WO2022172851A1 - 電池 - Google Patents
電池 Download PDFInfo
- Publication number
- WO2022172851A1 WO2022172851A1 PCT/JP2022/004213 JP2022004213W WO2022172851A1 WO 2022172851 A1 WO2022172851 A1 WO 2022172851A1 JP 2022004213 W JP2022004213 W JP 2022004213W WO 2022172851 A1 WO2022172851 A1 WO 2022172851A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- active material
- battery
- electrode active
- material layer
- Prior art date
Links
- 239000007774 positive electrode material Substances 0.000 claims abstract description 89
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 3
- 229910014367 LixNiyCozM1−y−zO2 Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 149
- 239000007773 negative electrode material Substances 0.000 description 33
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- -1 polyethylene Polymers 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000011230 binding agent Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 13
- 229920001973 fluoroelastomer Polymers 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 239000005062 Polybutadiene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
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- 239000003822 epoxy resin Substances 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
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- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
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- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- RXACTIULCNJUNO-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3-pentafluoroprop-1-ene Chemical group FC(F)=C.FC(F)C(F)=C(F)F RXACTIULCNJUNO-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
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- 239000005001 laminate film Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-NOHWODKXSA-N lead-200 Chemical compound [200Pb] WABPQHHGFIMREM-NOHWODKXSA-N 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001500 lithium hexafluoroborate Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
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- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 229940053662 nickel sulfate Drugs 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to batteries.
- a battery comprises a positive electrode, a negative electrode and a separator.
- the positive electrode has a positive electrode current collector and a positive electrode active material layer.
- the negative electrode has a negative electrode current collector and a negative electrode active material layer.
- a separator separates the positive and negative electrodes from each other.
- Patent Document 1 describes an example of a lithium ion secondary battery in which a positive electrode and a negative electrode are laminated.
- the positive electrode active material layer contains a lithium-nickel-based composite oxide having a layered crystal structure with a composition ratio of nickel element to the sum of nickel element, cobalt element and manganese element of 0.4.
- the length of the positive electrode in the longitudinal direction is 250 mm.
- the ratio of output to battery capacity is less than 25 W/Wh.
- Patent Document 2 describes an example of a lithium ion secondary battery in which a positive electrode and a negative electrode are laminated.
- the positive electrode active material contains a lithium-nickel-based composite oxide having a layered crystal structure with a composition ratio of nickel element to the sum of nickel element, cobalt element and manganese element of 0.8.
- Patent Document 3 describes an example of a lithium-ion secondary battery in which a positive electrode, a negative electrode, and a separator are wound.
- the positive electrode active material contains a lithium-nickel-based composite oxide having a layered structure with a composition ratio of nickel element to the sum of nickel element, cobalt element and aluminum element of 0.8.
- JP 2017-33827 A WO2015/156399 JP 2017-63041 A
- Batteries such as lithium-ion secondary batteries should have high capacity and high output. As a result of studies by the present inventors, it has become clear that the capacity and output of a battery are related to the length of the positive electrode active material layer in the longitudinal direction. On the other hand, Patent Documents 1 to 3 do not describe the relationship between the length of the positive electrode active material layer in the longitudinal direction and the capacity and output of the battery.
- One example of the object of the present invention is to provide a battery with high capacity and high output. Other objects of the present invention will become clear from the description herein.
- the positive electrode has the general formula Li x Ni y Co z M 1-yz O 2 (0.80 ⁇ y ⁇ 0.93, M is a metal element containing at least one element of Mn and Al).
- M is a metal element containing at least one element of Mn and Al.
- FIG. 1 is a plan view of a battery according to an embodiment
- FIG. FIG. 2 is a cross-sectional view taken along the line AA′ of FIG. 1
- It is a top view of the positive electrode which concerns on embodiment.
- 4 is a graph showing an example of the relationship between the length of the positive electrode active material layer in the longitudinal direction, the battery capacity, and the battery output when the battery has 16 positive electrode layers.
- 4 is a graph showing an example of the relationship between the length of the positive electrode active material layer in the longitudinal direction, the battery capacity, and the battery output when the battery has 23 positive electrode layers.
- 4 is a graph showing an example of the relationship between the length of the positive electrode active material layer in the longitudinal direction, the battery capacity, and the battery output when the battery has 31 positive electrode layers.
