the following method. First, a mold having a length of 5 cm, a width of 5 cm, and a thickness of 150 ⁇ m and about 1 g of a powdery vinylidene fluoride copolymer composition are sandwiched between two aluminum foils sprayed with a release agent, and pressed at 200 ° C. And got a press film. Then, the melting point was measured according to ASTM D3418 using a differential scanning calorimeter (“DSC-1” manufactured by METTLER).
- DSC-1 differential scanning calorimeter
- a temperature-modulated differential scanning calorimeter (Q-100, manufactured by TA Instruments) was used. It was measured. Specifically, about 5 mg of the vinylidene fluoride copolymer composition powdered by freeze-drying was packed in an aluminum pan to prepare a sample for measurement. The measurement conditions were an average temperature rise rate of 5 ° C./min, a modulation period of 40 seconds, and a modulation amplitude of ⁇ 0.531 ° C. so as to be heat-only conditions.
- the obtained rebirthing heat flow had a downwardly convex endothermic peak.
- a baseline was drawn linearly so as to overlap the linear heat flow on the high temperature side of the end set.
- the point where the distance is far is defined as the peak top of the endothermic peak, and the temperature of the peak top is specified.
- the number of minimum values of the endothermic peaks convex under the rebirthing heat flow was defined as the number of peak tops of the endothermic peaks.
- the region surrounded by the baseline and the reversing heat flow was defined as the melting enthalpy amount ( ⁇ Hm).
- the surface tension of an emulsion (when a surfactant is added to an emulsion, the emulsion after the surfactant is added to the emulsion) is measured by a surface tension meter (Sigma701 / 700, KSV instruments) using the Wilhelmy method. (Manufactured by the company). A platinum plate was used for the measurement, and the average value when the surface tension at 25 ° C. was measured three times was taken as the value of the surface tension.
- the turbidity of the dispersion liquid in which the vinylidene fluoride copolymer composition was dispersed in butyl butyrate was measured by the following method. First, 2 g of a powdered vinylidene fluoride copolymer composition is added to 18 g of butyl butyrate, and the mixture is stirred on a stirrer at 25 ° C. for 30 minutes to obtain a butyl butyrate dispersion of the vinylidene fluoride copolymer composition. The content of the vinylidene compound copolymer composition was 10% by mass).
- the turbidity of the dispersion liquid after allowing the sample to stand for 20 hours and then re-stirring was measured by NDH2000 (based on JIS K 7136) manufactured by Nippon Denshoku Kogyo.
- NDH2000 based on JIS K 7136
- the sample was placed in a quartz cell.
- the turbidity of the sample was calculated with the turbidity of butyl butyrate as 0%.
- the melting point of the vinylidene fluoride copolymer composition is 140 ° C. or lower, and the vinylidene fluoride copolymer composition has a melting enthalpy amount ( ⁇ Hm) of 2 mJ / g in the reversing heat flow.
- ⁇ Hm melting enthalpy amount
- the content of the upper vinylidene fluoride copolymer composition after standing for 20 hours in the dispersion dispersed in butyl butyrate (content of the vinylidene fluoride copolymer composition is 10% by mass) is 4.0% by mass. When it was 10% by mass or less, the dispersibility of the vinylidene fluoride copolymer composition was good (Examples 1 to 15).
- the fluorinated vinylidene copolymer weight of the upper part of the dispersion liquid in which the vinylidene fluoride copolymer composition is dispersed in butyl butyrate (content of the vinylidene fluoride copolymer composition: 10% by mass) is allowed to stand for 20 hours.
- content of the coalesced composition was 4.0% by mass or more and more than 10% by mass, the dispersibility was low in all cases (Comparative Examples 1 to 8).
- fluoride having desired physical properties is obtained by adding a certain amount of a surfactant to an emulsion of vinylidene fluoride copolymer (copolymer dispersion) or by heating the emulsion.
- a vinylidene copolymer composition was obtained (Examples 1 to 15).
- the surfactant was not added to the emulsion of the vinylidene fluoride copolymer and the emulsion was not heated, the vinylidene fluoride copolymer composition settled in butyl butyrate. It was easy (Comparative Example 1).
- the vinylidene fluoride copolymer composition of the present invention is easy to disperse in a dispersion medium having a low relative permittivity, and further, it is difficult to settle even if the dispersion liquid is stored for a long time. Therefore, it is very useful for producing an electrode layer and an electrolyte layer for a non-aqueous electrolyte secondary battery.
