WO2017175838A1 - 電気化学素子用バインダー - Google Patents
電気化学素子用バインダー Download PDFInfo
- Publication number
- WO2017175838A1 WO2017175838A1 PCT/JP2017/014406 JP2017014406W WO2017175838A1 WO 2017175838 A1 WO2017175838 A1 WO 2017175838A1 JP 2017014406 W JP2017014406 W JP 2017014406W WO 2017175838 A1 WO2017175838 A1 WO 2017175838A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- binder
- polymer
- lithium ion
- ion battery
- composition
- Prior art date
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- 239000011230 binding agent Substances 0.000 title claims abstract description 137
- 229920000642 polymer Polymers 0.000 claims abstract description 99
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 45
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- 229910001416 lithium ion Inorganic materials 0.000 claims description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 52
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- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
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- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 4
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/10—Alpha-amino-carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/04—Polyamides derived from alpha-amino carboxylic acids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a binder for an electrochemical element.
- Secondary batteries are batteries that can be repeatedly charged and discharged, and are being used not only in electronic devices such as mobile phones and laptop computers, but also in fields such as automobiles and aircraft. In response to the increasing demand for such secondary batteries, research is being actively conducted. In particular, light-weight, small, and high-energy density lithium ion batteries among secondary batteries are attracting attention from various industries, and are actively developed.
- a lithium ion battery is mainly composed of a positive electrode, an electrolyte, a negative electrode, and a separator.
- an electrode in which an electrode composition is applied on a current collector is used.
- the positive electrode composition used for forming the positive electrode mainly includes a positive electrode active material, a conductive additive, a binder, and a solvent.
- the binder polyvinylidene fluoride (PVDF), the solvent N-methyl-2-pyrrolidone (NMP) is generally used. This is because PVDF is chemically and electrically stable and NMP is a time-stable solvent that dissolves PVDF.
- Patent Document 1 an emulsion of polyamideimide and a fluororesin is used to replace the solvent at the time of electrode preparation from NMP to water.
- emulsions have room for improvement in dispersibility and stability over time.
- Polyamideimide is used as a water-soluble polymer, but aromatic compounds such as 4,4'-diaminodiphenyl ether are listed as constituent elements, and there still remains a problem in oxidation resistance.
- Patent Document 2 discloses improving the cycle characteristics of Si or an alloy-based negative electrode by forming poly- ⁇ -glutamate lithium or the like as a coating on the negative electrode, or by adding the negative electrode as an additive.
- NMP which has a large environmental load, is used in the production of a negative electrode containing lithium polyglutamate.
- the present invention provides a binder for an electrochemical device having high oxidation resistance, low environmental burden, and low production cost.
- the following binders for electrochemical devices and the like are provided.
- an electrochemical device comprising a polymer having a carboxyl group and / or a salt thereof and a polymer having an amide group and / or an amide bond, or a polymer having a carboxyl group and / or a salt thereof and an amide group and / or an amide bond binder.
- the binder for electrochemical elements of 1 containing water.
- the polymer having a carboxyl group and / or a salt thereof, and an amide group and / or an amide bond is a polymer containing 60% or more of a repeating unit represented by the following formula (1) or the following formula (2).
- x is an integer of 0 to 5
- y is an integer of 1 to 7
- z is an integer of 0 to 5.
- X is a hydrogen ion or a metal ion.
- R 1 is a hydrogen atom or a functional group having 10 or less carbon atoms.
- x is an integer of 1-12.
- R 2 is a functional group containing a carboxyl group or a carboxylate group having 10 or less carbon atoms. ) 4).
- one or more amino acids selected from a neutralized product of glutamic acid and a neutralized product of aspartic acid are ⁇ -position, ⁇ -position, or 8.
- Mw, PEG conversion weight average molecular weight
- 12 A lithium ion battery electrode composition comprising the lithium ion battery electrode binder according to 11. 13.
- 14 A binder for a composition for a lithium ion battery separator, comprising the binder for an electrochemical element according to any one of 1 to 10. 15.
- 15. A lithium ion battery separator using the lithium ion battery separator composition described in 15. 17.
- a binder for a protective film for a lithium ion battery electrode comprising the binder for an electrochemical element according to any one of 1 to 10. 18.
- 20. A lithium ion battery using the binder for electrochemical devices according to any one of 1 to 10. 21.
- 20. An electric device comprising the lithium ion battery according to 20. 22.
- a vehicle comprising the lithium ion battery according to 20.
- 23. A binder for an electric double layer capacitor comprising the binder for an electrochemical element according to any one of 1 to 10.
- 24. The composition for electric double layer capacitor electrodes containing the binder for electric double layer capacitors described in 23. 25.
- 26. An electric double layer capacitor comprising the electric double layer capacitor electrode described in 25. 27. 26.
- a vehicle using the electric double layer capacitor described in 26.
- the binder for an electrochemical device of the present invention includes a polymer having a carboxyl group and / or a salt thereof, a polymer having an amide group and / or an amide bond, or a carboxyl group and / or a salt thereof, and an amide group and / or an amide bond.
- the “electrochemical element” means a secondary battery such as a lithium ion battery and a capacitor.
- the polymer of the present invention a polymer having a carboxyl group and / or a salt thereof, a polymer having an amide group and / or an amide bond.
- the binder of the present invention is usually a binder containing a solvent, preferably containing water as the solvent.
- a solvent preferably containing water as the solvent.
- the binder of the present invention is a water-based binder containing a large amount of water, the environmental burden can be reduced and the solvent recovery cost can also be reduced.
- the solvent other than water that can be contained in the binder include alcohol solvents such as ethanol and 2-propanol, acetone, NMP, and ethylene glycol.
- solvents other than water are not limited to these.
- the polymer of the present invention has a carboxyl group and / or a salt thereof in a repeating unit.
- the unit having a carboxyl group and / or a salt thereof in the polymer is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more of the repeating unit of the polymer.
- a polymer having a carboxyl group and / or a salt thereof has a high polarity and can realize a good binding property with a metal foil, an active material and a conductive additive, and has a dispersing function and a thickening function.
- a composition containing a polymer having a carboxyl group and / or a salt thereof as a binder can exhibit good coating properties.
- the neutralization degree of the carboxyl group in the polymer is preferably 50% or more, 60% or more is more preferable, and 70% or more is more preferable. If the degree of neutralization of the carboxyl group site is 50% or more, the pH will not drop too much, and corrosion of the active material and the aluminum current collector can be prevented. Further, by improving the degree of neutralization, the solubility of the polymer in water can be improved, and the reduction of the swelling property in the electrolytic solution can be expected. There is no upper limit to the degree of neutralization, but it is not preferred that an excess of base is present.
- the neutralization degree of the carboxyl group site can be calculated by confirming the element ratio by, for example, neutralization titration or elemental analysis (CHN coder method and ICP spectroscopic analysis method).
- the salt that neutralizes the carboxyl group site of the polymer is preferably an alkali metal ion or alkaline earth metal ion, more preferably an alkali metal ion, and particularly preferably a Na ion or Li ion. If the salt to be neutralized is Na, the polymer can be produced at a particularly low cost, and if the salt to be neutralized is Li, the charge transfer resistance between the electrolyte and the active material can be reduced and the lithium conductivity in the electrode can be improved. We can expect to contribute.
- a binder containing a polymer having a carboxyl group and / or a salt thereof can be used as a positive electrode active material when the binder is used in a positive electrode composition for a lithium ion battery, for example, by suppressing an excessive increase in pH.
- the polymer contained in the binder of the present invention has an amide group and / or an amide bond in a repeating unit.
- the unit having an amide group and / or an amide bond site in the polymer is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more of the repeating unit of the polymer. If the unit having an amide group and / or an amide bond site is 30% or more, the amide group site in the polymer forms a hydrogen bond, suppresses dissolution in the electrolyte, and forms a network by hydrogen bond. Therefore, it can be expected to hold the active material strongly.
- the polymer of the present invention includes both a carboxyl group and / or a salt thereof and a polymer containing an amide group and / or an amide bond, both a carboxyl group and / or a salt thereof, and an amide group and / or an amide bond.
- One type of polymer having In the case of the polymer having both the carboxyl group and the amide bond, hydrogen bonds are generated at a plurality of points in the molecule and between the molecules, and strong binding can be expected, and the solubility in water is improved by improving the hydrophilicity. It can improve and can reduce the swelling property to electrolyte solution.
- the polymer which has both the said carboxyl group and an amide bond may be 2 or more types from which a structure mutually differs.
- the polymer having a carboxyl group and / or a salt thereof and an amide group and / or an amide bond preferably has an amide group site and / or an amide bond in the main chain, and a carboxyl group and / or a carboxylate in the side chain. It is a polymer which has a base part, More preferably, it is a polymer containing 60% or more of repeating units represented by the following formula (1) or the following formula (2). (In the formula (1), x is an integer of 0 to 5, y is an integer of 1 to 7, and z is an integer of 0 to 5.
- X is a hydrogen ion or a metal ion.
- R 1 is a hydrogen atom or an aliphatic hydrocarbon group having 10 or less carbon atoms. n is the number of repetitions.
- x is an integer of 1-12.
- R 2 is an aliphatic hydrocarbon group containing a carboxyl group or a carboxylate group having 10 or less carbon atoms. n is the number of repetitions.
- x, y and z are preferably x is an integer of 0 or more and 3 or less, y is an integer of 1 or more and 4 or less, z is an integer of 0 or more and 3 or less, more preferably x is An integer from 0 to 1, y is an integer from 1 to 2, and z is an integer from 0 to 1. If the numerical values of x, y, and z are within the above ranges, the aliphatic skeleton can exhibit flexibility, the flexibility of the resulting electrode is maintained, and the aliphatic skeleton that is a hydrophobic site is a hydrophilic site.
- X is a hydrogen ion or a metal ion.
- the metal ions are preferably alkali metal ions or alkaline earth metal ions, and more preferably Li ions or Na ions.
- a part of X may be an aliphatic hydrocarbon group, which means that a part of X is esterified.
- the content of the esterified unit structure is preferably 70% or less, more preferably 50% or less, and particularly preferably 30% or less. If it is 70% or less of the whole, the water solubility of the polymer will be sufficient.
- ester examples include, but are not limited to, methyl esters and ethyl esters in which X is a methyl group or an ethyl group.
- R 1 is a hydrogen atom or a functional group having 10 or less carbon atoms.
- the functional group includes an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, and the like.
- Examples of the functional group having 10 or less carbon atoms include a methyl group, an ethyl group, a linear or branched butyl group, a pentyl group, and a methoxymethyl group.
- the carbon number of the functional group is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less.
- a functional group which forms hydrogen bonds such as a hydroxyl group
- the carbon number is 10 or less, solubility in water can be ensured.
- functional groups such as hydroxyl groups improve water solubility.
- x is preferably an integer of 3 to 10, more preferably x is an integer of 4 to 9. If the value of x is within this range, the aliphatic skeleton can exhibit flexibility, the flexibility of the resulting electrode is maintained, and the amide group site where the aliphatic skeleton that is a hydrophobic site is a hydrophilic site and The solubility in water can be ensured sufficiently with respect to the carboxyl group or carboxylate group site.
- R 2 is an aliphatic hydrocarbon group containing a carboxyl group having 10 or less carbon atoms or a carboxylate group having 10 or less carbon atoms.
- Examples of the carboxyl group having 10 or less carbon atoms include a substituent in which a carboxyl group is bonded to an alkyl group having 1 to 9 carbon atoms.
- the salt of a carboxylate group having 10 or less carbon atoms is preferably a metal ion, more preferably an alkali metal ion or an alkaline earth metal ion, and even more preferably a Li ion or a Na ion.
- the carbon number of the functional group is preferably 10 or less, more preferably 7 or less, and particularly preferably 5 or less. If the carbon number of the functional group is 10 or less, sufficient water solubility can be obtained. Moreover, a part of carboxyl group may be esterified.