- 4 is a graph showing an example of the relationship between the length of the positive electrode active material layer in the longitudinal direction, the battery capacity, and the battery output when the battery has 42 positive electrode layers.
- 4 is a graph showing an example of the relationship between the length of the positive electrode active material layer in the longitudinal direction, the battery capacity, and the battery output when the battery has 50 positive electrode layers.
- 4 is a graph showing an example of the relationship between the length of the positive electrode active material layer in the longitudinal direction, the battery capacity, and the battery output when the battery has 54 layers of positive electrode.
- Relationship between the length of the positive electrode active material layer in the longitudinal direction and the ratio of the output to the capacity of the battery when the laminate has 16 layers, 23 layers, 31 layers, 42 layers, 50 layers, and 54 layers of the positive electrode It is a graph which shows an example of.
- An example of the relationship between the length of the positive electrode active material layer in the longitudinal direction and the cell temperature rise of the battery when the laminate has 16 layers, 23 layers, 31 layers, 42 layers, 50 layers, and 54 layers of the positive electrode. is a graph showing
- FIG. 1 is a plan view of the battery 10 according to the embodiment.
- FIG. 2 is a cross-sectional view taken along the line AA' of FIG.
- FIG. 3 is a plan view of the positive electrode 100 according to the embodiment.
- the first direction X indicates the length direction of the battery 10.
- the positive direction of the first direction X which is the direction indicated by the arrow indicating the first direction X, is the direction from the positive electrode lead 130 to the negative electrode lead 230, which will be described later.
- the negative direction of the first direction X which is opposite to the direction indicated by the arrow indicating the first direction X, is the direction from the negative lead 230 toward the positive lead 130 .
- the second direction Y intersects, or more specifically, is perpendicular to, the first direction X, and indicates the width direction of the battery 10 .
- a third direction Z intersects both the first direction X and the second direction Y, more specifically, is orthogonal to both, and indicates the thickness direction of the battery 10 .
- the white circle with a black dot indicating the third direction Z is the third direction Z positive direction from the back to the front of the paper, and the third direction is the direction from the front to the back of the paper. It indicates that it is in the negative Z direction.
- the white circle with X indicating the second direction Y indicates that the direction from the front to the back of the paper is the positive direction of the second direction Y, and the direction from the back to the front of the paper is the negative direction of the second direction Y. It shows that
- the battery 10 is arranged so that the thickness direction of the battery 10, that is, the third direction Z is parallel to the vertical direction. Also, the positive direction of the third direction Z, which is the direction indicated by the arrow indicating the third direction Z, is the upward direction in the vertical direction. On the other hand, the negative direction of the third direction Z, which is the opposite direction to the direction indicated by the arrow indicating the third direction Z, is downward in the vertical direction.
- the battery 10 will be described with reference to FIG.
- the battery 10 is a lithium ion secondary battery.
- the battery 10 includes a positive electrode lead 130, a negative electrode lead 230 and an exterior material 400.
- the positive lead 130 is electrically connected to the positive electrode 100 shown in FIG. 2 which will be described later.
- the positive electrode lead 130 is made of, for example, aluminum or an aluminum alloy.
- the negative electrode lead 230 is electrically connected to the negative electrode 200 shown in FIG. 2 which will be described later.
- the negative electrode lead 230 is made of, for example, copper, copper alloy, or nickel-plated material.
- the exterior material 400 has a rectangular shape with four sides.
- the positive electrode lead 130 is provided on the side of the exterior material 400 located on the negative direction side in the first direction X
- the negative electrode lead 230 is provided on the side of the exterior material 400 in the positive direction in the first direction X. It is provided on the side located on the side.
- the positive electrode lead 130 and the negative electrode lead 230 may be provided on a common side of the exterior material 400 (for example, the side located on the positive direction side or the negative direction side in the first direction X).
- the exterior material 400 accommodates the laminate 20 shown in FIG. 2, which will be described later, together with an electrolytic solution (not shown).
- the exterior material 400 includes, for example, a heat-fusible resin layer and a barrier layer, and is, for example, a laminated film including a heat-fusible resin layer and a barrier layer.
- the resin material that forms the heat-fusible resin layer is, for example, polyethylene (PE), polypropylene, or the like.
- the thickness of the heat-fusible resin layer is, for example, 20 ⁇ m or more and 200 ⁇ m or less.