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Abstract
Description
すなわち、本発明は、フッ化ビニリデン共重合体を含むフッ化ビニリデン共重合体組成物であって、前記フッ化ビニリデン共重合体は、フッ化ビニリデン由来の構成単位と、含フッ素アルキルビニル化合物由来の構成単位とを含み、前記フッ化ビニリデン共重合体組成物の融点が140℃以下であり、前記フッ化ビニリデン共重合体組成物は、前記フッ化ビニリデン共重合体組成物のリバーシングヒートフローを温度変調示差走査熱量計で測定したとき、融解エンタルピー量(ΔHm)が2J/g以上である吸熱ピークを有し、前記吸熱ピークのうち、最も大きい吸熱ピークのピークトップ温度と、前記フッ化ビニリデン共重合体組成物の前記融点との差の絶対値が10℃以下であり、酪酸ブチルと前記フッ化ビニリデン共重合体組成物とを含み、かつ前記フッ化ビニリデン共重合体組成物の含有率が10質量%である分散液を、25℃で30分間攪拌し、20時間静置した後の、前記分散液の上部20体積%における前記フッ化ビニリデン共重合体組成物の含有率が、4.0質量%以上10質量%以下である、フッ化ビニリデン共重合体組成物を提供する。
フッ化ビニリデン由来の構成単位と、含フッ素アルキルビニル化合物由来の構成単位とを含むフッ化ビニリデン共重合体を含有するフッ化ビニリデン共重合体組成物の製造方法であって、水性媒体中に未処理フッ化ビニリデン共重合体が分散したエマルションを準備する工程と、前記エマルションに界面活性剤を添加して攪拌し、25℃における表面張力が40mN/m以下の界面活性剤含有エマルションを得る工程と、を含み前記フッ化ビニリデン共重合体組成物の融点が140℃以下である、フッ化ビニリデン共重合体組成物の製造方法を提供する。
本発明のフッ化ビニリデン共重合体組成物は、所定の物性を有するフッ化ビニリデン共重合体を含む組成物である。フッ化ビニリデン共重合体組成物は、フッ化ビニリデン共重合体のみで構成されていてもよく、フッ化ビニリデン共重合体と例えば界面活性剤等の他の成分を含んでいてもよい。
本発明のフッ化ビニリデン共重合体組成物が含むフッ化ビニリデン共重合体は、フッ化ビニリデン由来の構造単位、および含フッ素アルキルビニル化合物由来の構成単位を含む。フッ化ビニリデン共重合体中のフッ化ビニリデン由来の構成単位の量は、フッ化ビニリデン共重合体の構成単位100質量%に対して、30質量%以上85質量%以下が好ましく、40質量%以上80質量%以下がより好ましい。フッ化ビニリデン由来の構造単位の質量分率が上述の範囲内であると、フッ化ビニリデン共重合体組成物の融点が所望の範囲に収まりやすくなる。上記フッ化ビニリデン由来の構造単位の質量分率は、フッ化ビニリデン共重合体を19F-NMRで分析することにより特定することができる。
上述のように、フッ化ビニリデン共重合体組成物は、フッ化ビニリデン共重合体だけでなく、界面活性剤をさらに含んでいてもよい。
本発明のフッ化ビニリデン共重合体組成物は、上述のように、その融点が140℃以下であればよいが、135℃以下が好ましく、130℃以下がより好ましい。フッ化ビニリデン共重合体組成物の融点は、上述のフッ化ビニリデン共重合体中の含フッ素アルキルビニル化合物由来の構成単位の量等によって調整可能である。また、本明細書において、フッ化ビニリデン共重合体組成物の融点は、以下の方法で測定する。まず、粉体状のフッ化ビニリデン共重合体組成物を200℃でプレスし、厚み150μmのフィルム状に成形する。示差走査熱量計を用い、ASTM D3418に準拠して、プレスしたフィルム状のフッ化ビニリデン共重合体組成物の融点を測定する。当該方法によって測定されるフッ化ビニリデン共重合体組成物の融点は、フッ化ビニリデン共重合体組成物を一度溶融した後に測定される値である。したがって、後述のフッ化ビニリデン共重合体の重合反応過程における製造履歴およびフッ化ビニリデン共重合体組成物の製造方法の影響を受けにくい。
上述の物性を満たすフッ化ビニリデン共重合体組成物は、例えば以下の3つの方法で製造できる。ただし、上述のフッ化ビニリデン共重合体組成物の製造方法は、以下の3つの方法に限定されない。
フッ化ビニリデン共重合体組成物の製造方法の第1の方法では、水性媒体中に未処理フッ化ビニリデン共重合体が分散したエマルションを準備する工程(以下、「エマルション準備工程」とも称する)と、当該エマルションにイオン性界面活性剤を添加して攪拌し、25℃における表面張力が40mN/m以下の界面活性剤含有エマルションを得る工程(以下、「界面活性剤添加工程」とも称する)と、を行う。