- the content of the esterified unit structure is preferably 70% or less, more preferably 50% or less, and particularly preferably 30% or less. If it is 70% or less of the whole, the water solubility of the polymer will be sufficient.
- esters include, but are not limited to, methyl esters and ethyl esters.
- the proportion of the repeating unit represented by the formula (1) or (2) is preferably 80% or more. More preferably, it is 90% or more.
- the ratio of the repeating unit represented by the formula (1) or (2) is most preferably 100%, and all the repeating units of the polymer of the present invention are preferably the formula (1) or (2). If the polymer contains 60% or more of the repeating unit represented by the formula (1) or (2), electrochemical stability and physical properties suitable for an electrochemical device can be provided.
- the number of repeating units containing an aromatic hydrocarbon group is preferably 20% or less, more preferably 15% or less, and particularly preferably 10% or less.
- the fewer the aromatic hydrocarbon group sites contained in the polymer the less the change in molecular weight due to oxidative degradation of the polymer due to the oxidation of the aromatic hydrocarbon group and the possibility of gas generation.
- the polymer of the present invention is preferably a polyamino acid. More preferably, the polymer includes a structure in which one or more amino acids selected from the group consisting of a neutralized product of glutamic acid and a neutralized product of aspartic acid are polymerized at the ⁇ -position, ⁇ -position, or ⁇ -position. These polymers are polymers obtained by utilizing naturally occurring amino acids and have high environmental harmony.
- the neutralized product is preferably a neutralized product of metal ions, more preferably a neutralized product of alkali metal ions or alkaline earth metal ions, and more preferably a neutralized product of Li ions or Na ions.
- the polymer of the present invention is preferably ⁇ -polyglutamic acid, more preferably an atactic polymer in which L-form glutamic acid and D-form glutamic acid coexist. Since an atactic polymer has low crystallinity and high flexibility, it is difficult to cause cracks when formed into an electrode, and a good electrode sheet can be constructed.
- the weight average molecular weight (Mw, PEG conversion) of the polymer of the present invention is preferably 50,000 or more and 9,000,000 or less, more preferably 80,000 or more and 7,000,000 or less, and 100,000 More preferably, it is 6,000,000 or less. If the molecular weight of the polymer is 50,000 or more, it is difficult to elute into the electrolyte solution, and a binding action due to the entanglement of molecular chains can be obtained, so that it can be expected that the binding property is also improved. When the molecular weight of the polymer is 9,000,000 or less, solubility of the polymer in water can be obtained, and an electrode composition having a viscosity that can be applied can be prepared.
- the weight average molecular weight of the polymer can be measured by gel permeation chromatography.
- two TSKgel GMPWXL made by Tosoh are used in the column, and 0.2M NaNO 3 aq.
- RI-1530 manufactured by JASCO Corporation as a differential refractive index (RI) detector
- RI differential refractive index
- a TSKgel std PEO manufactured by Tosoh and a PEG manufactured by Agilent are used as standard samples, and a third calibration curve is drawn and measured in PEG conversion.
- the sample concentration is preferably about 0.3% by weight (hereinafter referred to as wt%).
- the polymer of the present invention can be used after being crosslinked when used as a binder.
- crosslinking include, but are not limited to, crosslinking by addition of a polyvalent metal ion, chemical crosslinking by adding a substance having a site that reacts with a carboxylic acid site such as carbodiimide, and electron beam crosslinking.
- the binder of the present invention contains the polymer of the present invention, and the content of the polymer is preferably 10 wt% or more, more preferably 30 wt% or more, and particularly preferably 50% wt or more. If the polymer content is 10 wt% or more, good binding properties of the binder can be expected.
- the binder of the present invention may be composed of the polymer of the present invention, other components and a solvent, or may be composed of only the polymer and solvent of the present invention. Other components include emulsions, dispersants, and other water-soluble polymers.
- the emulsion contained in the binder of the present invention is not particularly limited, but non-fluorine polymers such as (meth) acrylic polymers, nitrile polymers, and diene polymers; fluorine polymers (fluorine such as PVDF and PTFE (polytetrafluoroethylene)) Containing polymer); and the like.
- the emulsion is preferably excellent in binding properties and flexibility (film flexibility) between particles. From this viewpoint, (meth) acrylic polymers, nitrile polymers, and (meth) acryl-modified fluoropolymers are exemplified.
- the dispersant contained in the binder of the present invention is not particularly limited, and is an anionic, nonionic or cationic surfactant, or a copolymer of styrene and maleic acid (including a half ester copolymer-ammonium salt).
- Various dispersing agents such as a polymer dispersing agent such as can be used.
- the binder contains a dispersant, it is preferably contained in an amount of 5 to 20 wt% with respect to 100 wt% of the conductive aid described later.
- the conductive auxiliary agent can be made sufficiently fine and the dispersibility when the active material is mixed can be sufficiently secured.
- water-soluble polymers contained in the binder of the present invention include polyoxyalkylene, water-soluble cellulose, polyacrylic acid and neutralized products thereof.
- the pH of the binder of the present invention is preferably 4.0 or more, more preferably 5.0 or more. On the other hand, the pH of the binder preferably does not exceed 9.0.
- the pH of the binder can be confirmed by measuring a 1 wt% aqueous solution of the binder at 25 ° C. with a glass electrode type hydrogen ion meter TES-1380 (product name, manufactured by Custom).
- a polymer contained in the binder and a conductive additive described later are mixed at a mass ratio of 1: 1, and 4.8 V in the electrolytic solution is obtained. s.
- the current value when oxidized with Li + / Li is preferably 0.045 mA / mg or less, more preferably 0.03 mA / mg or less, and further preferably 0.02 mA / mg or less.
- the oxidation current at 4.8 V of the binder is 0.045 mA / mg or less, deterioration in long-term use can be suppressed even if it is used as a high-voltage material, and a normal 4 V class positive electrode composition (layered lithium composite oxidation) In the case of a product, deterioration at a high temperature can be suppressed.
- the current value can be measured by the method described in the examples.
- the binder of this invention can be used suitably as a binder of the electrode composition which forms the electrode of a secondary battery.
- the binder of the present invention can be used for any of a positive electrode composition containing a positive electrode active material and a negative electrode composition containing a negative electrode active material, and can be particularly suitably used for a positive electrode composition.
- the electrode composition containing the binder of the present invention (hereinafter sometimes referred to as the electrode composition of the present invention) contains an active material and a conductive additive in addition to the binder.
- the conductive assistant is used to increase the output of the secondary battery, and includes conductive carbon.
- the conductive carbon include carbon black such as ketjen black and acetylene black; fiber-like carbon; graphite and the like. Among these, ketjen black and acetylene black are preferable.
- Ketjen Black has a hollow shell structure and is easy to form a conductive network. Therefore, compared with the conventional carbon black, equivalent performance can be expressed with an addition amount of about half.
- Acetylene black is preferable because it uses a high-purity acetylene gas, so that there are very few impurities by-produced and surface crystallites are developed.
- Carbon black which is a conductive aid, preferably has an average particle size of 1 ⁇ m or less.
- a conductive additive having an average particle size of 1 ⁇ m or less an electrode having excellent electrical characteristics such as output characteristics can be obtained when the electrode composition of the present invention is used as an electrode.
- the average particle size of the conductive assistant is more preferably 0.01 to 0.8 ⁇ m, and further preferably 0.03 to 0.5 ⁇ m.
- the average particle diameter of the conductive additive can be measured by a dynamic light scattering particle size distribution meter (for example, the conductive additive refractive index is set to 2.0).
- the fibrous carbon preferably has a thickness of 0.8 nm to 500 nm and a length of 1 ⁇ m to 100 ⁇ m. If the thickness is in the range, sufficient strength and dispersibility can be obtained, and if the length is in the range, it is possible to secure a conductive path with a fiber shape.
- the positive electrode active material is preferably an active material that can occlude and release lithium ions. By using such a positive electrode active material, the positive electrode composition becomes suitable as a positive electrode of a lithium ion battery.
- the positive electrode active material include various oxides and sulfides. Specific examples include manganese dioxide (MnO 2 ), lithium manganese composite oxide (for example, LiMn 2 O 4 or LiMnO 2 ), and lithium nickel composite oxide.
- LiNiO 2 lithium cobalt composite oxide
- LiCoO 2 lithium nickel cobalt composite oxide
- LiNi 1-x Co x O 2 lithium-nickel-cobalt-aluminum composite oxide
- LiNi 0.8 Co lithium manganese cobalt composite oxides
- LiMn x Co 1-x O 2 lithium-nickel-cobalt-manganese composite oxide
- polyanionic lithium compounds e.g., LiFePO 4 LiCoPO 4 F, Li 2 MnSiO 4, etc.
- vanadium oxide e.g.
- Li excess type nickel - cobalt - manganese composite oxide e.g., Li x Ni A Co B MnCO 2 solid solution
- lithium cobalt phosphate examples thereof include compounds (for example, LiCoPO 4 ) and lithium nickel manganese composite oxides (for example, LiNi 0.5 Mn 1.5 O 4 ).
- organic materials such as a conductive polymer material and a disulfide-type polymer material, are also mentioned.
- a sulfur compound material such as lithium sulfide is also included.
- lithium manganese composite oxide LiMn 2 O 4
- lithium nickel composite oxide LiNiO 2
- lithium cobalt composite oxide LiCoO 2
- lithium nickel cobalt composite oxide LiNi 0.8 Co 0. 2 O 2
- lithium-nickel-cobalt-aluminum composite oxide LiNi 0.8 Co 0.15 Al 0.05 O 2
- lithium manganese cobalt composite oxide LiMnxCo 1-x O 2
- lithium nickel cobalt Manganese composite oxide for example, LiNi x Mn y Co 1-xy O 2
- Li-rich nickel-cobalt-manganese composite oxide LiNi 0.5 Mn 1.5 O 4 is preferred.
- the positive electrode active material from the viewpoint of the battery voltage, LiMO 2, LiM 2 O 4 , Li 2 MO 3 or Li composite oxide represented by LiMXO 3or4 are preferred.
- M is composed of one or more transition metal elements selected from Ni, Co, Mn and Fe, but besides transition metals, Al, Ga, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc. may be added.
- X is composed of one or more elements selected from P, Si and B.
- M is Ni, preferably a composite oxide of 1 or higher is LiMO 2, LiM 2 O 4 or Li 2 MO 3 selected from Co and Mn, M is Ni, Co, and Mn More preferred is a composite oxide of LiMO 2 that is 1 or more.
- Li composite oxide has a larger electric capacity per volume (Ah / L) than a positive electrode material such as a conductive polymer, and is effective in improving energy density.
- the positive electrode active material is preferably a Li composite oxide represented by LiMO 2 from the viewpoint of battery capacity.
- M preferably contains Ni, more preferably 25% or more of M is Ni, and even more preferably 45% or more of M is Ni. When M contains Ni, the electric capacity per unit weight (Ah / kg) of the positive electrode active material is larger than when M is Co and Mn, which is effective in improving the energy density.
- the positive electrode active material is a layered lithium composite oxide containing Ni
- the electrode composition containing the positive electrode active material shows an increase in pH due to excess Li salt and the like, and the current collector (aluminum, etc.) corrodes. Therefore, the original characteristics of the active material may not be obtained.
- the binder of the present invention in the electrode composition, the carboxyl group portion of the binder polymer can suppress the increase in pH and can prevent corrosion of the current collector of the layered lithium composite oxide containing Ni.
- the original characteristics of the positive electrode active material can also be obtained in the electrode composition.
- the lithium composite oxide may cause capacity degradation due to elution of metal ions and precipitation at the negative electrode.
- the metal ions eluted from the carboxyl group portion of the polymer of the present invention the eluted metal ions are reduced. It can be expected to reach the negative electrode and prevent the capacity deterioration.
- the positive electrode active material can also be coated with a metal oxide, carbon, or the like.
- a metal oxide, carbon, or the like By covering the positive electrode active material with a metal oxide or carbon, deterioration when the positive electrode active material comes into contact with water can be suppressed, and oxidative decomposition of the binder or the electrolyte during charging can be suppressed.