- the barrier layer has, for example, a barrier property such as prevention of leakage of an electrolytic solution or entry of moisture from the outside. It is a barrier layer formed by The thickness of the barrier layer is, for example, 10 ⁇ m or more and 100 ⁇ m or less.
- the heat-sealable resin layer of the laminated film may be one layer, or two or more layers.
- the barrier layer of the laminated film may be one layer, or two or more layers.
- the electrolyte is, for example, a non-aqueous electrolyte.
- This non-aqueous electrolyte contains, for example, a lithium salt and a solvent that dissolves the lithium salt.
- Lithium salts are, for example, LiClO4, LiBF4 , LiBF6 , LiPF6 , LiCF3SO3 , LiCF3CO2 , LiAsF6 , LiSbF6 , LiB10Cl10 , LiAlCl4 , LiCl , LiBr, LiB ( C2 H5 ) 4 , CF3SO3Li , CH3SO3Li , LiC4F9SO3 , Li ( CF3SO2 ) 2N , Li ( C2F5SO2 ) 2N , lower fatty acid carboxylic acid Lithium and the like.
- Solvents that dissolve lithium salts include, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and methyl ethyl carbonate.
- EC ethylene carbonate
- PC propylene carbonate
- BC butylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- DEC diethyl carbonate
- DEC diethyl carbonate
- carbonates such as (MEC) and vinylene carbonate (VC); lactones such as ⁇ -butyrolactone and ⁇ -valerolactone; ethers such as trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran sulfoxides such as dimethylsulfoxide; oxolanes such as 1,3-dioxolane and 4-methyl-1,3-dioxolane; nitrogen-containing solvents such as acetonitrile, nitromethane, formamide, dimethylformamide; methyl formate, methyl acetate, acetic acid Organic acid esters such as ethyl, butyl acetate, methyl propionate, and ethyl propionate; phosphoric acid triesters and diglymes; triglymes; sulfolane such as sulfolane and methylsulfolane;
- the laminate 20 will be described with reference to FIG.
- the laminate 20 has a plurality of positive electrodes 100 , a plurality of negative electrodes 200 and separators 300 .
- the plurality of positive electrodes 100 and the plurality of negative electrodes 200 are alternately arranged in the third direction Z.
- the total number of positive electrodes 100 can be, for example, 16 or more and 54 or less.
- the total number of the plurality of negative electrodes 200 may be, for example, one more than the total number of positive electrodes 100 .
- the separator 300 separates the positive electrode 100 and the negative electrode 200 that are adjacent in the third direction Z from each other. In one example, the separator 300 is folded along the second direction Y and extended in a meandering manner so as to pass between the adjacent positive electrode 100 and negative electrode 200 . Alternatively, each of the plurality of separators 300 may be positioned between the adjacent positive electrode 100 and negative electrode 200 . Note that the laminate 20 may have only one positive electrode 100 and only one negative electrode 200 .
- the cathode electrode 100 has a cathode current collector 110 , a first cathode active material layer 122 and a second cathode active material layer 124 .
- the first positive electrode active material layer 122 is located on the upper surface of the positive electrode current collector 110 .
- the second positive electrode active material layer 124 is located on the lower surface of the positive electrode current collector 110 .
- the end of the positive current collector 110 on the negative side in the first direction X is connected to the positive lead 130 shown in FIG.
- the positive electrode current collector 110 is made of, for example, aluminum, stainless steel, nickel, titanium, or alloys thereof.
- the shape of the positive electrode current collector 110 is, for example, foil, flat plate, or mesh.
- the thickness of the positive electrode current collector 110 is, for example, 1 ⁇ m or more and 50 ⁇ m or less.
- the first positive electrode active material layer 122 contains a positive electrode active material, a binder resin, and a conductive aid.
- the details of the first positive electrode active material layer 122 are as follows. Unless otherwise specified, the following details describing the first positive electrode active material layer 122 also apply to the second positive electrode active material layer 124 .
- the positive electrode active material has the general formula Li x Ni y Co z M 1-yz O 2 (0.80 ⁇ y ⁇ 0.93, M is a metal element containing at least one element of Mn and Al). There is.)
- the composition ratio y is within the above range, the capacity per unit weight can be increased at low cost, and the crystal structure of the positive electrode active material can be stabilized.
