JP7434165B2 - 少なくとも部分的にコーティングされた電極活物質の製造方法 - Google Patents
少なくとも部分的にコーティングされた電極活物質の製造方法 Download PDFInfo
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- JP7434165B2 JP7434165B2 JP2020551277A JP2020551277A JP7434165B2 JP 7434165 B2 JP7434165 B2 JP 7434165B2 JP 2020551277 A JP2020551277 A JP 2020551277A JP 2020551277 A JP2020551277 A JP 2020551277A JP 7434165 B2 JP7434165 B2 JP 7434165B2
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- SGLVSFQJGWNNJH-UHFFFAOYSA-N cyclopentane;tungsten Chemical compound [W].[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 SGLVSFQJGWNNJH-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
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- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PPJPTAQKIFHZQU-UHFFFAOYSA-N bis(tert-butylimino)tungsten;dimethylazanide Chemical compound C[N-]C.C[N-]C.CC(C)(C)N=[W]=NC(C)(C)C PPJPTAQKIFHZQU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- YQZUTDPJTAZPQJ-UHFFFAOYSA-L cyclopentane;dichloromolybdenum Chemical compound Cl[Mo]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 YQZUTDPJTAZPQJ-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ABGLZESYHATICB-UHFFFAOYSA-N ethanol;molybdenum Chemical compound [Mo].CCO.CCO.CCO.CCO.CCO ABGLZESYHATICB-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- XWAZCLPCQDERBK-UHFFFAOYSA-N hexamethyltungsten Chemical compound C[W](C)(C)(C)(C)C XWAZCLPCQDERBK-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- BEXBKUKHTOBXHW-LBPRGKRZSA-N tert-butyl n-[(2s)-3-hydroxy-1-oxo-1-(phenylmethoxyamino)propan-2-yl]carbamate Chemical compound CC(C)(C)OC(=O)N[C@@H](CO)C(=O)NOCC1=CC=CC=C1 BEXBKUKHTOBXHW-LBPRGKRZSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 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
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- YKSLVGGUXOMSLN-UHFFFAOYSA-N tris(oxomethylidene)tungsten Chemical compound O=C=[W](=C=O)=C=O YKSLVGGUXOMSLN-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- FZFRVZDLZISPFJ-UHFFFAOYSA-N tungsten(6+) Chemical class [W+6] FZFRVZDLZISPFJ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
-
- 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