- the metal oxide used for coating is not particularly limited, a metal oxide such as Al 2 O 3 , ZrO 2 , TiO 2 , SiO 2 , AlPO 4, or a compound represented by Li ⁇ M ⁇ O ⁇ containing Li But you can.
- M is selected from the group consisting of Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ag, Ta, W, and Ir. These metal elements are 0 ⁇ ⁇ ⁇ 6, 1 ⁇ ⁇ ⁇ 5, and 0 ⁇ ⁇ 12.
- other components refers to components other than the polymer, positive electrode active material, conductive additive, and emulsion of the present invention, and includes a dispersant, a water-soluble polymer other than the polymer of the present invention, and the like.
- the positive electrode composition containing the positive electrode active material and the binder of the present invention may consist essentially of the polymer of the present invention, a solvent, a positive electrode active material, and optionally a conductive auxiliary agent and an emulsion.
- 70% by weight or more, 80% by weight or more, or 90% by weight or more of the positive electrode composition containing the positive electrode active material and the binder of the present invention is composed of the polymer of the present invention, the solvent, the positive electrode active material, and optionally the conductive assistant. Agents and emulsions may be used.
- the positive electrode composition may consist only of the polymer of the present invention, a solvent, a positive electrode active material, and optionally a conductive additive and an emulsion (consisting of). In this case, inevitable impurities may be included.
- the positive electrode composition containing the binder of the present invention ensures the dispersion stability of filler components such as a positive electrode active material and a conductive additive, and further has excellent coating film forming ability and adhesion to a substrate. . And the positive electrode formed from such a positive electrode composition can exhibit sufficient performance as a positive electrode for secondary batteries.
- the positive electrode composition contains the binder of the present invention, the positive electrode active material, the conductive auxiliary agent, the emulsion and water, the positive electrode aqueous composition and the conductive auxiliary agent are uniformly dispersed as a method for producing the positive electrode aqueous composition. It is not particularly limited as long as it is used, and it can be manufactured by using a bead mill, a ball mill, a stirring type mixer, or the like.
- the negative electrode active material is a carbon material such as graphite, natural graphite, or artificial graphite; a polyacene conductive polymer, a composite metal oxide such as lithium titanate; a lithium ion such as silicon, a silicon alloy, a silicon composite oxide, or a lithium alloy Materials that are usually used in secondary batteries can be used. Of these, carbon materials, silicon, silicon alloys, and silicon composite oxides are preferable.
- the content ratio (weight ratio) of the polymer of the present invention, the negative electrode active material, the conductive additive, the emulsion, and other components in the solid content of the negative electrode composition is 0.3 to 15/85 to 99/0 to 10/0 to 9/0 to 5 is preferable. With such a content ratio, it is possible to improve output characteristics and electrical characteristics when an electrode formed from the negative electrode composition is used as a negative electrode of a battery. More preferably, it is 0.5 to 12/90 to 98.7 / 0 to 5/0 to 3/0 to 3. More preferably, it is 1.0 to 8/85 to 98/0 to 4/0 to 2.5 / 0 to 1.5.
- “other components” means components other than a binder such as a negative electrode active material, a conductive aid, a polymer or an emulsion of the present invention, and includes a dispersant, a thickener and the like.
- the negative electrode composition containing the negative electrode active material and the binder of the present invention may consist essentially of the polymer of the present invention, a solvent, a negative electrode active material, and optionally a conductive additive and an emulsion.
- 70% by weight or more, 80% by weight or more, or 90% by weight or more of the negative electrode composition containing the negative electrode active material and the binder of the present invention comprises the polymer of the present invention, the solvent, the negative electrode active material, and optionally the conductive assistant. Agents and emulsions may be used.
- the negative electrode composition may consist only of the polymer of the present invention, a solvent, a negative electrode active material, and optionally a conductive additive and an emulsion (consisting of). In this case, inevitable impurities may be included.
- the negative electrode composition containing the binder of the present invention ensures the dispersion stability of the negative electrode active material, and is excellent in the ability to form a coating film and the adhesion to the substrate. And the negative electrode formed from such a negative electrode composition can exhibit sufficient performance as a negative electrode for secondary batteries.
- the negative electrode composition contains the binder, negative electrode active material, conductive auxiliary agent, emulsion and water of the present invention, the negative electrode aqueous composition and the conductive auxiliary agent are uniformly dispersed as a method for producing the negative electrode aqueous composition. It is not particularly limited as long as it is to be produced, and it can be produced by using beads, a ball mill, a stirring type mixer or the like.
- the electrode composition of the present invention can be applied to a current collector and dried to obtain an electrode. More specifically, when the electrode composition is a positive electrode composition containing a positive electrode active material, the positive electrode composition can be applied to a positive electrode current collector and dried to form a positive electrode, and the electrode composition is a negative electrode In the case of a negative electrode composition containing an active material, the negative electrode composition can be applied to a negative electrode current collector and dried to form a negative electrode.
- the positive electrode current collector is not particularly limited as long as it is a material having electronic conductivity and capable of supplying electricity to the held positive electrode material.
- the positive electrode current collector for example, conductive materials such as C, Ti, Cr, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, and Al; including two or more kinds of these conductive materials Alloys such as stainless steel can be used.
- the positive electrode current collector is preferably C, Al, stainless steel or the like, and Al is more preferable from the viewpoint of material cost.
- the negative electrode current collector can be used without any particular limitation as long as it is a conductive material, but it is preferable to use an electrochemically stable material during the battery reaction, for example, copper, stainless steel, or the like can be used. .
- a foil-like base material, a three-dimensional base material, etc. can be used.
- a three-dimensional substrate fused metal, mesh, woven fabric, nonwoven fabric, expanded, etc.
- high capacity density high rate charge / discharge characteristics are also improved.
- the capacity can be increased by forming a primer layer on the current collector surface in advance.
- the primer layer only needs to have good adhesion between the active material layer and the current collector and have conductivity.
- the primer layer can be formed by applying a binder mixed with a carbon-based conductive aid on the current collector in a thickness of 0.1 ⁇ m to 50 ⁇ m.
- the conductive auxiliary for the primer layer is preferably carbon powder.
- the capacity density can be increased with a metal-based conductive aid, the input / output characteristics may be deteriorated.
- a carbon-based conductive aid the input / output characteristics can be improved.
- the carbon-based conductive auxiliary agent include ketjen black, acetylene black, vapor grown carbon fiber, graphite, graphene, and carbon tube. These may be used alone or in combination of two or more. Good. Of these, ketjen black or acetylene black is preferred from the viewpoint of conductivity and cost.
- the primer layer primer is not particularly limited as long as it can bind the carbon-based conductive aid.
- an aqueous binder such as PVA, CMC, sodium alginate, etc. in addition to the binder of the present invention
- the primer layer may be melted when the active material layer is formed, and the effect may not be exhibited remarkably. is there. Therefore, when using such an aqueous binder, the primer layer may be crosslinked in advance.
- the cross-linking material include a zirconia compound, a boron compound, a titanium compound, and the like, and it is preferable to add 0.1 to 20 wt% with respect to the binder amount when forming the primer layer slurry.
- the primer layer is a foil-shaped current collector that not only can increase the capacity density using an aqueous binder, but also has a high polarization rate and good high-rate charge / discharge characteristics even when charged and discharged at a high current. Can be.
- the primer layer is not only effective for the foil-shaped current collector, but the same effect can be obtained even with a three-dimensional substrate.
- FIG. 1 is a schematic cross-sectional view showing one embodiment when the positive electrode composition of the present invention is used as a positive electrode of a lithium ion secondary battery.
- a lithium ion secondary battery 10 has a positive electrode current collector 7, a positive electrode 6, a separator and an electrolytic solution 5, a lithium metal 4 (negative electrode), and a SUS spacer 3 stacked in this order on a positive electrode can 9.
- the laminated body is fixed by gaskets 8 on both side surfaces in the laminating direction and negative electrode cans 1 in the laminating direction via wave washers 2.
- a non-aqueous electrolytic solution that is a solution in which an electrolyte is dissolved in an organic solvent
- the organic solvent include carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactones such as ⁇ -butyrolactone; trimethoxymethane, 1,2-dimethoxyethane, diethyl ether Ethers such as 2-ethoxyethane, tetrahydrofuran and 2-methyltetrahydrofuran; sulfoxides such as dimethyl sulfoxide; oxolanes such as 1,3-dioxolane and 4-methyl-1,3-dioxolane; acetonitrile, nitromethane, NMP and the like Nitrogens such as methyl formate, methyl acetate, butyl acetate, methyl propionate
- the electrolyte for example LiClO 4, LiBF 4, LiI, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) 4, LiCH 3 SO 3, LiC 4 F 9 SO 3, Li (CF 3 SO 2) 2N, Li [(CO 2) 2] 2B , and the like.
- the non-aqueous electrolyte a solution in which LiPF 6 is dissolved in carbonates is preferable, and the solution is particularly suitable as an electrolyte for a lithium ion secondary battery.
- a separator for preventing a short circuit of current due to contact between both electrodes of the positive electrode and the negative electrode it is preferable to use a material that can reliably prevent contact between both electrodes and can pass or contain an electrolyte solution.
- a nonwoven fabric made of a synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, a glass filter, a porous ceramic film, or a porous thin film can be used.
- the separator may be coated with a composition (coating liquid) containing the binder of the present invention.
- a composition coating liquid
- the heat resistance of the separator can be improved by mixing ceramic particles such as silica, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, niobium oxide, and barium oxide and coating them on the separator.
- separator substrate in the above-mentioned coat those described above can be used without limitation, but a porous thin film is preferable, and a polyolefin porous film prepared by a wet method or a dry method can be suitably used.
- the above composition can be coated on the positive electrode or the negative electrode and used as a protective film.
- a protective film By forming such a protective film on the positive electrode or the negative electrode, an improvement in the cycle characteristics of the battery can be expected.
- a secondary battery can be manufactured, for example, by putting a negative electrode, a separator impregnated with an electrolyte, and a positive electrode into an outer package and sealing the same.
- a known method such as caulking or laminate sealing may be used.
- sodium polyglutamate weight average molecular weight 230,000
- pH of a 1 wt% aqueous solution of sodium polyglutamate was 5.72.
- a 1 wt% aqueous solution of sodium polyglutamate was separately prepared, and the value at 25 ° C. was measured with a glass electrode type hydrogen ion meter TES-1380 (product name, manufactured by Custom).
- a positive electrode which is a working electrode manufactured by fitting a gasket to a positive electrode can of a coin cell (manufactured by Hosen Co., Ltd., coin cell 2032) in an Ar-substituted glove box controlled to an oxygen concentration of 10 ppm or less and a moisture concentration of 5 ppm or less, The separator was laminated in order, and the electrolytic solution was added. Furthermore, a coin cell was produced by stacking a negative electrode, a SUS spacer, a wave washer, and a negative electrode can and sealing them using a coin cell caulking machine (manufactured by Hosen Co., Ltd.). A schematic cross-sectional view of the obtained coin cell is shown in FIG. Each component of the coin cell is as follows.
- the manufactured coin cell was evaluated by measuring the current value at 4.8V (lithium standard) under the following conditions, and standardizing the current value per 1 mg of binder on the electrode. The results are shown in Table 1.
- Example 1-2 Acetylene black (manufactured by Denka Co., Ltd., HS-100) and distilled water were added to an 18 wt% aqueous solution of lithium poly- ⁇ -glutamate (weight average molecular weight 190,000, hereinafter referred to as lithium polyglutamate), and acetylene black: polyglutamic acid The mixture was mixed so that lithium was 1: 1 (weight ratio) to obtain a slurry. Using the resulting slurry, coin cells were produced and evaluated in the same manner as in Example 1-1. The results are shown in Table 1.
- Comparative Example 1 Instead of an aqueous solution of sodium polyglutamate, an N-methyl-2-pyrrolidone (NMP) solution (weight average molecular weight 280,000, a homopolymer of vinylidene fluoride) with 12 wt% PVDF was used, and NMP was used instead of distilled water. A slurry was prepared in the same manner as in Example 1-1 except that the coin cell was manufactured and evaluated. The results are shown in Table 1.