- the composition ratio y is within the above range, it is possible to suppress deterioration in thermal stability in a charged state, compared to when the composition ratio y is larger than the above range.
- x is 1 ⁇ x ⁇ 1.2
- y and z are positive numbers satisfying y+z ⁇ 1.
- the positive electrode active material is, for example, a lithium-nickel-based composite oxide such as a lithium-nickel-cobalt-manganese composite oxide having a layered crystal structure represented by the above general formula.
- the first positive electrode active material layer 122 contains, for example, 90% by weight or more and 99% by weight or less of the positive electrode active material with respect to 100% by weight of the total weight of the first positive electrode active material layer 122 .
- the total basis weight of the first positive electrode active material layer 122 and the second positive electrode active material layer 124 is, for example, 25 mg/cm 2 or more and 50 mg/cm 2 or less.
- the binder resin contained in the first positive electrode active material layer 122 is, for example, polyethylene, polypropylene, polyethylene terephthalate (PET), polyethernitrile, polyacrylonitrile, polyimide, polyamide, cellulose, carboxymethylcellulose (CMC), ethylene-vinyl acetate Polymers, polyvinyl chloride, styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene copolymers, styrene-butadiene-styrene block copolymers and hydrogenated products thereof, Thermoplastic polymers such as styrene/isoprene/styrene block copolymers and hydrogenated products thereof; polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), tetrafluoroethylene/hexafluoropropylene copolymer
- binder resins are excellent in heat resistance, have a very wide potential window, are stable in both the positive electrode potential and the negative electrode potential, and can be used for the active material layer.
- binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.
- the amount of the binder resin contained in the first positive electrode active material layer 122 can be determined as appropriate.
- the first positive electrode active material layer 122 contains, for example, 0.1% by weight or more and 10.0% by weight or less of a binder resin with respect to 100% by weight of the total weight of the first positive electrode active material layer 122 .
- the conductive aid contained in the first positive electrode active material layer 122 is, for example, carbon black, ketjen black, acetylene black, natural graphite, artificial graphite, carbon fibers such as carbon nanotubes, carbon nanofibers, and carbon nanohorns.
- Graphite is, for example, flake graphite or spherical graphite. These substances may be used alone or in combination.
- the amount of the conductive aid contained in the first positive electrode active material layer 122 can be determined as appropriate.
- the first positive electrode active material layer 122 contains, for example, 0.1% by weight or more and 8.0% by weight or less of the conductive aid with respect to 100% by weight of the total weight of the first positive electrode active material layer 122 .
- the first positive electrode active material layer 122 contains a pH adjuster (eg, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, and fumaric acid).
- a pH adjuster eg, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, and fumaric acid.
- the longitudinal length L of the first positive electrode active material layer 122 is within a predetermined range as described later. When the longitudinal length L of the first positive electrode active material layer 122 is within the predetermined range, high capacity and high output of the battery 10 can be achieved.
- the length W of the first positive electrode active material layer 122 in the lateral direction is 70 mm or more and 120 mm or less.
- the thickness of the first positive electrode active material layer 122 can be determined as appropriate.
- the thickness of the first positive electrode active material layer 122 is, for example, 35 ⁇ m or more and 65 ⁇ m or less.
- the negative electrode 200 has a negative electrode current collector 210 , a first negative electrode active material layer 222 and a second negative electrode active material layer 224 .
- the first negative electrode active material layer 222 is located on the upper surface of the negative electrode current collector 210 .
- the second negative electrode active material layer 224 is located on the lower surface of the negative electrode current collector 210 .
- the end of the negative electrode current collector 210 on the positive side in the first direction X is connected to the negative electrode lead 230 shown in FIG.
- the negative electrode current collector 210 is made of, for example, copper, stainless steel, nickel, titanium, or alloys thereof.
- the shape of the negative electrode current collector 210 is, for example, foil, flat plate, or mesh.
- the thickness of the negative electrode current collector 210 in the third direction Z (third direction Z) is, for example, 1 ⁇ m or more and 50 ⁇ m or less.
- the first negative electrode active material layer 222 contains a negative electrode active material and a binder resin.
- the first negative electrode active material layer 222 may further contain a conductive aid, if necessary. Details of the first negative electrode active material layer 222 are as follows. Unless otherwise specified, the following details describing the first anode active material layer 222 also apply to the second anode active material layer 224 .