エマルション準備工程では、水性媒体中に未処理フッ化ビニリデン共重合体が分散したエマルションを準備する。なお、当該エマルションは市販品であってもよい。本明細書において、未処理フッ化ビニリデン共重合体とは、一般的な方法によって調製されたフッ化ビニリデンと含フッ素アルキルビニル化合物との共重合体を指し、フッ化ビニリデン共重合体の重合後、残存モノマーや残存開始剤の分解を目的とする以外の加熱処理や界面活性剤との混合等が行われていないものをいう。当該未処理フッ化ビニリデン共重合体は、上述のフッ化ビニリデン共重合体と実質的に同様の組成を有する。ただし、水性媒体中に未処理フッ化ビニリデン共重合体が分散したエマルションに後述の界面活性剤添加工程等を行うことによって、当該未処理フッ化ビニリデン共重合体の比誘電率が15以下である分散媒に対する分散性が変化する。
界面活性剤添加工程では、上述のエマルション準備工程で準備したエマルションに、イオン性界面活性剤を添加して攪拌し、25℃における表面張力が40mN/m以下の界面活性剤含有エマルションを得る。本工程で添加するイオン性界面活性剤は、添加後のエマルション(界面活性剤含有エマルション)の表面張力を40mN/m以下とすることが可能であれば特に制限されない。ここで、イオン性界面活性剤添加後のエマルション(界面活性剤含有エマルション)の25℃における表面張力は、5mN/m以上40mN/m以下が好ましく、10mN/m以上40mN/m以下がより好ましい。
乾燥工程では、上記界面活性剤含有エマルションから水性媒体を除去する。水性媒体の除去方法は特に制限されないが、界面活性剤含有エマルション中のフッ化ビニリデン共重合体組成物の物性等に影響を及ぼさない温度で乾燥させることが好ましい。乾燥工程は、大気圧下で行ってもよく、減圧下で行ってもよい。当該乾燥によって、上述の固体状(粉体状)のフッ化ビニリデン共重合体組成物が得られる。また、水性媒体を除去するための装置は特に制限されず、棚段式乾燥器、コニカルドライヤー、流動層乾燥器、気流乾燥器、噴霧乾燥器、凍結乾燥機等を用いることができる。
フッ化ビニリデン共重合体組成物の製造方法の第2の方法では、水性媒体中に未処理フッ化ビニリデン共重合体が分散したエマルションを準備する工程(以下、「エマルション準備工程」とも称する)と、当該未処理フッ化ビニリデン共重合体のヒートフローを示差走査熱量計で測定したときに、185℃以下に見られる当該未処理フッ化ビニリデン共重合体の吸熱ピークのうち最も高温のピークのエンドセットより低い温度で前記エマルションを加熱する工程(以下、「加熱工程」とも称する)と、を少なくとも行う。なお、上記エマルション加熱工程後、エマルションを乾燥させて、フッ化ビニリデン共重合体を取り出す工程(以下、「乾燥工程」とも称する)を行うことで、上述の固体状(粉体状)のフッ化ビニリデン共重合体組成物が得られる。なお、本方法においても、固体状のフッ化ビニリデン共重合体組成物を得た後、フッ化ビニリデン共重合体組成物の融点以上の温度での加熱は行わないものとする。以下、各工程について説明する。
エマルション準備工程では、水性媒体中に未処理フッ化ビニリデン共重合体が分散したエマルションを準備する。当該エマルション準備工程は、上述の第1の方法のエマルション準備工程と同様とすることができる。上述のように、市販のエマルションを使用してもよい。
加熱工程では、エマルション準備工程後に、エマルションを加熱する。上述のエマルション準備工程で重合を行う場合、重合の後、そのまま連続して加熱工程を実施してもよく、重合と加熱工程を分けて実施してもよい。重合で得たエマルションを加熱する場合、重合の後、かつ、加熱工程の前に、少なくとも、未反応のフッ化ビニリデンおよび含フッ素アルキルビニル化合物を系外にパージし、除去することが好ましい。当該作業を行うことで、加熱工程中にフッ化ビニリデン共重合体を形成するための重合反応が再度開始することがない。また未処理フッ化ビニリデン共重合体の結晶性領域の状態を加熱工程で調整しやすくなる。
乾燥工程では、上記エマルションから水性媒体を除去する。水性媒体の除去方法は特に制限されないが、エマルション中のフッ化ビニリデン共重合体組成物の物性等に影響を及ぼさない温度で乾燥させることが好ましい。乾燥工程は、大気圧下で行ってもよく、減圧下で行ってもよい。当該乾燥によって、上述の固体状(粉体状)のフッ化ビニリデン共重合体組成物が得られる。乾燥方法は、第1の方法における乾燥工程と同様とすることができる。