- NMP N-methyl-2-pyrrolidone
- the sodium polyglutamate used in Example 1-1 and the lithium polyglutamate used in Example 1-2 had a current value lower than that of PVDF used in Comparative Example 1, and were 4.8 V (based on lithium). ) was found to be electrically stable even when a high voltage was applied. This indicates that the binder containing sodium polyglutamate or lithium polyglutamate is more durable than the binder containing PVDF and is a positive electrode binder for a secondary battery that can withstand repeated charge and discharge.
- Example 2-1 Water (3.6 parts) and sodium polyglutamate (3.6 parts) were mixed to form a homogeneous solution, and LiNi 0.5 Co 0.2 Mn 0.3 O 2 (63 parts) and acetylene black HS-100 ( Denka) (3.4 parts) was added to obtain a mixed dispersion. Further, water (26 parts) was added to obtain a positive electrode composition (1).
- the obtained positive electrode composition (1) was applied to 20 ⁇ m Al foil. , Dried at 80 ° C. for 10 minutes, and pressed at room temperature to produce an electrode with 1 mAh / cm 2 and a porosity of 35%. The obtained electrode was punched out to 13 mm ⁇ and vacuum-dried at 120 ° C. for 5 hours.
- a positive electrode and a separator which are electrodes manufactured by fitting a gasket to a positive electrode can of a coin cell (manufactured by Hosen Co., Ltd., coin cell 2032) in an Ar-substituted glove box controlled to an oxygen concentration of 10 ppm or less and a water concentration of 5 ppm or less. Were sequentially laminated, and an electrolytic solution was added. Furthermore, a coin cell was produced by stacking a negative electrode, a SUS spacer, a wave washer, and a negative electrode can and sealing them using a coin cell caulking machine (manufactured by Hosen Co., Ltd.). A schematic cross-sectional view of the obtained coin cell is shown in FIG. Each component of the coin cell is as follows.
- the discharge capacity which is the charge / discharge characteristics of the obtained coin cell, was evaluated under the following measurement conditions. The results are shown in Table 2.
- the discharge capacity of the 2nd cycle was employ
- the capacity retention rate was calculated as (capacity retention rate) ((40th discharge capacity) / (10th discharge capacity)) in the following cycle charge / discharge.
- the battery capacity was calculated as 160 mAh per gram of LiNi 0.5 Co 0.2 Mn 0.3 O 2, and 1 C (current value for complete discharge in 1 hour) was calculated based on the capacity.
- Example 2-2 Uniform solution of water (13 parts) and lithium polyglutamate (3.0 parts) (lithium polyglutamate 18 wt% solution), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (55 parts) and acetylene black HS— 100 (Denka) (3.0 parts) was added to obtain a mixed dispersion. Further, water (26 parts) was added to obtain a positive electrode composition (2).
- Comparative Example 2 A homogeneous solution (PVDF 12 wt% NMP solution) of 2.5 parts of PVDF (weight average molecular weight 280,000, homopolymer of vinylidene fluoride) and 19 parts of NMP was added to LiNi 0.5 Co 0.2 Mn 0.3 O 2 (45 parts). ) And acetylene black HS-100 (2.5 parts by Denka) and mixed and dispersed. Further, NMP (32 parts) was added and mixed to obtain a positive electrode composition (3).
- PVDF 12 wt% NMP solution 2.5 parts of PVDF (weight average molecular weight 280,000, homopolymer of vinylidene fluoride) and 19 parts of NMP was added to LiNi 0.5 Co 0.2 Mn 0.3 O 2 (45 parts).
- acetylene black HS-100 2.5 parts by Denka
- the items of the active material, the conductive additive, and the binder represent (content ratio in the positive electrode composition (wt%)) / (content ratio in the solid content (wt%)), respectively.
- the content ratio of acetylene black in the positive electrode composition of Example 2-1 is 3.4 wt%
- the content ratio of acetylene black in the solid content in the positive electrode composition of Example 2 is 5 wt%.
- the item of the solvent of Table 2 represents the content rate (wt%) of the solvent in a positive electrode composition, respectively.
- Table 3-5 below have the same meaning as in Table 2.
- Example 2-3 Water (2.5 parts) and sodium polyglutamate (2.5 parts) were mixed to obtain a homogeneous solution, and graphite (48 parts) was added to obtain a mixed dispersion. Further, water (47.3 parts) was added to obtain a negative electrode composition.
- the obtained negative electrode composition was coated on 11 ⁇ m Cu foil, and 80 ° C.
- the film was dried for 10 minutes and pressed at room temperature to produce an electrode with 1.1 mAh / cm 2 and a porosity of 35%.
- the obtained electrode was punched out to 14 mm ⁇ and vacuum-dried at 150 ° C. for 5 hours.
- a negative electrode and a separator which are electrodes manufactured by fitting a gasket to a positive electrode can of a coin cell (manufactured by Hosen Co., Ltd., coin cell 2032) in an Ar-substituted glove box controlled to an oxygen concentration of 10 ppm or less and a moisture concentration of 5 ppm or less. Were sequentially laminated, and an electrolytic solution was added. Furthermore, Li metal, a SUS spacer, a wave washer, and a negative electrode can were piled up, and it sealed using the coin cell crimping machine (made by Hosen Co., Ltd.), and produced the coin cell. A schematic cross-sectional view of the obtained coin cell is shown in FIG. Each component of the coin cell is as follows.
- Negative electrode 14 mm ⁇ sheet separator prepared above: 16 mm ⁇ glass separator (GA-100 manufactured by Advantech)
- the discharge capacity which is the charge / discharge characteristic of the obtained coin cell, was evaluated under the following measurement conditions.
- the discharge capacity of the 2nd cycle was employ
- the capacity cycle retention rate was calculated as (capacity cycle retention rate) in the following cycle charge / discharge (40th discharge capacity) / (10th discharge capacity).
- the battery capacity was calculated as 320 mAh per 1 g of graphite, and 1 C (current value for complete discharge in 1 hour) was calculated based on the capacity.
- Comparative Example 2-2 Other than using PVDF (weight average molecular weight 280,000, homopolymer of vinylidene fluoride) instead of sodium polyglutamate as the binder, and preparing the negative electrode composition so that the ratio of the active material, binder and solvent is as shown in Table 3. Manufactured and evaluated electrodes and coin cells in the same manner as in Example 2-3. The results are shown in Table 3.
- PVDF weight average molecular weight 280,000, homopolymer of vinylidene fluoride
- Comparative Example 2-3 As the binder, PVDF # 2 (modified with a homopolymer of vinylidene fluoride having a weight average molecular weight of 280,000) was used instead of sodium polyglutamate, and the ratio of active material, binder and solvent was as shown in Table 3. An electrode and a coin cell were produced and evaluated in the same manner as in Example 2-3 except that the composition was prepared. The results are shown in Table 3.
- Example 2-3 using sodium polyglutamate as a binder shows a higher capacity retention rate than those using PVDF and PVDF # 2.
- Example 2-4 As the active material, LiNi 0.5 Mn 1.5 O 4 was used instead of LiNi 0.5 Co 0.2 Mn 0.3 O 2 , and the ratio of the active material, the conductive assistant, the binder and the solvent was as shown in Table 4.
- a positive electrode composition was prepared in the same manner as in Example 2-1, except for the above. Separately, a negative electrode composition of Comparative Example 2-2 was also prepared.
- the obtained positive electrode composition was coated on 20 ⁇ m Al foil, and 80 ° C.
- the film was dried for 10 minutes, pressed at room temperature, and an electrode with 1 mAh / cm 2 and a porosity of 35% was produced.
- the obtained electrode was punched out to 13 mm ⁇ and vacuum dried at 150 ° C. for 5 hours. This was used for the positive electrode.
- the negative electrode composition of Comparative Example 2-2 was applied to 11 ⁇ m Cu foil. , Dried at 80 ° C. for 10 minutes, and pressed at room temperature to produce an electrode with 1 mAh / cm 2 and a porosity of 35%. The obtained electrode was punched out to 14 mm ⁇ and vacuum-dried at 150 ° C. for 5 hours. This was used for the negative electrode.
- a gasket is put on the positive electrode can of a coin cell (manufactured by Hosen Co., Ltd., coin cell 2032), and a positive electrode and a separator are sequentially laminated.
- the electrolyte was added.
- a coin cell was produced by stacking a negative electrode, a SUS spacer, a wave washer, and a negative electrode can and sealing them using a coin cell caulking machine (manufactured by Hosen Co., Ltd.).
- a schematic cross-sectional view of the obtained coin cell is shown in FIG.
- Each component of the coin cell is as follows.
- the discharge capacity which is the charge / discharge characteristics of the obtained coin cell, was evaluated under the following measurement conditions. The results are shown in Table 4. Since the evaluated discharge capacity has a large irreversible capacity for the first charge / discharge under the following conditions, the discharge capacity at the second cycle was adopted. Further, the capacity cycle maintenance rate was calculated as (capacity cycle maintenance rate) in the following cycle charge / discharge (60th discharge capacity) / (10th discharge capacity). The battery capacity was calculated as 135 mAh per gram of LiNi 0.5 Mn 1.5 O 4, and 1C (current value for complete discharge in 1 hour) was calculated based on the capacity.
- a coin cell separately manufactured under the same conditions was subjected to a cycle test at a high temperature (60 ° C.).
- the capacity retention ratio was calculated as (capacity cycle retention ratio) in the following cycle charge / discharge (discharge capacity at 60th time at 1C) / (discharge capacity at 10th time at 1C).
- the battery capacity was calculated as 135 mAh per gram of LiNi 0.5 Mn 1.5 O 4, and 1C (current value for complete discharge in 1 hour) was calculated based on the capacity.
- Comparative Example 2-4 PVDF (weight average molecular weight 280,000, homopolymer of vinylidene fluoride) is used in place of sodium polyglutamate as a binder, NMP is used in place of water as a solvent, active material, conductive additive, binder and solvent A positive electrode composition was prepared in the same manner as in Example 2-4 except that the ratio was as shown in Table 4, and a coin cell was produced and evaluated. The results are shown in Table 4.
- Example 2-4 using sodium polyglutamate as a binder showed a higher capacity retention rate than that using PVDF. Moreover, also about the cycle test at high temperature (60 degreeC), the high capacity
- Example 2-5 Example 2-4 except that LiFePO 4 was used instead of LiNi 0.5 Mn 1.5 O 4 as the active material, and the ratio of the active material, the conductive additive, the binder and the solvent was as shown in Table 5.
- a positive electrode composition was prepared in the same manner as described above. Using the obtained positive electrode composition, an electrode and a coin cell were produced and evaluated in the same manner as in Example 2-4. The results are shown in Table 5.
- the discharge capacity which is the charge / discharge characteristics of the obtained coin cell, was evaluated under the following measurement conditions. The results are shown in Table 5.
- the discharge capacity of the 2nd cycle was employ
- the capacity cycle retention rate was calculated as (capacity cycle retention rate) in the following cycle charge / discharge (40th discharge capacity) / (10th discharge capacity).
- the battery capacity was calculated as 150 mAh per 1 g of LiFePO 4 , and 1C (current value for complete discharge in 1 hour) was calculated based on the capacity.
- a coin cell separately manufactured under the same conditions was subjected to a cycle test at a high temperature (60 ° C.).
- the capacity retention rate was calculated as (capacity cycle retention rate) in the following cycle charge / discharge (discharge capacity at 100th time at 1C) / (discharge capacity at 10th time at 1C).
- the battery capacity was calculated as 150 mAh per 1 g of LiFePO 4 , and 1C (current value for complete discharge in 1 hour) was calculated based on the capacity.