- negative electrode active materials include, but are not limited to, metals such as Si and Sn; metal oxides such as TiO, Ti2O3 , TiO2 , SiO2 , SiO, and SnO2 ; Composite oxides of lithium and transition metals such as Ti 5 O 12 and Li 7 MnN; Li—Pb alloys, Li—Al alloys, Li; carbon powder, graphite (natural graphite, artificial graphite), carbon black, activated carbon , carbon fiber, coke, soft carbon, hard carbon, and other carbon materials.
- metals such as Si and Sn
- metal oxides such as TiO, Ti2O3 , TiO2 , SiO2 , SiO, and SnO2
- Composite oxides of lithium and transition metals such as Ti 5 O 12 and Li 7 MnN
- These negative electrode active materials may be used singly or in combination of two or more.
- Elements to be alloyed with lithium are not limited to the following, but specific examples include Si, Ge, Sn, Pb, Al, In, Zn, H, Ca, Sr, Ba, Ru, Rh, Ir, Pd, Pt, Ag, Au, Cd, Hg, Ga, Tl, C, N, Sb, Bi, O, S, Se, Te, Cl and the like.
- the first negative electrode active material layer 222 contains, for example, 90% by weight or more and 99% by weight or less of the negative electrode active material with respect to 100% by weight of the total weight of the first negative electrode active material layer 222 .
- the total basis weight of the first negative electrode active material layer 222 and the second negative electrode active material layer 224 is, for example, 12 mg/cm 2 or more and 28 mg/cm 2 or less.
- the binder resin contained in the first negative electrode active material layer 222 may be, for example, the binder resin exemplified for the binder resin contained in the first positive electrode active material layer 122. can be done.
- the binder resin contained in the first negative electrode active material layer 222 is, for example, a styrene-based polymer (styrene-butadiene rubber, styrene-vinyl acetate copolymer, styrene -acrylic copolymer, etc.), acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, (meth)acrylic polymers (polyethyl acrylate, polyethyl methacrylate, polypropyl acrylate, polymethyl methacrylate (methyl methacrylate rubber), poly propyl methacrylate, polyisopropyl acrylate, polyisopropyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyhexyl acrylate, polyhexyl methacrylate, polyethylhexyl acrylate, polyethylhexyl acrylate, polyethyl
- polyvinylpyrrolidone polyacrylic acid (salt), polyethylene glycol, copolymer of (meth)acrylamide and/or (meth)acrylic acid salt [(meth)acrylamide polymer, (meth)acrylamide-(meth)acrylic acid Salt copolymer, alkyl (meth)acrylate (C1-4) ester-(meth)acrylate copolymer etc.], styrene-maleate copolymer, Mannich-modified polyacrylamide, formalin condensation type resin (urea-formalin resin, melamine-formalin resin, etc.), polyamide polyamine or dialkylamine-epichlorohydrin copolymer, polyethyleneimine, Casein, soybean protein, synthetic protein, and water-soluble polymers such as mannangalactan derivatives can be used.
- These water-based binder resins may be in the form of an emulsion.
- these water-based binders may be used individually by 1 type, and may be used in combination
- the amount of the binder resin contained in the first negative electrode active material layer 222 can be determined as appropriate.
- the first negative electrode active material layer 222 contains, for example, 0.1% by weight or more and 10.0% by weight or less of binder resin with respect to 100% by weight of the total weight of the first negative electrode active material layer 222 .
- the longitudinal length of the first negative electrode active material layer 222 can be appropriately determined according to the longitudinal length L of the first positive electrode active material layer 122 .
- the length of the first negative electrode active material layer 222 in the short direction can be appropriately determined according to the length W of the first positive electrode active material layer 122 in the short direction.
- the thickness of the first negative electrode active material layer 222 can be determined as appropriate.
- the thickness of the first negative electrode active material layer 222 is, for example, 40 ⁇ m or more and 75 ⁇ m or less.
- the separator 300 has a function of electrically insulating the positive electrode 100 and the negative electrode 200 and allowing ions (for example, lithium ions) to pass through.
- Separator 300 can be, for example, a porous separator.
- the shape of the separator 300 can be appropriately determined according to the shape of the positive electrode 100 or the negative electrode 200, and can be rectangular, for example.