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
-
- 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
-
- 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
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- 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
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
Description
(a)一般式Li1+xTM1-xO2(式中、TMは、Ni、Coと、場合によりMnと、場合によりAl、TiおよびZrから選択される少なくとも1種の金属との組み合わせであり、xは、0~0.2の範囲である)で表される電極活物質を提供する工程、
(b)前記電極活物質を、該電極活物質粒子の表面と反応させた場合に交換または置換される少なくとも1種の基またはイオンを有する、WまたはMoの少なくとも1種の化合物で処理する工程、
(c)工程(b)で得られた物質を化学剤で処理して、前記のWまたはMoの化合物を分解する工程、
(d)一連の工程(b)および(c)を1回~100回繰り返す工程
を含み、
得られるコーティングの平均厚さが、0.1~50nmの範囲である。
Li1+xTM1-xO2(式中、TMは、Ni、Co、および場合によりMn、および場合によりAl、TiおよびZrから選択される少なくとも1種の金属の組み合わせであり、xは、0~0.2の範囲である)
に従って、電極活物質を提供することを含む。
(NiaCobMnc)1-dMd(I)
(式中、aは、0.5~0.95、好ましくは0.6~0.95の範囲であり、
bは、0.025~0.2の範囲であり、
cは、0.025~0.3、好ましくは0.1~0.2の範囲であり、
dは、0~0.1の範囲であり、
Mは、Al、TiまたはZr、好ましくはAlであり、そして
a+b+c=1)
による金属の組み合わせである。
- Moのハロゲン化物(例えば、オキシハロゲン化物を含めた、フッ化物、塩化物、臭化物およびヨウ化物)、例えば、MoF6、MoCl5、MoOCl4、MoCl3、
- MoC1-C5アルキル化合物(C1-C5アルキルは同じであるかまたは異なる(例えば、ジメチルモリブデン)、または、ハロゲン化物と組み合わせて結合されたもの(例えば、ビス(シクロペンタジエニル)モリブデン(IV)二塩化物およびシクロペンタジエニルモリブデン(V)四塩化物)
- Moアルコキシドまたはオキソ錯体(好ましくは、C1-C5アルコキシド(C1-C5アルキルは同じであるかまたは異なる))、例えば、モリブデン(V)エトキシドおよびMo(thd)3(式中、thd=2,2,6,6-テトラメチルヘプタン-3,5-ジオナト)、
- Moのアミド(特に、Moのアルキルアミド)、例えば、ビス(tert-ブチルイミド)-ビス(ジメチルアミド)-モリブデン、
- Moカルボニル化合物(特に、Mo(CO)6)、および、アルコキシドまたはC1-C5アルキル化合物との組み合わせで結合物(例えば、シクロペンタジエニルモリブデン(II)トリカルボニル二量体との結合物)、
および、特に、Mo(CO)6。
- Wのハロゲン化物(例えば、オキシハロゲン化物を含めた、フッ化物、塩化物、臭化物およびヨウ化物)、例えば、WF6、WCl4、WOCl4、
- WC1-C5アルキル化合物(C1-C5アルキルは同じであるかまたは異なる(例えば、ヘキサメチルタングステン)、または、ハロゲン化物と組み合わせて結合物(例えば、ビス(シクロペンタジエニル)タングステン(IV)ジクロリドの結合物、またはビス(シクロペンタジエニル)タングステン(IV)ジヒドリドの結合物と同じハイドライド、
- Wアルコキシドまたはオキソ錯体(好ましくは、C1-C5アルコキシド(C1-C5アルキルは同じであるかまたは異なる)、例えば、一般式WO(OR)4(式中、Rは部分的にハロゲン化されていることがあるC1-C5アルキルを表す)を有するオキソアルコキシドタングステン(VI)錯体およびβ-ジケトナートジオキソタングステン(VI)錯体、
- Wのアミド(特に、Wのアルキルアミド)、例えば、ビス(tert-ブチルイミノ)ビス(ジメチルアミノ)タングステン(VI)、WN(N(CH3)2)3およびW2(N(CH3)2)6、
- Wカルボニル化合物(特に、W(CO)6)、および、C1-C5アルキル化合物またはアルコキシドとの組み合わせの結合物(例えば、ビス(アセチルアセトナト)トリカルボニルタングステン(II)の結合物)、
および、特に、W(CO)6。
Al(O-sec-C4H9)3、およびAl(OC2H5)(O-sec-C4H9)2である。
t=1、Yが酸素および硫黄の中から選択される場合、