- Comparative Example 2-5 PVDF (weight average molecular weight 280,000, homopolymer of vinylidene fluoride) is used in place of sodium polyglutamate as a binder, NMP is used in place of water as a solvent, active material, conductive additive, binder and solvent
- a positive electrode composition was prepared in the same manner as in Example 2-5 except that the ratio was as shown in Table 5, and a coin cell was produced and evaluated. The results are shown in Table 5.
- Example 2-5 using sodium polyglutamate as a binder showed a higher capacity retention rate than that using PVDF. Moreover, also about the cycle test at high temperature (60 degreeC), the high capacity
- Example 2-6 A coin cell was manufactured in the same manner as in Example 2-1, except that the negative electrode manufactured in Comparative Example 2-3 was used instead of the Li foil.
- the discharge capacity which is the charge / discharge characteristics of the obtained coin cell, was evaluated under the following measurement conditions. The results are shown in Table 6.
- the discharge capacity of the 2nd cycle was employ
- the capacity cycle retention rate was calculated as (capacity cycle retention rate) in the following cycle charge / discharge (40th discharge capacity) / (10th discharge capacity).
- the battery capacity was calculated as 160 mAh per gram of LiNi 0.5 Co 0.2 Mn 0.3 O 2, and 1 C (current value for complete discharge in 1 hour) was calculated based on the capacity.
- a cycle test at a high voltage was performed on a coin cell separately manufactured under the same conditions.
- the capacity retention ratio was calculated as (capacity cycle retention ratio) in the following cycle charge / discharge (discharge capacity at 60th time at 1C) / (discharge capacity at 10th time at 1C).
- the battery capacity was calculated as 190 mAh per gram of LiNi 0.5 Co 0.2 Mn 0.3 O 2, and 1C (current value for complete discharge in 1 hour) was calculated based on the capacity.
- Comparative Example 2-6 A coin cell was manufactured in the same manner as in Comparative Example 2 except that the negative electrode manufactured in Comparative Example 2-3 was used instead of the Li foil as the negative electrode, and the same evaluation as in Example 2-6 was performed. The results are shown in Table 6.
- Example 2-6 using sodium polyglutamate as a binder showed a higher capacity retention rate in a cycle at 4.3 V than that using PVDF. Furthermore, in the cycle of 4.5V, the difference in capacity retention ratio was large, and the deterioration of the average voltage was suppressed.
- Example 2-7 The coin cells manufactured in Example 2-6 were charged to 4.3 V, 4.4 V, and 4.5 V, respectively, under the following conditions. The charged coin cell was allowed to stand for 96 hours at 60 ° C. and 80 ° C., respectively, and the self-discharge amount during the leaving period was compared. The results are shown in Table 7.
- Comparative Example 2-7 The coin cell manufactured in Comparative Example 2-6 was evaluated in the same manner as in Example 2-7. The results are shown in Table 7.
- Example 2-7 using sodium polyglutamate as a binder has a smaller amount of self-discharge, and the difference is particularly large at high potential and high temperature.
- the sodium polyglutamate binder may improve the durability of the lithium ion battery at high potential and high temperature.
- the present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects).
- the present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration.
- the present invention includes a configuration that achieves the same effect as the configuration described in the above embodiment or a configuration that can achieve the same object.
- the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.
- the binder for the positive electrode of the lithium ion secondary battery As an example, the present invention is not limited to this, and other electrochemical elements, for example, the binder for the negative electrode of the lithium ion battery, the separator of the lithium ion battery It can also be suitably used as a binder for coating, a binder for electric double layer capacitors, and the like. In particular, it can be suitably used for other electrical devices that are exposed to an oxidizing environment, such as a separator coating binder for lithium ion batteries and a binder for capacitors.
- Electrochemical elements such as lithium ion batteries and electric double layer capacitors produced using the binder of the present invention can be used in various electric devices and vehicles.
- Examples of the electric device include a mobile phone and a notebook computer, and examples of the vehicle include an automobile, a railroad, and an airplane, but are not limited to the above.
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Abstract
Description
電極組成物のうち、正極の形成に用いられる正極組成物は、主に正極活物質、導電助剤、バインダー及び溶媒からなっており、当該バインダーとしては、ポリフッ化ビニリデン(PVDF)、当該溶媒としては、N-メチル-2-ピロリドン(NMP)が一般に用いられている。これは、PVDFが化学的、電気的に安定であり、NMPがPVDFを溶解する経時安定性のある溶媒であることが理由である。
1. カルボキシル基及び/若しくはその塩を有するポリマーと、アミド基及び/若しくはアミド結合を有するポリマー、又は
カルボキシル基及び/若しくはその塩、並びにアミド基及び/若しくはアミド結合を有するポリマーを含有する電気化学素子用バインダー。
2. さらに水を含む1に記載の電気化学素子用バインダー。
3. 前記カルボキシル基及び/又はその塩、並びにアミド基及び/又はアミド結合を有するポリマーが、下記式(1)又は下記式(2)で表される繰り返し単位を60%以上含むポリマーである1又は2に記載の電気化学素子用バインダー。
Xは、水素イオン又は金属イオンである。
R1は、水素原子又は炭素数10以下の官能基である。)
R2は、炭素数10以下のカルボキシル基又はカルボキシレート基を含む官能基である。)
4. 前記金属イオンが、アルカリ金属イオン又はアルカリ土類金属イオンである3に記載の電気化学素子用バインダー。
5. 前記金属イオンが、アルカリ金属イオンである3又は4に記載の電気化学素子用バインダー。
6. 前記金属イオンが、Liイオン又はNaイオンである3~5のいずれかに記載の電気化学素子用バインダー。
7. 前記カルボキシル基の一部がエステル化している1~6のいずれかに記載の電気化学素子用バインダー。
8. 前記カルボキシル基及び/又はその塩、並びにアミド基及び/又はアミド結合を有するポリマーが、グルタミン酸の中和物及びアスパラギン酸の中和物から選択される1以上のアミノ酸がα位、β位、又はγ位でアミド結合した重合体である1~7のいずれかに記載の電気化学素子用バインダー。
9. 前記ポリマーに含まれる芳香族炭化水素基を含む繰り返し単位が20%以下である1~8のいずれかに記載の電気化学素子用バインダー。
10. 前記ポリマーの重量平均分子量(Mw、PEG換算)が50,000~9,000,000である1~9のいずれかに記載の電気化学素子用バインダー。
11.1~10のいずれかに記載の電気化学素子用バインダーを含むリチウムイオン電池電極用バインダー。
12. 11に記載のリチウムイオン電池電極用バインダーを含有するリチウムイオン電池用電極組成物。
13. 12に記載のリチウムイオン電池用電極組成物を用いた、リチウムイオン電池用電極。
14. 1~10のいずれかに記載の電気化学素子用バインダーを含有するリチウムイオン電池セパレータ用組成物用バインダー。