- the base material 310 includes a porous resin layer containing polyolefin as a main component.
- the porous resin layer contains 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more of polyolefin with respect to 100% by weight of the total weight of the porous resin layer. , may contain 100% by weight of polyolefin with respect to 100% by weight of the total weight of the porous resin layer.
- the porous resin layer may be a single layer or two or more layers. Examples of polyolefin include polypropylene and polyethylene.
- the thickness (third direction Z) of the separator 300 can be determined as appropriate, and can be, for example, 8.0 ⁇ m or more and 45.0 ⁇ m or less.
- FIG. 4 is a graph showing an example of the relationship between the length of the positive electrode active material layer in the longitudinal direction, the battery capacity, and the battery output when the battery has 16 positive electrode layers.
- FIG. 5 is a graph showing an example of the relationship between the longitudinal length of the positive electrode active material layer, the battery capacity, and the battery output when the battery has 23 positive electrode layers.
- FIG. 6 is a graph showing an example of the relationship between the longitudinal length of the positive electrode active material layer, the battery capacity, and the battery output when the battery has 31 positive electrode layers.
- FIG. 7 is a graph showing an example of the relationship between the longitudinal length of the positive electrode active material layer, the battery capacity, and the battery output when the battery has 42 positive electrode layers.
- FIG. 8 is a graph showing an example of the relationship between the longitudinal length of the positive electrode active material layer, the battery capacity, and the battery output when the battery has 50 positive electrode layers.
- FIG. 9 is a graph showing an example of the relationship between the length of the positive electrode active material layer in the longitudinal direction, the battery capacity, and the battery output when the battery has 54 layers of positive electrodes.
- the horizontal axis of the graph indicates the length (unit: mm) of the positive electrode active material layer in the longitudinal direction.
- the vertical axis on the left side of the graph indicates the battery capacity (unit: Wh).
- the vertical axis on the right side of the graph indicates battery output (unit: W).
- the mixture was thoroughly mixed, heated at a temperature increase rate of 5°C/min, pre-fired at 700°C for 2 hours in an oxygen atmosphere, then heated at a temperature increase rate of 3°C/min, and fired at 750°C for 10 hours. Then, it was cooled to room temperature to obtain an NMC composite oxide as a lithium-nickel-cobalt-manganese composite oxide.
- SBR styrene-butadiene rubber
- CMC carboxymethyl cellulose
- a positive electrode was obtained by cutting out a part of the positive electrode plate produced as described above.
- As the positive electrode 12 kinds of positive electrode having different longitudinal directions of the positive electrode active material layer were prepared as plotted in each graph of FIGS. For these positive electrodes, the length of the positive electrode active material layer in the lateral direction was 88 mm.
- a negative electrode was obtained by cutting out a part of the negative electrode plate produced as described above.
- As the negative electrode 12 types were prepared for each of the 12 types of positive electrode described above, the longitudinal direction of the negative electrode active material layer being 102% of the longitudinal direction of the positive electrode active material layer. For these negative electrodes, the length of the negative electrode active material layer in the lateral direction was 90 mm.
- a laminate was produced by alternately laminating a predetermined number of layers of the positive electrode and a predetermined number of layers of the negative electrode with separators interposed therebetween. 4, 5, 6, 7, 8 and 9, the total number of positive electrodes was 16, 23, 31, 42, 50 and 54, respectively. In any of FIGS. 4 to 9, the total number of negative electrodes is one more than the total number of positive electrodes.
- This laminate was housed in a laminate film as an exterior material, and an electrolytic solution was injected into the laminate to fabricate a battery.
- the capacity of the battery 10 was measured as follows. First, the battery was charged from 1/3C to 4.2V under constant current-constant voltage (CC-CV) conditions at 25°C. After that, under constant current conditions, the battery was discharged to 2.5 V at 1/3 C and the capacity was measured.
- CC-CV constant current-constant voltage
- the output of the battery 10 was measured as follows. First, the battery was charged from 1/3C to 4.2V under constant current-constant voltage (CC-CV) conditions at 25°C. After that, it was discharged at 1 C for 30 minutes under constant current conditions to adjust the charge depth to 50%. After that, it was discharged at 1C for 10 seconds.