フッ化ビニリデン共重合体組成物の製造方法の第3の方法では、前記第2の方法におけるエマルション準備工程後、加熱工程前にエマルションに界面活性剤を添加(以下、界面活性剤を添加したエマルションを「界面活性剤含有エマルション」とも称する)する工程(以下、「界面活性剤添加工程」とも称する)、を少なくとも行う。つまり、エマルション準備工程、界面活性剤添加工程、および加熱工程の順に行う。なお、上記加熱工程後、エマルションを乾燥させて、フッ化ビニリデン共重合体を取り出す工程(以下、「乾燥工程」とも称する)を行うことで、上述の固体状のフッ化ビニリデン共重合体組成物が得られる。なお、本方法においても、固体状のフッ化ビニリデン共重合体組成物を得た後、フッ化ビニリデン共重合体組成物の融点以上の温度での加熱は行わないものとする。以下、各工程について説明する。
エマルション準備工程では、水性媒体中に未処理フッ化ビニリデン共重合体が分散したエマルションを準備する。当該エマルション準備工程は、上述の第1の方法のエマルション準備工程と同様とすることができる。
界面活性剤添加工程では、上述のエマルション準備工程で準備したエマルションに界面活性剤を添加し、界面活性剤含有エマルションを調製する。また、エマルション準備工程で重合を行う場合、界面活性剤の添加前、または添加後、もしくは添加中にエマルション(もしくは界面活性剤含有エマルション)の冷却を行ってもよい。
加熱工程では、上述の界面活性剤添加工程で得られた界面活性剤含有エマルションを加熱する。当該加熱工程は、上述の第2の方法の加熱工程と同様とすることができる。
乾燥工程では、上記界面活性剤含有エマルションから水性媒体を除去する。乾燥方法は、第1の方法における乾燥工程と同様とすることができる。
上述のフッ化ビニリデン共重合体組成物は、上述のフッ化ビニリデン共重合体組成物と、分散媒と、を混合したポリマー分散液の形態で、後述の電極層を形成するための電極合剤あるいは電解質層を形成するための電解質合剤に用いることができる。
脱水処理が容易であるという観点から、酪酸ブチルが好ましい。
上述のポリマー分散液は、各種非水電解質二次電池等の電極の電極層の形成に使用できる。非水電解質二次電池の電極は、例えば、集電体と、当該集電体上に配置された電極層とを含む。このとき、電極層の形成に、上述のポリマー分散液を用いることができる。なお、当該電極は、正極用であってもよく、負極用であってもよい。
負極および正極用の集電体は、電気を取り出すための端子である。集電体の材質としては、特に限定されるものではなく、アルミニウム、銅、鉄、ステンレス鋼、鋼、ニッケル、チタン等の金属箔あるいは金属網等を用いることができる。また、他の媒体の表面に上記金属箔あるいは金属網等を施したものであってもよい。
電極層は、上述のフッ化ビニリデン共重合体組成物もしくはポリマー分散液と、活物質と、必要に応じて分散媒と、を混合して、電極合剤を調製し、当該電極合剤を集電体上に塗布し、乾燥させた層とすることができる。電極層は、上記集電体の一方の面のみに形成されていてもよく、両方の面に配置されていてもよい。電極合剤中の分散媒は、上述のポリマー分散液で説明したものと同様である。
上記電極層は、上述のフッ化ビニリデン共重合体組成物もしくはポリマー分散液と、活物質と、必要に応じて固体電解質、分散媒、溶媒、導電助剤や各種添加剤等とを混合した電極合剤を調製する工程と、当該電極合剤を集電体上に塗布する工程と、これを乾燥させる工程と、を行うことで形成できる。
上述のフッ化ビニリデン共重合体組成物もしくはポリマー分散液は、例えば非水電解質二次電池用電解質層の製造にも使用できる。非水電解質二次電池用電解質層(以下、単に「電解質層」とも称する)は、例えば、電解質層のみを含んでいてもよい。上述のポリマー分散液(フッ化ビニリデン共重合体)は、当該電解質層の材料として用いることができる。
上述のフッ化ビニリデン共重合体組成物もしくはポリマー分散液は、上述のように、全固体電池を含む各種非水電解質二次電池等の電極や、電解質層に使用可能であるが、非水電解質二次電池の他の層の形成に使用してもよい。
(1)エマルション1の調製
オートクレーブにイオン交換水280質量部を入れ、30分間の窒素バブリングによって脱気を行った。次に、リン酸水素二ナトリウム0.2質量部、およびパーフルオロオクタン酸アンモニウム塩(PFOA)1.0質量部を仕込み、4.5MPaまで加圧して窒素置換を3回行った。その後、酢酸エチル0.1質量部、フッ化ビニリデン(VDF)11質量部、ヘキサフルオロプロピレン(HFP)24質量部を上記オートクレーブ中に添加した。撹拌しながら80℃まで昇温させた。そして、5質量%過硫酸アンモニウム(APS)水溶液を、APS量が0.06質量部となるように添加し、重合を開始させた。缶内圧力が2.5MPaで維持されるように重合開始直後にVDF65質量部を連続的に添加した。添加終了後、1.5MPaまで圧力が降下したところで重合を完了とし、40℃以下に冷却した後、残留モノマーをオートクレーブからパージして除去し、未処理フッ化ビニリデン共重合体が水に分散されたエマルション1を得た。当該エマルション1の固形分濃度(フッ化ビニリデン共重合体の濃度)は21.0質量%であった。また、凍結乾燥によって未処理フッ化ビニリデン共重合体を取り出し、後述の方法に基づき当該フッ化ビニリデン共重合体の185℃以下にみられる吸熱ピークのエンドセットを測定したところ、132℃であった。