15. 14に記載のリチウムイオン電池セパレータ組成物用バインダーを含むリチウムイオン電池セパレータ用組成物。
16. 15に記載したリチウムイオン電池セパレータ用組成物を用いたリチウムイオン電池用セパレータ。
17. 1~10のいずれかに記載の電気化学素子用バインダーを含むリチウムイオン電池電極保護膜用バインダー。
18. 17に記載のリチウムイオン電池電極保護膜用バインダーを含むリチウムイオン電池電極保護膜用組成物。
19. 18に記載のリチウムイオン電池電極保護膜用組成物を用いたリチウムイオン電池電極保護膜。
20. 1~10のいずれかに記載の電気化学素子用バインダーを用いたリチウムイオン電池。
21. 20に記載のリチウムイオン電池を備える電気機器。
22. 20に記載のリチウムイオン電池を備える車両。
23. 1~10のいずれかに記載の電気化学素子用バインダーを含む電気二重層キャパシタ用バインダー。
24. 23に記載した電気二重層キャパシタ用バインダーを含む電気二重層キャパシタ電極用組成物。
25. 24に記載の電気二重層キャパシタ電極用組成物を用いた電気二重層キャパシタ電極。
26. 25に記載した電気二重層キャパシタ電極を備える電気二重層キャパシタ。
27. 26に記載した電気二重層キャパシタを用いた電気機器。
28. 26に記載した電気二重層キャパシタを用いた車両。
本発明の電気化学素子用バインダーは、カルボキシル基及び/若しくはその塩を有するポリマーと、アミド基及び/若しくはアミド結合を有するポリマー、又はカルボキシル基及び/若しくはその塩、並びにアミド基及び/若しくはアミド結合を有するポリマーを含有する。
ここで「電気化学素子」とは、リチウムイオン電池等の二次電池、及びキャパシタを含む意味である。
以下、(1)カルボキシル基及び/若しくはその塩を有するポリマーと、アミド基及び/若しくはアミド結合を有するポリマー、(2)カルボキシル基及び/若しくはその塩、並びにアミド基及び/若しくはアミド結合を有するポリマーをまとめて「本発明のポリマー」という場合がある。
本発明のバインダーが水を多く含む水系バインダーであることで、環境負荷を小さくすることができ、且つ、溶媒回収コストも低減することができる。
バインダーが含みうる水以外の溶媒としては、例えば、エタノール、2-プロパノールなどのアルコール系溶媒、アセトン、NMP、エチレングリコールなどが挙げられる。但し、水以外の溶媒はこれらに限定されるものではない。
カルボキシル基及び/又はその塩の部位を有するポリマーは極性が高く、金属箔、活物質及び導電助剤との良好な結着性を実現できるとともに、分散機能及び増粘機能を有する。カルボキシル基及び/又はその塩の部位を有するポリマーをバインダーとして含む組成物は、良好な塗工性を発現することができる。
カルボキシル基部位の中和度が50%以上であればpHが下がりすぎず、活物質及びアルミ集電体の腐食を防ぐことができる。また、中和度が向上することで、ポリマーの水への溶解性が向上するとともに、電解液への膨潤性の低減が期待できる。中和度に上限はないが、過剰の塩基が存在することは好ましくない。
上記カルボキシル基部位の中和度は、例えば中和滴定や元素分析(CHNコーダー法及びICP分光分析法)で元素比を確認することで計算できる。
中和する塩がNaであれば、ポリマーを特に安価に製造でき、中和する塩がLiであれば、電解液-活物質間の電荷移動抵抗の低減や電極内のリチウム伝導性の向上に寄与することが期待できる。
アミド基及び/又はアミド結合の部位を有する単位が30%以上であると、ポリマー中のアミド基部位は水素結合を形成し、電解液への溶解を抑制するとともに、水素結合によるネットワークを形成することで、活物質を強く保持することが期待できる。
上記カルボキシル基及びアミド結合の両方を有するポリマーの場合、分子内及び分子間において水素結合が複数の点で発生し、強固な結着が期待できるとともに、親水性の向上によって水への溶解性が向上し、電解液への膨潤性を低減することができる。
尚、バインダーがカルボキシル基及びアミド結合の両方を有するポリマーを含む場合、当該カルボキシル基及びアミド結合の両方を有するポリマーは、互いに構造が異なる2種以上でもよい。
Xは、水素イオン又は金属イオンである。
R1は、水素原子又は炭素数10以下の脂肪族炭化水素基である。
nは、繰り返し数である。)
R2は、炭素数10以下のカルボキシル基又はカルボキシレート基を含む脂肪族炭化水素基である。
nは、繰り返し数である。)
x、y及びzの数値が上記範囲であれば、脂肪族骨格が柔軟性を示すことができ、得られる電極の柔軟性が保たれ、疎水性部位である脂肪族骨格が親水性部位であるアミド部位とカルボキシル基又はカルボキシレート基部位に対して十分に少なく、水への溶解性を確保することができる。
Xは、水素イオン又は金属イオンである。当該金属イオンは、アルカリ金属イオン又はアルカリ土類金属イオンであると好ましく、Liイオン又はNaイオンであるとより好ましい。
また、Xの一部は脂肪族炭化水素基でもよく、これはXの一部がエステル化されていることを意味する。エステル化された単位構造の含有率は全体の70%以下が好ましく、さらに好ましくは50%以下、特に好ましくは30%以下である。全体の70%以下であれば、当該ポリマーの水溶性が十分なものとなる。また、エステルとしては、Xがメチル基、エチル基であるメチルエステル、エチルエステルなどが挙げられるが、これらに限定されるものではない。
R1は、水素原子又は炭素数10以下の官能基である。当該官能基は、アルキル基、アルコキシアルキル基、ヒドロキシアルキル基等を含む。当該炭素数10以下の官能基としては、メチル基、エチル基、直鎖もしくは分岐のブチル基、ペンチル基、メトキシメチル基などが挙げられる。官能基の炭素数は10以下が好ましく、さらに好ましくは7以下であり、特に好ましくは5以下である。また、官能基中にヒドロキシル基などの水素結合を形成する官能基を有してもよい。炭素数が10以下であると水への溶解性が確保できる。またヒドロキシル基などの官能基は水溶性を向上させる。
R2は炭素数10以下のカルボキシル基又は炭素数10以下のカルボキシレート基を含む脂肪族炭化水素基である。当該炭素数10以下のカルボキシル基としては、炭素数1~9のアルキル基にカルボキシル基が結合した置換基が挙げられる。また、炭素数10以下のカルボキシレート基の塩としては、金属イオンが好ましく、アルカリ金属イオン又はアルカリ土類金属イオンがより好ましく、Liイオン又はNaイオンがさらに好ましい。官能基の炭素数は10以下が好ましく、さらに好ましくは7以下であり、特に好ましくは5以下である。官能基の炭素数が10以下であれば十分な水溶性が得られる。
また、カルボキシル基の一部がエステル化されていてもよい。エステル化された単位構造の含有率は全体の70%以下が好ましく、さらに好ましくは50%以下、特に好ましくは30%以下が良い。全体の70%以下であれば、当該ポリマーの水溶性が十分なものとなる。また、エステルとしてはメチルエステル、エチルエステルなどが挙げられるが、これらに限定されるものではない。
式(1)又は(2)で表される繰り返し単位を60%以上含むポリマーであれば、電気化学素子に好適な電気化学的安定性及び物理特性を与えることができる。
ポリマーに含まれる芳香族炭化水素基部位が少ないほど、芳香族炭化水素基の酸化によるポリマーの酸化劣化による分子量の変化、ガス発生のおそれがなくなる。
本発明のポリマーは、好ましくはγ-ポリグルタミン酸であり、さらに好ましくはL体のグルタミン酸とD体のグルタミン酸が共存するアタクチックなポリマーである。アタクチックなポリマーは結晶性が低く、柔軟性が高いため、電極にした際に割れが生じにくく、良好な電極シートを構築できる。
ポリマーの分子量が50,000以上であれば電解液へ溶出しにくくなり、また分子鎖の絡み合いによる結着作用が得られるので、結着性も良好になることが期待できる。ポリマーの分子量が9,000,000以下であれば、ポリマーの水への溶解性が得られ、塗工可能な粘度の電極組成物を調製することが可能となる。
ポリマーの重量平均分子量の測定は、ゲルパーミッションクロマトグラフィーで行うことができる。例えば、カラムに東ソー製TSKgel GMPWXL 2本、溶媒として0.2M NaNO3 aq.、示差屈折率(RI)検出器として日本分光製 RI-1530を用いて、標準サンプルとして東ソー製 TSKgel std PEO及びAgilent製 PEGを用いて3次の検量線を引いてPEG換算で測定できる。サンプル濃度は0.3重量%(以降wt%と記載する。)程度とするとよい。
本発明のバインダーは、本発明のポリマー、その他の成分及び溶媒からなってもよく、本発明のポリマー及び溶媒のみからなってもよい。その他の成分とは、エマルション、分散剤、その他の水溶性高分子などである。
バインダーが分散剤を含む場合には、後述する導電助剤100wt%に対して5~20wt%含有することが好ましい。分散剤の含有量がこのような範囲であると、導電助剤を充分に微粒子化でき、且つ活物質を混合した場合の分散性を充分に確保することが可能となる。
バインダーのpHは、バインダーの1wt%水溶液をガラス電極式水素イオン度計TES-1380(製品名、カスタム社製)で25℃で測定することにより確認できる。
上記電流値の測定は実施例に記載の方法で測定できる。
本発明のバインダーは、二次電池の電極を形成する電極組成物のバインダーとして好適に用いることができる。本発明のバインダーは、正極活物質を含む正極組成物及び負極活物質を含む負極組成物のいずれにも用いることができるが、特に正極組成物に好適に用いることができる。
本発明のバインダーを含む電極組成物(以下、本発明の電極組成物という場合がある)は、バインダーの他に活物質及び導電助剤を含む。
導電性カーボンとしては、ケッチェンブラック、アセチレンブラック等のカーボンブラック;ファイバー状カーボン;黒鉛等がある。これらの中でもケッチェンブラック、アセチレンブラックが好ましい。ケッチェンブラックは中空シェル構造を持ち、導電性ネットワークを形成しやすい。そのため、従来のカーボンブラックに比べ、半分程度の添加量で同等性能を発現することができる。アセチレンブラックは高純度のアセチレンガスを用いることで副生される不純物が非常に少なく、表面の結晶子が発達しているため好ましい。
導電助剤の平均粒子径は、より好ましくは0.01~0.8μmであり、さらに好ましくは0.03~0.5μmである。導電助剤の平均粒子径は、動的光散乱の粒度分布計(例えば導電助剤屈折率を2.0とする)により測定することができる。
ファイバー状カーボンは、太さ0.8nm以上、500nm以下、長さ1μm以上100μm以下が好ましい。太さが当該範囲であれば、十分な強度と分散性が得られ、長さが当該範囲内であれば、ファイバー形状による導電パスの確保が可能となる。
正極活物質としては、種々の酸化物、硫化物が挙げられ、具体例としては、二酸化マンガン(MnO2)、リチウムマンガン複合酸化物(例えばLiMn2O4又はLiMnO2)、リチウムニッケル複合酸化物(例えばLiNiO2)、リチウムコバルト複合酸化物(LiCoO2)、リチウムニッケルコバルト複合酸化物(例えばLiNi1-xCoxO2)、リチウム-ニッケル-コバルト-アルミニウム複合酸化物(LiNi0.8Co0.15Al0.05O2)、リチウムマンガンコバルト複合酸化物(例えばLiMnxCo1-xO2)、リチウムニッケルコバルトマンガン複合酸化物(例えばLiNixMnyCo1-x-yO2)、ポリアニオン系リチウム化合物(例えば、LiFePO4、LiCoPO4F、Li2MnSiO4等)、バナジウム酸化物(例えばV2O5)、Li過剰系ニッケル-コバルト-マンガン複合酸化物(例えばLixNiACoBMnCO2固溶体)、リチウムコバルトリン酸化合物(例えばLiCoPO4)、リチウムニッケルマンガン複合酸化物(例えばLiNi0.5Mn1.5O4)等が挙げられる。また、導電性ポリマー材料、ジスルフィド系ポリマー材料、等の有機材料も挙げられる。硫化リチウム等のイオウ化合物材料も挙げられる。
これらのうち、リチウムマンガン複合酸化物(LiMn2O4)、リチウムニッケル複合酸化物(LiNiO2)、リチウムコバルト複合酸化物(LiCoO2)、リチウムニッケルコバルト複合酸化物(LiNi0.8Co0.2O2)、リチウム-ニッケル-コバルト-アルミニウム複合酸化物(LiNi0.8Co0.15Al0.05O2)、リチウムマンガンコバルト複合酸化物(LiMnxCo1-xO2)、リチウムニッケルコバルトマンガン複合酸化物(例えばLiNixMnyCo1-x-yO2)、Li過剰系ニッケル-コバルト-マンガン複合酸化物(LixNiACoBMnCO2固溶体)、LiCoPO4、LiNi0.5Mn1.5O4が好ましい。
上記正極活物質のうち、MがNi、Co及びMnから選択される1以上であるLiMO2、LiM2O4又はLi2MO3の複合酸化物が好ましく、MがNi、Co及びMnから選択される1以上であるLiMO2の複合酸化物がより好ましい。Li複合酸化物は導電性ポリマー等の正極物質と比較して体積当たりの電気容量(Ah/L)が大きく、エネルギー密度の向上に有効である。
正極活物質は、電池容量の観点から、LiMO2で表されるLi複合酸化物が好ましい。ここで、MはNiを含むと好ましく、Mのうち25%以上がNiであるとより好ましく、Mの45%以上がNiであるとさらに好ましい。MがNiを含むと、MがCo及びMnの場合に比べて、正極活物質の重量当たりの電気容量(Ah/kg)が大きくなり、エネルギー密度の向上に効果的である。
また、リチウム複合酸化物は、金属イオンの溶出、負極での析出による容量劣化のおそれがあるが、本発明のポリマーのカルボキシル基部位が溶出した金属イオンを補足することで、溶出した金属イオンが負極に到達し、容量劣化が起こることを防止することが期待できる。