- V1 (unit: V) be the voltage immediately before discharging at 1 C for 10 seconds after adjustment to a charge depth of 50%.
- the voltage after discharging at 1C for 10 seconds is assumed to be V2 (unit: V).
- ⁇ V (unit: V1) be the difference between the voltage V1 and the voltage V2.
- a DC resistance DCR (unit: ⁇ ) was calculated by dividing this difference ⁇ V by the discharged current value.
- the capacity of the battery increases in proportion to the length of the positive electrode active material layer in the longitudinal direction. Also, the constant of proportionality is constant regardless of the number of positive electrodes.
- the output of the battery is maximized when the length of the positive electrode active material layer in the longitudinal direction is 400 mm to 600 mm. is a concave function in the range of about 200 mm to 1000 mm.
- the maximum value of the battery output and the longitudinal length of the positive electrode active material layer at which the battery output reaches the maximum value vary depending on the number of positive electrodes.
- the battery output when the length of the positive electrode active material layer in the longitudinal direction is 300 mm or more and 740 mm or less is about 80% or more of the maximum value of the battery output.
- the output of the battery is about 90% or more of the maximum value of the output of the battery. Therefore, from the viewpoint of high capacity and high output of the battery, the longitudinal length of the positive electrode active material layer can be 300 mm or more and 740 mm or less, preferably 390 mm or more and 640 mm or less.
- FIG. 10 shows the ratio of the length of the positive electrode active material layer in the longitudinal direction and the output to the capacity of the battery when the laminate has 16 layers, 23 layers, 31 layers, 42 layers, 50 layers, and 54 layers of the positive electrode. , and is a graph showing an example of the relationship between .
- the horizontal axis of the graph indicates the longitudinal length (unit: mm) of the positive electrode active material layer.
- the vertical axis of the graph indicates the ratio (unit: W/Wh) of the output (unit: W) to the battery capacity (unit: Wh).
- the ratio of output to battery capacity is approximately 3 W/ Wh or more and 17 W/Wh or less.
- the ratio of output to capacity of the battery is less than 3 W/Wh, the resistance of the battery is too high, and the battery cannot follow the load characteristics when used as a vehicle battery.
- the number of positive electrodes can be 23 or more, preferably 31 or more.
- the ratio of output to capacity of the battery is greater than 17 W/Wh, the capacity per unit area of the battery may be insufficient.
- the number of positive electrodes can be 54 or less, preferably 50 or less.
- FIG. 11 shows the length of the positive electrode active material layer in the longitudinal direction, the cell temperature rise of the battery, and the It is a graph which shows an example of the relationship of.
- the horizontal axis of the graph indicates the length (unit: mm) of the positive electrode active material layer in the longitudinal direction.
- the vertical axis of the graph indicates the cell temperature rise (unit: K) of the battery.
- the cell temperature rise of the battery was measured as follows. First, the battery was charged from 1/3C to 4.2V under constant current-constant voltage (CC-CV) conditions at 25°C. After that, under constant current conditions, the maximum cell temperature was measured when the battery was continuously discharged at 6C to 2.5V. The difference between this maximum cell temperature and the cell temperature after charging and before continuous discharging was taken as the cell temperature rise.
- CC-CV constant current-constant voltage
- the cell temperature rise of the battery is approximately 230 K or less when the length of the positive electrode active material layer in the longitudinal direction is 300 mm or more and 740 mm or less.
- the number of positive electrodes 100 can be 23 or more, preferably 31 or more.