まず、エマルションを凍結乾燥し、粉体状のフッ化ビニリデン共重合体を得た。次に、剥離剤を噴霧した2枚のアルミ箔の間に、縦5cm×横5cm×厚み150μmの鋳型と、粉体状のフッ化ビニリデン共重合体約1gとを挟み、200℃でプレスしてフィルムを作製した。そして、示差走査熱量計(METTLER社製「DSC-1」)を用いてASTM D3418に準拠して測定し、フッ化ビニリデン共重合体のヒートフローを得た。得られたヒートフローにおいて、185℃以下にみられるフッ化ビニリデン共重合体の吸熱ピークのうち、最も高温のピークトップよりも高温側の温度域で直線状のヒートフローと重なるようにベースラインを直線状に引いた。そして、185℃以下にみられるフッ化ビニリデン共重合体の吸熱ピークのうち、最も高温のピークトップより高温側の温度域で、かつ、ヒートフローとベースラインとが重なる温度の最小温度より低温側の温度域において、ヒートフローに接線を引き、その接線とベースラインとの交点を、フッ化ビニリデン共重合体のエンドセットとした。
重合開始前に、オートクレーブ中に一括添加するVDFの量を11質量部から15質量部に変更し、HFPの量を24質量部から20質量部に変更した以外はエマルション1の調製と同様に重合し、未処理フッ化ビニリデン共重合体が水に分散されたエマルション2を得た。当該エマルション2の固形分濃度(フッ化ビニリデン共重合体の濃度)は20.8質量%であった。また、エマルション1と同様の方法で特定した当該未処理フッ化ビニリデン共重合体の185℃以下にみられるフッ化ビニリデン共重合体の吸熱ピークのうち最も高温のピークのエンドセットは、134℃であった。
重合開始前に、オートクレーブ中に一括添加するVDFの量を11質量部から25質量部に変更し、HFPの量を24質量部から10質量部に変更した以外はエマルション1の調製と同様に重合し、未処理フッ化ビニリデン共重合体が水に分散されたエマルション3を得た。当該エマルション3の固形分濃度(フッ化ビニリデン共重合体の濃度)は21.3質量%であった。またエマルション1と同様の方法で特定した未処理フッ化ビニリデン共重合体の吸熱ピークのうち最も高温のピークのエンドセットは、152℃であった。
オートクレーブにエマルション1を入れ、さらにエマルション中の水に対するドデシル硫酸ナトリウム(SDS)の濃度が1質量%となるようにSDSを入れて界面活性剤含有エマルションを得た。このとき、界面活性剤含有エマルションの25℃における表面張力を測定した。結果を表1に示す。
エマルション1中の水に対するSDSの濃度を1質量%から0.5質量%に変更した以外は実施例1と同様に熱処理および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は141μmであった。
エマルション1に添加する界面活性剤をSDSからエマルゲンLS-110(花王社製、ポリオキシアルキレンアルキルエーテル)に変更した以外は実施例2と同様に熱処理および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は197μmであった。
エマルション1に添加する界面活性剤をSDSからPFOA(ペルフルオロオクタン酸)に変更した以外は実施例2と同様に熱処理および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は163μmであった。
エマルション1の加熱温度を125℃から95℃に変更した以外は実施例2と同様に熱処理および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は391μmであった。
エマルション1の加熱温度を125℃から75℃に変更した以外は実施例2と同様に熱処理および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は364μmであった。