被覆に用いる金属酸化物は特に限定されないが、Al2O3、ZrO2、TiO2、SiO2、AlPO4等の金属酸化物や、Liを含有するLiαMβOγで表される化合物でもよい。尚、LiαMβOγにおいて、Mは、Al、Ti、Cr、Mn、Fe、Co、Ni、Cu、Zr、Nb、Mo、Ag、Ta、W、Irからなる群から選択される1以上の金属元素であり、0≦α≦6、1≦β≦5、0<γ≦12である。
このような含有割合であると、正極組成物から形成される電極を電池の正極として用いた場合の出力特性や電気特性を優れたものとすることが可能となる。より好ましくは、0.5~12/80~97/1~10/0~6/0~2である。さらに好ましくは、1.0~8/85~97/1.5~8/0~4/0~1.5である。尚、ここでいう「その他の成分」は、本発明のポリマー、正極活物質、導電助剤、エマルション以外の成分を指し、分散剤、本発明のポリマー以外の水溶性高分子等が含まれる。
正極組成物が、本発明のバインダー、正極活物質、導電助剤、エマルションと水とを含むものである場合、当該正極水系組成物の製造方法としては、正極活物質と導電助剤とが均一に分散されることになる限り特に制限されず、ビーズミル、ボールミル、攪拌型混合機等を用いることで製造できる。
負極組成物が、本発明のバインダー、負極活物質、導電助剤、エマルションと水とを含むものである場合、当該負極水系組成物の製造方法としては、負極活物質と導電助剤とが均一に分散されることになる限り特に制限されず、ビーズ、ボールミル、攪拌型混合機等を用いることで製造できる。
より具体的には、電極組成物が正極活物質を含む正極組成物である場合、正極組成物を正極集電体上に塗布及び乾燥することで正極とすることができ、電極組成物が負極活物質を含む負極組成物である場合、負極組成物を負極集電体上に塗布及び乾燥することにより負極とすることができる。
電気伝導性が高く、電解液中の安定性と耐酸化性がよい観点から、正極集電体としてはC、Al、ステンレス鋼等が好ましく、さらに材料コストの観点からAlが好ましい。
炭素系導電助剤としては、ケッチェンブラック、アセチレンブラック、気相法炭素繊維、グラファイト、グラフェン、カーボンチューブ等が挙げられ、これら一種単独で用いてもよいし、二種以上を併用してもよい。これらのうち、導電性とコストの観点から、ケッチェンブラック又はアセチレンブラックが好ましい。
尚、プライマー層は箔状の集電体だけに効果があるのではなく、三次元基材でも同様の効果が得られる。
図1は、本発明の正極組成物をリチウムイオン二次電池の正極とした場合の一実施形態を示す概略断面図である。
図1において、リチウムイオン二次電池10は、正極缶9上に正極集電体7、正極6、セパレータ及び電解液5、リチウム金属4(負極)及びSUSスペーサ3がこの順に積層しており、当該積層体は、積層方向両側面をガスケット8によって、及び積層方向をウェーブワッシャー2を介した負極缶1によって固定されている。
有機溶媒としては、例えばプロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等のカーボネート類;γ-ブチロラクトン等のラクトン類;トリメトキシメタン、1,2-ジメトキシエタン、ジエチルエーテル、2-エトキシエタン、テトラヒドロフラン、2-メチルテトラヒドロフラン等のエーテル類;ジメチルスルホキシド等のスルホキシド類;1,3-ジオキソラン、4-メチル-1,3-ジオキソラン等のオキソラン類;アセトニトリル、ニトロメタン、NMP等の含窒素類;ギ酸メチル、酢酸メチル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、リン酸トリエステル等のエステル類;ジグライム、トリグライム、テトラグライム等のグライム類;アセトン、ジエチルケトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類;スルホラン等のスルホン類;3-メチル-2-オキサゾリジノン等のオキサゾリジノン類;1,3-プロパンスルトン、4-ブタンスルトン、ナフタスルトン等のスルトン類等が挙げられる。これらの有機溶媒は、1種単独で用いてもよいし、2種以上を併用してもよい。
非水系電解液としては、カーボネート類にLiPF6を溶解した溶液が好ましく、該溶液はリチウムイオン二次電池の電解液として特に好適である。
本発明のバインダーに加えて、シリカ、酸化チタン、酸化アルミニウム、酸化ジルコニウム、酸化マグネシウム、酸化ニオブ、酸化バリウム等のセラミック粒子を混合しセパレータ上にコートすることで、セパレータの耐熱性を向上できる。
ポリ-γ-グルタミン酸ナトリウム(重量平均分子量230,000、以降「ポリグルタミン酸ナトリウム」と記載)の50wt%水溶液にアセチレンブラック(デンカ株式会社製、HS-100)及び蒸留水を添加し、アセチレンブラック:ポリグルタミン酸ナトリウム=1:1(重量比)となるように混合して、スラリーを得た。以降、特別に記載しない限り、混合の際には泡取り練太郎(THINKY製 ARE-310)を用いた。得られたスラリーをアルミニウム箔に塗布し80℃で乾燥し、さらに真空乾燥を行い、φ13mmで打ち抜いて作用電極とした。
尚、コインセルの各構成部材は以下の通りである。
<コインセルの各構成部材>
正極:上記で製造した13mmφのシート
セパレーター:16mmφガラスセパレータ(アドバンテック製 GA-100)
負極(対極兼、参照極):15mmφのLi箔
電解液:1mol/L LiPF6 EC/DEC=3/7(キシダ化学製)
<測定条件>
測定器:BAS製 ALS660E 電気化学アナライザー
開始電位:自然電位
終了電位:5V v.s.Li+/Li
スイープ速度:1mV/sec
測定温度:25℃
ポリ-γ-グルタミン酸リチウム(重量平均分子量190,000、以降ポリグルタミン酸リチウムと記載)の18wt%水溶液にアセチレンブラック(デンカ株式会社製、HS-100)及び蒸留水を添加し、アセチレンブラック:ポリグルタミン酸リチウム=1:1(重量比)となるように混合して、スラリーを得た。
得られたスラリーを用いて、実施例1-1と同様にしてコインセルを製造し、評価した。結果を表1に示す。
ポリグルタミン酸ナトリウムの水溶液の代わりにPVDFが12wt%の、N-メチル-2-ピロリドン(NMP)溶液(重量平均分子量280,000、フッ化ビニリデンのホモポリマー)を、蒸留水の代わりにNMPをそれぞれ用いた他は実施例1-1と同様にしてスラリーを調製し、コインセルの製造及び評価を行った。結果を表1に示す。
水(3.6部)及びポリグルタミン酸ナトリウム(3.6部)を混合して均一溶液とし、LiNi0.5Co0.2Mn0.3O2(63部)とアセチレンブラックHS-100(デンカ製)(3.4部)を加えて混合分散液とした。さらに水(26部)を加えて、正極組成物(1)を得た。
酸素濃度10ppm以下、水分濃度5ppm以下に管理された、Ar置換のグローブボックス中にて、コインセル(宝泉株式会社製、コインセル2032)の正極缶にガスケットをはめ、製造した電極である正極、セパレータを順に積層し、電解液を加えた。さらに負極、SUSスペーサー、ウェーブワッシャー、負極缶を重ね、コインセルかしめ機(宝泉株式会社製)を用いて、密閉することでコインセルを作製した。得られたコインセルの概略断面図を図1に示す。
尚、コインセルの各構成部材は以下の通りである。
<コインセルの各構成部材>
正極:上記で用意した13mmφのシート
セパレータ:16mmφガラスセパレータ(アドバンテック製 GA-100)
負極(対極兼、参照極):15mmφのLi箔
電解液:1mol/L LiPF6EC/DEC=3/7(キシダ化学製)
尚、LiNi0.5Co0.2Mn0.3O2 1gあたり160mAhとして電池容量を算出し、その容量をもとに1C(1時間で完全に放電する電流値)を算出した。
<測定条件>
充放電測定装置:BTS-2004(株式会社ナガノ製)
初期充放電
充電条件:0.1C-CC・CV Cut-off 4.3V
充電終了条件:電流値0.02C以下
放電条件:0.1C-CC Cut-off 2.0V
サイクル充放電
充電条件:1C-CC・CV Cut-off 4.3V
充電終了条件:電流値0.02C以下
放電条件:1C-CC Cut-off 2.0V
[塗膜の均一性]
正極組成物をAl箔に塗工した際に得られた塗膜を目視で確認した。Al箔上にダマやアルミの腐食等が確認できない場合を、均一な塗膜が形成されたとして「○」と評価した。
[結着性]
上述の正極組成物をAl箔に塗工及び乾燥して得られたプレス前の電極箔(20mm×90mm)について、セロテープ(ニチバン製 CT-15)を指の腹で滑らかになるように貼り、50mm/min、180°で引きはがし、引きはがし前後でそれぞれ13mmφの電極を2枚打ち抜き、Al集電体上の電極合材の残存率を算出した。尚、残存率は、平均50%以上残存しているのが好ましく、さらに好ましくは70%以上、特に好ましくは90%以上である。実施例2-1、及び後述する2-2では共に90%以上の残存率であり、電極加工時の粉落ちの抑制などにより、電池の歩留まり向上や良好なサイクル寿命が期待できる。一方で後述する比較例2では残存率が50%を大きく下回っており、電池の歩留り低下やサイクル寿命の低下につながるおそれがある。
水(13部)及びポリグルタミン酸リチウム(3.0部)の均一溶液(ポリグルタミン酸リチウム18wt%溶液)、LiNi0.5Co0.2Mn0.3O2(55部)とアセチレンブラックHS-100(デンカ製)(3.0部)を加えて混合分散液とした。さらに水(26部)を加えて、正極組成物(2)を得た。
PVDF(重量平均分子量280,000、フッ化ビニリデンのホモポリマー)2.5部とNMP19部の均一溶液(PVDF12wt%NMP溶液)をLiNi0.5Co0.2Mn0.3O2(45部)とアセチレンブラックHS-100(デンカ製2.5部)に加えて混合分散した。さらにNMP(32部)を加えて混合し、正極組成物(3)を得た。
また、表2の溶媒の項目は、それぞれ正極組成物中の溶媒の含有割合(wt%)を表している。
下記表3-5の各項目も表2と同じ意味である。
また、製造における溶媒コスト、溶媒回収コストの観点から、水を溶媒として用いた実施例2-1及び2-2の正極組成物の製造コストを「○」と評価した。NMPを溶媒として用いた比較例2の正極組成物では、有機溶媒の回収の必要があるため製造コストを「×」と評価した。
初期放電容量は実施例2-1及び実施例2-2と比較例2とで同等の特性を示していることが分かる。
水(2.5部)及びポリグルタミン酸ナトリウム(2.5部)を混合して均一溶液とし、黒鉛(48部)を加えて混合分散液とした。さらに水(47.3部)を加えて、負極組成物を得た。
酸素濃度10ppm以下、水分濃度5ppm以下に管理された、Ar置換のグローブボックス中にて、コインセル(宝泉株式会社製、コインセル2032)の正極缶にガスケットをはめ、製造した電極である負極、セパレータを順に積層し、電解液を加えた。さらにLi金属、SUSスペーサー、ウェーブワッシャー、負極缶を重ね、コインセルかしめ機(宝泉株式会社製)を用いて、密閉することでコインセルを作製した。得られたコインセルの概略断面図を図1に示す。
尚、コインセルの各構成部材は以下の通りである。
<コインセルの各構成部材>
負極:上記で用意した14mmφのシート
セパレータ:16mmφガラスセパレータ(アドバンテック製 GA-100)
対極兼、参照極:15mmφに打ち抜いたLi金属
電解液:1mol/L LiPF6EC/DEC=3/7(キシダ化学製)
尚、評価した放電容量は、下記条件では初回の充放電の不可逆容量が大きいため、2サイクル目の放電容量を採用した。また、容量サイクル維持率は下記サイクル充放電において(40回目の放電容量)/(10回目の放電容量)を容量サイクル維持率として算出した。
尚、黒鉛1gあたり320mAhとして電池容量を算出し、その容量をもとに1C(1時間で完全に放電する電流値)を算出した。
<測定条件>
30℃雰囲気下
初期充放電
充電条件:0.1C-CC・CV Cut-off 0.01V
充電終了条件:電流値0.02C以下
放電条件:0.1C-CC Cut-off 1.0V
サイクル充放電
充電条件:1C-CC・CV Cut-off 0.01V
充電終了条件:電流値0.02C以下
放電条件:1C-CC Cut-off 1.0V
[塗膜の均一性]
負極組成物をCu箔に塗工した際に得られた塗膜を目視で確認した。Cu箔上にダマやアルミの腐食等が確認できない場合を、均一な塗膜が形成されたとして「○」と評価した。
バインダーとして、ポリグルタミン酸ナトリウムの代わりにPVDF(重量平均分子量280,000、フッ化ビニリデンのホモポリマー)を用い、活物質、バインダー及び溶媒の比が表3となるように負極組成物を調製した以外は実施例2-3と同様にして電極及びコインセルを製造し、評価した。結果を表3に示す。
バインダーとして、ポリグルタミン酸ナトリウムの代わりにPVDF#2(重量平均分子量280,000、フッ化ビニリデンのホモポリマーを変性したもの)を用い、活物質、バインダー及び溶媒の比が表3となるように負極組成物を調製した以外は実施例2-3と同様にして電極及びコインセルを製造し、評価した。結果を表3に示す。
活物質として、LiNi0.5Co0.2Mn0.3O2の代わりにLiNi0.5Mn1.5O4を用い、活物質、導電助剤、バインダー及び溶媒の比が表4となるにした以外は、実施例2-1と同様にして正極組成物を調製した。別途、比較例2-2の負極組成物も用意した。
マイクロメーター付フィルムアプリケーター(テスター産業製、SA-204)と自動塗工装置(テスター産業製、PI-1210)を用いて、比較例2-2の負極組成物を11μmのCu箔に塗工し、80℃×10分乾燥し、プレスを室温で行い、1mAh/cm2、空隙率35%の電極を作製した。得られた電極を14mmφに打ち抜いて、150℃5時間真空乾燥を行った。これを負極に用いた。