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Abstract
Description
正極電極を備え、
前記正極電極は、一般式LixNiyCozM1-y-zO2(0.80≦y≦0.93、Mは、Mn及びAlのうちの少なくとも1つの元素を含む金属元素である。)によって示される正極活物質を含む正極活物質層を有し、
前記正極活物質層の長手方向の長さが300mm以上740mm以下である、電池である。
硫酸ニッケル、硫酸コバルト及び硫酸マンガンを溶解した水溶液(1.0mol/L)にpH11.0となるように水酸化ナトリウム及びアンモニアを連続的に共有し、共沈法によりニッケルとコバルトとマンガンとのモル比が80:10:10で固溶してなる金属複合水酸化物を作製した。この金属複合酸化物と、水酸化リチウムと、を、Li以外の金属(Ni、Co、Mn)の合計のモル数と、Liのモル数と、の比が1:1となるように秤量した後、充分混合し、昇温速度5℃/minで昇温し、酸素雰囲気で700℃、2時間仮焼成した後、昇温速度3℃/minで昇温し、750℃で10時間本焼成し、室温まで冷却して、リチウムニッケルコバルトマンガン複合酸化物としてNMC複合酸化物を得た。
上記のようにして得られた正極活物質を97重量%と、導電助剤であるカーボンナノチューブ1.2重量%と、バインダー樹脂であるポリフッ化ビニリデン(PVdF)1.8重量%と、スラリー粘度調整溶媒であるN-メチル-2ピロリドン(NMP)を適量と、混合して、正極活物質スラリーを作製した。この正極活物質スラリーを正極集電体であるアルミニウム箔の両面に塗布し乾燥させた。その後、プレス処理を行い、正極板を、正極板の両面における正極活物質層の目付量が32.1mg/cm2となるように作製した。
負極活物質として、黒鉛粉末と、SiO粉末と、を用いた。これらの粉末と、バインダー樹脂であるスチレンブタジエンラバー(SBR)及びカルボキシメチルセルロース(CMC)と、を、黒鉛:SiO:SBR:CMC=94:3:2:1の割合となるように均一に混合し、溶媒であるNMPに添加して負極活物質スラリーを作製した。この負極活物質スラリーを負極集電体である銅箔の両面に塗布し乾燥させた。その後、プレス処理を行い、負極板を、負極板の負極活物質層の目付量が19.8mg/cm2となるように作製した。
上記のように作製した正極板の一部を切り出して正極電極を得た。正極電極としては、図4~図9の各グラフでプロットされているように、正極活物質層の長手方向が異なる12種類を用意した。これらの正極電極について、正極活物質層の短手方向の長さは、いずれも88mmとした。また、上記のように作製した負極板の一部を切り出して負極電極を得た。負極電極としては、上述した12種類の正極電極の各々に対して、負極活物質層の長手方向が正極活物質層の長手方向の102%となる12種類を用意した。これらの負極電極について、負極活物質層の短手方向の長さは、いずれも90mmとした。セパレータを介して所定の層数の正極電極及び所定の層数の負極電極を交互に積層することで積層体を作製した。図4、図5、図6、図7、図8及び図9において、正極電極の総数は、それぞれ、16、23、31、42、50及び54とした。図4~図9のいずれにおいても、負極電極の総数は正極電極の総数よりも1つだけ多くした。この積層体を外装材であるラミネートフィルムに格納し、電解液を注入することで電池を作製した。
20 積層体
100 正極電極
110 正極集電体
122 第1正極活物質層
124 第2正極活物質層
130 正極リード
200 負極電極
210 負極集電体
222 第1負極活物質層
224 第2負極活物質層
230 負極リード
300 セパレータ
310 基材
400 外装材
X 第1方向
Y 第2方向
Z 第3方向
Claims (8)
- 正極電極を備え、
前記正極電極は、一般式LixNiyCozM1-y-zO2(0.80≦y≦0.93、Mは、Mn及びAlのうちの少なくとも1つの元素を含む金属元素である。)によって示される正極活物質を含む正極活物質層を有し、
前記正極活物質層の長手方向の長さが300mm以上740mm以下である、電池。 - 請求項1に記載の電池において、
16枚以上54枚以下の前記正極電極を備える、電池。 - 請求項1又は2に記載の電池において、
23枚以上54枚以下の前記正極電極を備える、電池。 - 請求項1~3のいずれか一項に記載の電池において、
前記正極活物質層の短手方向の長さが70mm以上120mm以下である、電池。 - 請求項1~4のいずれか一項に記載の電池において、
前記正極活物質層は、前記一般式で示される層状結晶構造を有するリチウムニッケルコバルトマンガン複合酸化物を含む、電池。 - 請求項1~5のいずれか一項に記載の電池において、
前記正極活物質層は、前記正極活物質層の総重量100重量%に対して、90重量%以上の前記正極活物質を含む、電池。 - 請求項1~6のいずれか一項に記載の電池において、
前記正極活物質層の目付量が25mg/cm2以上50mg/cm2以下である、電池。 - 請求項1~7のいずれか一項に記載の電池において、
複数の前記正極電極と、複数の負極電極とが交互に積層されている、電池。
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