エマルション1中の水に対するSDSの濃度を0.5質量%から0質量%に変更した以外は実施例2と同様に熱処理および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は173μmであった。
エマルション1中の水に対するSDSの濃度を0.5質量%から0質量%に変更した以外は実施例6と同様に熱処理および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は424μmであった。
オートクレーブに入れるエマルションをエマルション1からエマルション2に変更し、界面活性剤を添加した後のエマルション(界面活性剤含有エマルション)の加熱温度を125℃から130℃に変更した以外は実施例2と同様に熱処理および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は52μmであった。
オートクレーブにエマルション1を入れ、さらにエマルション中の水に対するPFOAの濃度が0.5質量%となるようにPFOAを入れた。そして、室温(24℃)下、500rpmで攪拌することでエマルションにPFOAを溶解させた。当該エマルションを凍結乾燥し、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は160μmであった。
オートクレーブにエマルション1を入れ、さらにエマルション中の水に対するSDSの濃度が1質量%となるようにSDSを入れ、室温(24℃)下、500rpmで攪拌することでエマルションにSDSを溶解させた。当該エマルションを凍結乾燥し、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は148μmであった。
エマルション中の水に対するSDSの濃度を1質量%から0.5質量%に変更した以外は実施例11と同様に溶解および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は126μmであった。
エマルション中の水に対するPFOAの濃度を0.5質量%から1質量%に変更した以外は実施例10と同様に溶解および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は219μmであった。
エマルション中の水に対するPFOAの濃度を0.5質量%から0.1質量%に変更した以外は実施例10と同様に溶解および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は178μmであった。
オートクレーブにエマルション1を入れ、さらにエマルション中の水に対するアセタミン86の濃度が0.05質量%となるようにアセタミン86(花王社製、ステアリルアミンアセテート)を入れ、室温(24℃)下、500rpmで攪拌することでエマルションにアセタミン86を溶解させた。当該エマルションを凍結乾燥し、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は821μmであった。
エマルション1を凍結乾燥し、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は215μmであった。
実施例11で得られた粉体状のフッ化ビニリデン共重合体組成物を125℃、1時間熱処理することで、粉体状のフッ化ビニリデン共重合体組成物を得た。当該フッ化ビニリデン共重合体組成物は凝集が激しいため、平均二次粒子径は測定不可であった。
比較例1で得られた粉体状のフッ化ビニリデン共重合体組成物を125℃、1時間熱処理することで、粉体状のフッ化ビニリデン共重合体組成物を得た。当該フッ化ビニリデン共重合体組成物は凝集が激しいため、平均二次粒子径は測定不可であった。
エマルションに入れる界面活性剤をPFOAからエマルゲンLS-110に変更した以外は実施例10と同様に溶解および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は127μmであった。
オートクレーブに入れるエマルションをエマルション1からエマルション3に変更し、エマルションの加熱温度を125℃から150℃に変更した以外は実施例2と同様に熱処理および凍結乾燥を行い、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は39μmであった。
比較例1で得られた粉体状のフッ化ビニリデン共重合体組成物に、凍結乾燥前のエマルション中の水に対して、1質量%となる量のドデシル硫酸ナトリウム(SDS)を入れ、粉体状のフッ化ビニリデン共重合体組成物を得た。当該粉体状のフッ化ビニリデン共重合体組成物の平均二次粒子径は215μmであった。