酸素濃度10ppm以下、水分濃度5ppm以下に管理された、Ar置換のグローブボックス中にて、コインセル(宝泉株式会社製、コインセル2032)の正極缶にガスケットをはめ、正極、セパレータを順に積層し、電解液を加えた。さらに負極、SUSスペーサー、ウェーブワッシャー、負極缶を重ね、コインセルかしめ機(宝泉株式会社製)を用いて、密閉することでコインセルを作製した。得られたコインセルの概略断面図を図1に示す。
尚、コインセルの各構成部材は以下の通りである。
<コインセルの各構成部材>
正極:実施例2-4の正極組成物を用いて製造した13mmφのシート
セパレータ:16mmφガラスセパレータ(アドバンテック製 GA-100)
負極:比較例2-2の負極組成物を用いて製造した14mmφのシート
電解液:1mol/L LiPF6EC/DEC=3/7(キシダ化学製)
尚、LiNi0.5Mn1.5O4 1gあたり135mAhとして電池容量を算出し、その容量をもとに1C(1時間で完全に放電する電流値)を算出した。
<測定条件>
30℃雰囲気下
初期充放電
充電条件:0.1C-CC・CV Cut-off 4.8V
充電終了条件:電流値0.02C以下
放電条件:0.1C-CC Cut-off 2.0V
×2回
サイクル充放電
充電条件:1C-CC・CV Cut-off 4.8V
充電終了条件:電流値0.02C以下
放電条件:1C-CC Cut-off 2.0V
尚、LiNi0.5Mn1.5O4 1gあたり135mAhとして電池容量を算出し、その容量をもとに1C(1時間で完全に放電する電流値)を算出した。
<測定条件>
高温サイクル試験
60℃雰囲気下
初期充放電
充電条件:0.1C-CC・CV Cut-off 4.8V
充電終了条件:電流値0.02C以下
放電条件:0.1C-CC Cut-off 2.0V
×4回
サイクル充放電
充電条件:1C-CC・CV Cut-off 4.8V
充電終了条件:電流値0.02C以下
放電条件:1C-CC Cut-off 2.0V
[塗膜の均一性]
正極組成物をAl箔に塗工した際に得られた塗膜を目視で確認した。Al箔上にダマやアルミの腐食等が確認できない場合を、均一な塗膜が形成されたとして「○」と評価した。
バインダーとして、ポリグルタミン酸ナトリウムの代わりにPVDF(重量平均分子量280,000、フッ化ビニリデンのホモポリマー)を用い、溶媒として、水の代わりにNMPを用い、活物質、導電助剤、バインダー及び溶媒の比が表4となるようした以外は、実施例2-4と同様にして正極組成物を調製し、且つコインセルを製造し、評価した。結果を表4に示す。
活物質として、LiNi0.5Mn1.5O4の代わりにLiFePO4を用い、活物質、導電助剤、バインダー及び溶媒の比が表5となるようにした以外は、実施例2-4と同様にして正極組成物を調製した。
得られた正極組成物を用いて、実施例2-4と同様にして電極及びコインセルを製造し、評価した。結果を表5に示す。
尚、LiFePO4 1gあたり150mAhとして電池容量を算出し、その容量をもとに1C(1時間で完全に放電する電流値)を算出した。
<測定条件>
30℃雰囲気下
初期充放電
充電条件:0.1C-CC・CV Cut-off 4.8V
充電終了条件:電流値0.02C以下
放電条件:0.1C-CC Cut-off 2.0V
×2回
サイクル充放電
充電条件:1C-CC・CV Cut-off 4.8V
充電終了条件:電流値0.02C以下
放電条件:1C-CC Cut-off 2.0V
尚、LiFePO4 1gあたり150mAhとして電池容量を算出し、その容量をもとに1C(1時間で完全に放電する電流値)を算出した。
<測定条件>
高温サイクル試験
60℃雰囲気下
初期充放電
充電条件:0.1C-CC Cut-off 3.8V
放電条件:0.1C-CC Cut-off 2.0V
×2回
サイクル充放電
充電条件:1C-CC Cut-off 3.8V
放電条件:1C-CC Cut-off 2.0V
バインダーとして、ポリグルタミン酸ナトリウムの代わりにPVDF(重量平均分子量280,000、フッ化ビニリデンのホモポリマー)を用い、溶媒として、水の代わりにNMPを用い、活物質、導電助剤、バインダー及び溶媒の比が表5となるようした以外は、実施例2-5と同様に正極組成物を調製し、且つコインセルを製造し、評価した。結果を表5に示す。
負極として、Li箔の代わりに比較例2-3で製造した負極を用いた他は、実施例2-1と同様にしてコインセルを製造した。
尚、LiNi0.5Co0.2Mn0.3O2 1gあたり160mAhとして電池容量を算出し、その容量をもとに1C(1時間で完全に放電する電流値)を算出した。
<測定条件>
30℃雰囲気下
初期充放電
充電条件:0.1C-CC・CV Cut-off 4.3V
充電終了条件:電流値0.02C以下
放電条件:0.1C-CC Cut-off 2.0V
×2回
サイクル充放電
充電条件:1C-CC・CV Cut-off 4.3V
充電終了条件:電流値0.02C以下
放電条件:1C-CC Cut-off 2.0V
尚、LiNi0.5Co0.2Mn0.3O2 1gあたり190mAhとして電池容量を算出し、その容量をもとに1C(1時間で完全に放電する電流値)を算出した。
<測定条件>
高電圧サイクル試験
30℃雰囲気下
初期充放電
充電条件:0.1C-CC Cut-off 4.5V
充電終了条件:電流値0.02C以下
放電条件:0.1C-CC Cut-off 2.0V
×2回
サイクル充放電
充電条件:1C-CC Cut-off 4.5V
充電終了条件:電流値0.02C以下
放電条件:1C-CC Cut-off 2.0V
×60回
負極として、Li箔の代わりに比較例2-3で製造した負極を用いた他は、比較例2と同様にしてコインセルを製造し、実施例2-6と同じ評価を実施した。結果を表6に示す。
実施例2-6で製造したコインセルについて、下記条件で4.3V、4.4V及び4.5Vまでそれぞれ充電した。充電したコインセルを60℃及び80℃のそれぞれで96時間それぞれ放置し、放置期間の自己放電量を比較した。結果を表7に示す。
<測定条件>
充電条件:0.1C-CC Cut-off 4.5V、4.4V、4.3V
充電終了条件:電流値0.02C以下
放電条件:0.1C-CC Cut-off 2.0V
×2回
充電条件:0.1C-CC Cut-off 4.5V、4.4V、4.3V
充電終了条件:電流値0.02C以下
60℃又は80℃で96時間放置
放電条件:0.1C-CC Cut-off 2.0V
充電条件:0.1C-CC Cut-off 4.5V、4.4V、4.3V
充電終了条件:電流値0.02C以下
×2回
比較例2-6で製造したコインセルについて、実施例2-7と同様の評価を実施した。結果を表7に示す。
以上のことから、ポリグルタミン酸ナトリウムバインダーは、高電位・高温においてリチウムイオン電池の耐久性を向上させる可能性がある。
本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。
例えば、実施例はリチウムイオン二次電池の正極用バインダーを例にとって説明したが、これに限定されるものではなく、その他の電気化学素子、例えばリチウムイオン電池の負極用バインダー、リチウムイオン電池のセパレータコート用バインダー、電気二重層キャパシタのバインダー等としても好適に用いることができる。特に、リチウムイオン電池のセパレータコート用バインダーやキャパシタ用バインダー等、酸化環境にさらされる他の電気デバイスには好適に用いることができる。
Claims (28)
- カルボキシル基及び/若しくはその塩を有するポリマーと、アミド基及び/若しくはアミド結合を有するポリマー、又は
カルボキシル基及び/若しくはその塩、並びにアミド基及び/若しくはアミド結合を有するポリマーを含有する電気化学素子用バインダー。 - さらに水を含む請求項1に記載の電気化学素子用バインダー。
- 前記金属イオンが、アルカリ金属イオン又はアルカリ土類金属イオンである請求項3に記載の電気化学素子用バインダー。
- 前記金属イオンが、アルカリ金属イオンである請求項3又は4に記載の電気化学素子用バインダー。
- 前記金属イオンが、Liイオン又はNaイオンである請求項3~5のいずれかに記載の電気化学素子用バインダー。
- 前記カルボキシル基の一部がエステル化している請求項1~6のいずれかに記載の電気化学素子用バインダー。
- 前記カルボキシル基及び/又はその塩、並びにアミド基及び/又はアミド結合を有するポリマーが、グルタミン酸の中和物及びアスパラギン酸の中和物から選択される1以上のアミノ酸がα位、β位、又はγ位でアミド結合した重合体である請求項1~7のいずれかに記載の電気化学素子用バインダー。
- 前記ポリマーに含まれる芳香族炭化水素基を含む繰り返し単位が20%以下である請求項1~8のいずれかに記載の電気化学素子用バインダー。
- 前記ポリマーの重量平均分子量(Mw、PEG換算)が50,000~9,000,000である請求項1~9のいずれかに記載の電気化学素子用バインダー。
- 請求項1~10のいずれかに記載の電気化学素子用バインダーを含むリチウムイオン電池電極用バインダー。
- 請求項11に記載のリチウムイオン電池電極用バインダーを含有するリチウムイオン電池用電極組成物。
- 請求項12に記載のリチウムイオン電池用電極組成物を用いた、リチウムイオン電池用電極。
- 請求項1~10のいずれかに記載の電気化学素子用バインダーを含有するリチウムイオン電池セパレータ用組成物用バインダー。
- 請求項14に記載のリチウムイオン電池セパレータ組成物用バインダーを含むリチウムイオン電池セパレータ用組成物。
- 請求項15に記載したリチウムイオン電池セパレータ用組成物を用いたリチウムイオン電池用セパレータ。
- 請求項1~10のいずれかに記載の電気化学素子用バインダーを含むリチウムイオン電池電極保護膜用バインダー。
- 請求項17に記載のリチウムイオン電池電極保護膜用バインダーを含むリチウムイオン電池電極保護膜用組成物。
- 請求項18に記載のリチウムイオン電池電極保護膜用組成物を用いたリチウムイオン電池電極保護膜。
- 請求項1~10のいずれかに記載の電気化学素子用バインダーを用いたリチウムイオン電池。
- 請求項20に記載のリチウムイオン電池を備える電気機器。
- 請求項20に記載のリチウムイオン電池を備える車両。
- 請求項1~10のいずれかに記載の電気化学素子用バインダーを含む電気二重層キャパシタ用バインダー。
- 請求項23に記載した電気二重層キャパシタ用バインダーを含む電気二重層キャパシタ電極用組成物。
- 請求項24に記載の電気二重層キャパシタ電極用組成物を用いた電気二重層キャパシタ電極。
- 請求項25に記載した電気二重層キャパシタ電極を備える電気二重層キャパシタ。
- 請求項26に記載した電気二重層キャパシタを用いた電気機器。
- 請求項26に記載した電気二重層キャパシタを用いた車両。
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CN112094372A (zh) * | 2019-06-17 | 2020-12-18 | 荒川化学工业株式会社 | 锂离子电池用粘合剂水溶液、负极用浆料、负极、负极用材料以及锂离子电池及其制造方法 |
WO2024033741A1 (ja) * | 2022-08-10 | 2024-02-15 | 株式会社半導体エネルギー研究所 | 電池および二次電池の作製方法 |
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EP4301372A1 (en) | 2021-03-03 | 2024-01-10 | United Therapeutics Corporation | A dry powder composition of trestinil and its prodrug thereof and further comprising comprising (e)-3,6-bis[4-(n-carbonyl-2-propenyl)amidobutyl]-2,5-diketopiperazine (fdkp) |
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JP2020205257A (ja) * | 2019-06-17 | 2020-12-24 | 荒川化学工業株式会社 | リチウムイオン電池用熱架橋性バインダー水溶液、リチウムイオン電池負極用熱架橋性スラリー、リチウムイオン電池用負極、リチウムイオン電池負極用材料、並びにリチウムイオン電池及びその製造方法 |
JP7238854B2 (ja) | 2019-06-17 | 2023-03-14 | 荒川化学工業株式会社 | リチウムイオン電池用熱架橋性バインダー水溶液、リチウムイオン電池負極用熱架橋性スラリー、リチウムイオン電池用負極、リチウムイオン電池負極用材料、並びにリチウムイオン電池及びその製造方法 |
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JPWO2017175838A1 (ja) | 2019-02-28 |
US10752733B2 (en) | 2020-08-25 |
EP3442062A1 (en) | 2019-02-13 |
EP3442062A4 (en) | 2019-12-18 |
KR20180133401A (ko) | 2018-12-14 |
CN108886149A (zh) | 2018-11-23 |
US20190085126A1 (en) | 2019-03-21 |
TW201807144A (zh) | 2018-03-01 |
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