エマルション1の加熱温度を125℃から180℃に変更した以外は実施例2と同様に熱処理を行った。当該加熱工程によって、分散安定性のあるエマルションとして回収できなかったため、粉体状のフッ化ビニリデン共重合体組成物を得られなかった。
エマルション1の加熱温度を125℃から180℃に変更した以外は実施例7と同様に熱処理を行った。当該加熱工程によって分散安定性のあるエマルションとして回収できなかったため、粉体状のフッ化ビニリデン共重合体組成物を得られなかった。
上記フッ化ビニリデン共重合体組成物や、エマルション等の物性は、それぞれ、以下のように測定した。
得られたエマルション約5gをアルミ製のカップに入れ、80℃で3時間乾燥させた。そして、乾燥前後の重量を測定することで、エマルション中のフッ化ビニリデン共重合体の濃度(固形分濃度)を算出した。
フッ化ビニリデン共重合体組成物の平均二次粒子径は、粉体状のフッ化ビニリデン共重合体組成物について、レーザー回折・散乱法にて体積基準で測定し、その粒度分布の累積平均径(D50)を算出した。具体的には、マイクロトラック・ベル社製 Microtrac MT3300EXIIを使用し、粉体状のフッ化ビニリデン共重合体組成物約0.5mgを撹拌によって水中に分散させ、測定用試料とした。測定媒体は水とし、媒体屈折率は1.333、粒子形状は非球形、粒子屈折率は1.42、測定時間30秒とし、透過モードで5回測定した時のD50の平均値を平均二次粒子径とした。
フッ化ビニリデン共重合体組成物の融点は、以下の方法で作製されるフィルムの形態で測定した。まず、剥離剤を噴霧した2枚のアルミ箔の間に、縦5cm×横5cm×厚み150μmの鋳型と、粉体状のフッ化ビニリデン共重合体組成物約1gとを挟み、200℃でプレスし、プレスフィルムを得た。そして、示差走査熱量計(METTLER社製「DSC-1」)を用いてASTM D3418に準拠して融点を測定した。
フッ化ビニリデン共重合体組成物のリバーシングヒートフロー(RHF)のピークトップおよび融解エンタルピーは、温度変調示差走査熱量計(Q-100、TAインスツルメンツ社製)を用いて測定した。具体的には、凍結乾燥により粉体化したフッ化ビニリデン共重合体組成物約5mgをアルミニウムパンに詰め、測定用サンプルとした。測定条件はヒートオンリー条件となるように、平均昇温速度5℃/min、モジュレイション周期40秒、モジュレイション振幅±0.531℃とした。得られたリバーシングヒートフローは下に凸の吸熱ピークを有していた。得られたリバーシングヒートフローにおいて、エンドセットより高温側の直線状のヒートフローと重なるようにベースラインを直線状に引いた。そして、リバーシングヒートフローの下に凸な吸熱ピークのうち、当該ベースラインからリバーシングヒートフローに向けて、垂直に線を引いたとき、リバーシングヒートフロー上であって、当該ベースラインから最も距離が遠い点を吸熱ピークのピークトップとし、当該ピークトップの温度を特定した。また、リバーシングヒートフローの下に凸な吸熱ピークの極小値の数を吸熱ピークのピークトップの数とした。一方で、当該ベースラインとリバーシングヒートフローとに囲まれた領域を融解エンタルピー量(ΔHm)とした。
エマルション(エマルションに界面活性剤を添加する場合は、エマルションに界面活性剤を添加した後のエマルション)の表面張力はWilhelmy法を用いて表面張力計(Sigma701/700、KSV instruments社製)によって測定した。測定には白金プレートを使用し、25℃における表面張力を3回測定したときの平均値を表面張力の値とした。
まず、粉体状のフッ化ビニリデン共重合体組成物2gを18gの酪酸ブチルに添加し、25℃のスターラー上で30分撹拌し、フッ化ビニリデン共重合体組成物の酪酸ブチル分散液(フッ化ビニリデン共重合体組成物の含有率10質量%)を調製した。当該分散液20mLを20mLメスシリンダーに入れ、パラフィルムで蓋をして20時間静置した。メスシリンダーの上澄みから4mLをピペットで採取し、アルミカップに入れ、135℃、1時間乾燥させ、これをデシケータ内で1時間放冷した。そして、乾燥前後の重量を測定することで、フッ化ビニリデン共重合体組成物の酪酸ブチル分散液の上澄みのフッ化ビニリデン共重合体組成物の含有率を特定した。
フッ化ビニリデン共重合体組成物を酪酸ブチルに分散させた分散液の濁度は、以下の方法で測定した。まず、粉体状のフッ化ビニリデン共重合体組成物2gを18gの酪酸ブチルに添加し、25℃のスターラー上で30分撹拌し、フッ化ビニリデン共重合体組成物の酪酸ブチル分散液(フッ化ビニリデン共重合体組成物の含有率10質量%)を調製した。そして、当該サンプルを20時間静置した後再攪拌した当該分散液の濁度を、日本電色工業製のNDH2000(JIS K 7136に準拠)で測定した。なお、サンプルは石英セルに入れた。また、酪酸ブチルの濁度を0%とし、サンプルの濁度を算出した。
Claims (13)
- フッ化ビニリデン共重合体を含むフッ化ビニリデン共重合体組成物であって、
前記フッ化ビニリデン共重合体は、フッ化ビニリデン由来の構成単位と、含フッ素アルキルビニル化合物由来の構成単位とを含み、
前記フッ化ビニリデン共重合体組成物の融点が140℃以下であり、
前記フッ化ビニリデン共重合体組成物は、前記フッ化ビニリデン共重合体組成物のリバーシングヒートフローを温度変調示差走査熱量計で測定したとき、融解エンタルピー量(ΔHm)が2J/g以上である吸熱ピークを有し、
前記吸熱ピークのうち最も大きい吸熱ピークのピークトップ温度と、前記フッ化ビニリデン共重合体組成物の前記融点との差の絶対値が10℃以下であり、
酪酸ブチルと前記フッ化ビニリデン共重合体組成物とを含み、かつ前記フッ化ビニリデン共重合体組成物の含有率が10質量%である分散液を、25℃で30分間攪拌し、20時間静置した後の、前記分散液の上部20体積%における前記フッ化ビニリデン共重合体組成物の含有率が、4.0質量%以上10質量%以下である、
フッ化ビニリデン共重合体組成物。 - 前記フッ化ビニリデン共重合体組成物は、前記リバーシングヒートフローを測定したとき、融解エンタルピー量(ΔHm)が2J/g以上で、かつ、ピークトップを2つ以上有する吸熱ピークを有し、
前記分散液を25℃で30分攪拌し、20時間静置した後の前記分散液の上部20体積%における前記フッ化ビニリデン共重合体組成物の含有率が7.0質量%以上10質量%以下である、
請求項1に記載のフッ化ビニリデン共重合体組成物。 - 前記含フッ素アルキルビニル化合物が、ヘキサフルオロプロピレンである、
請求項1または2に記載のフッ化ビニリデン共重合体組成物。 - 前記フッ化ビニリデン共重合体の構成単位100質量%に対して、前記ヘキサフルオロプロピレン由来の構成単位を15質量%以上70質量%以下含む、
請求項3に記載のフッ化ビニリデン共重合体組成物。 - 界面活性剤をさらに含む、
請求項1~4のいずれか一項に記載のフッ化ビニリデン共重合体組成物。 - 前記界面活性剤が、アニオン性界面活性剤を含む、
請求項5に記載のフッ化ビニリデン共重合体組成物。 - 請求項1~6のいずれか一項に記載のフッ化ビニリデン共重合体組成物と、
比誘電率が15以下である分散媒と、
を含む、ポリマー分散液。 - 請求項1~6のいずれか一項に記載のフッ化ビニリデン共重合体組成物を含む、
非水電解質二次電池用電極。 - 請求項1~6のいずれか一項に記載のフッ化ビニリデン共重合体組成物を含む、
非水電解質二次電池用電解質層。 - 請求項1~6のいずれか一項に記載のフッ化ビニリデン共重合体組成物を含む、
非水電解質二次電池。 - フッ化ビニリデン由来の構成単位と、含フッ素アルキルビニル化合物由来の構成単位とを含むフッ化ビニリデン共重合体を含有するフッ化ビニリデン共重合体組成物の製造方法であって、
水性媒体中に未処理フッ化ビニリデン共重合体が分散したエマルションを準備する工程と、
前記エマルションにイオン性界面活性剤を添加して攪拌し、25℃における表面張力が40mN/m以下の界面活性剤含有エマルションを得る工程と、を含み、
前記フッ化ビニリデン共重合体組成物の融点が140℃以下である、
フッ化ビニリデン共重合体組成物の製造方法。 - フッ化ビニリデン由来の構成単位と、含フッ素アルキルビニル化合物由来の構成単位とを含むフッ化ビニリデン共重合体を含有するフッ化ビニリデン共重合体組成物の製造方法であって、
水性媒体中に未処理フッ化ビニリデン共重合体が分散したエマルションを準備する工程と、
前記未処理フッ化ビニリデン共重合体のヒートフローを示差走査熱量計で測定したときに、185℃以下にみられる吸熱ピークのうち最も高温のピークのエンドセットより低い温度、かつ、40℃以上の温度で前記エマルションを加熱する工程と、を含み、
前記フッ化ビニリデン共重合体組成物の融点が140℃以下である、
フッ化ビニリデン共重合体組成物の製造方法。 - 前記エマルションを準備する工程後、かつ前記エマルションを加熱する工程前において、
前記エマルションに界面活性剤を添加する工程をさらに含む、
請求項12に記載のフッ化ビニリデン共重合体組成物の製造方法。
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