t=2、Yが窒素およびリンの中から選択される場合、および
t=3、Yが炭素およびシリコンの中から選択される場合)。
sccm:標準立方センチメートル/分(標準:20℃/1atm)
ICP-OES:誘導結合プラズマ発光分析
I.1 正極活物質の前駆体の調製
撹拌槽型反応器は、脱イオン水で満たされていた。混合された遷移金属水酸化物前駆体の沈殿は、水性遷移金属溶液とアルカリ沈殿剤とが1.9の流量比で、および8時間の滞留時間の結果となった総流量で、同時に供給することによって開始された。遷移金属水溶液は、Ni、Co、およびMnを含み、各々が硫酸塩として6:2:2のモル比で、1.65mol/kgの総遷移金属濃度であった。アルカリ性沈殿剤は、25重量%の水酸化ナトリウム溶液および25重量%のアンモニア溶液からなり、重量比は25であった。水酸化ナトリウム水溶液を別に供給することにより、pH値を12.0に維持した。粒子サイズが安定した後、得られた懸濁液を撹拌容器から連続的に取り出した。混合された遷移金属(TM)オキシ水酸化物前駆体は、得られた懸濁液を濾過し、蒸留水で洗浄し、空気中において120℃で乾燥し、ふるいにかけることによって得られた。
I.1によって得られた混合された遷移金属オキシ水酸化物前駆体をAl2O3(平均粒子径6nm)およびLiOH一水和物と混合して、Ni+Co+Mn+AlおよびLi/(TM+Al)(これらのモル比は1.03である)に対して0.3モル%のAl濃度を得た。混合物を885℃に加熱し、酸素の強制流中に8時間保持して、電極活物質C-CAM1を得た。
II.1 本発明による電極活物質CAM.2の製造
外部加熱ジャケットを備えた流動床反応器に100gのC-CAM.1を充填し、5mbarの平均圧力下でC-CAM.1をArで20sccmの一定流量に流動化した。流動床反応器を200℃に加熱し、200℃で4時間保持した(工程(a.1))。フィルターの詰まりを減らして粉末の流動化を助けるために、堆積には、空気圧ハンマーの衝撃と交互に行われるキャリアガスの規則的な逆パルスが包含されている。
工程(b.2)および(c.2)を200℃で行うこと以外は、実験II.1を繰り返した。次に、反応器を25℃に冷却し、そのようにして得られた物質を排出した。得られたCAM.3は、次の特性を示した。D50=10μm(MalvernInstrumentsからのMastersize3000機器でレーザー回折の手法を使用して決定された);W含有量:300ppm(ICP-OESで決定された)。
工程(b.3)および(c.3)を240℃で行うこと以外は、実験II.1を繰り返した。次に、反応器を25℃に冷却し、そのようにして得られた物質を排出した。得られたCAM.4は、次の特性を示しました。D50=10μm(MalvernInstrumentsのMastersize3000機器でレーザー回折の手法を使用して決定された);W含有量:250ppm(ICP-OESで決定された)。
流動床反応器が連続するW(CO)6/オゾン処理の最後に排出されない以外は、実験II.1を繰り返した。代わりに、工程(f.4)を行った。
CAM.4の代わりにC-CAM.1を出発材料として使用したこと以外は、実験II.4を繰り返した。比較物質C-CAM.6が得られた。C-CAM.6は、いかなるWを含んでいない。Al含有量:420ppm(ICP-OESで決定された)。
Claims (8)
- 少なくとも部分的にコーティングされた電極活物質を製造する方法であって、前記方法が、以下の工程:
(a)一般式Li1+xTM1-xO2(式中、TMは、Ni、Coと、場合によりMnと、場合によりAl、TiおよびZrから選択される少なくとも1種の金属との組み合わせであり、xは0~0.2の範囲である)で表される電極活物質を提供する工程、
(b)前記電極活物質を、該電極活物質粒子の表面と反応させた場合に交換または置換される少なくとも1種の基またはイオンを有する、少なくとも1種のWまたはMoの化合物で処理する工程、
(c)工程(b)で得られた前記物質を、WまたはMoの化合物の分解剤で処理する工程、
(d)一連の工程(b)および(c)を1回~100回繰り返す工程
を含み、
得られるコーティングの平均厚さが、0.1~50nmの範囲であり、
工程(b)、(c)および(d)が気相で行われ、
工程(b)による処理のための化合物が、WまたはMoの、カルボニル、C1-C5アルキル、アミド、アルコキシド、ハロゲン化物、またはこれらの少なくとも2種の組み合わせから選択され、
工程(c)の分解剤が、酸素、過酸化物、オゾン、水素、水、およびC1-C4アルキルアルコールから選択される、
方法。 - 工程(b)による処理のための化合物が、W(CO)6およびMo(CO)6から選択される、請求項1に記載の方法。
- 前記方法が熱の後処理工程(e)を更に含む、請求項1又は2に記載の方法。
- 工程(b)~(d)が、ロータリーキルン、自由落下ミキサー、連続振動床、または流動床で行われる、請求項1~3のいずれか一項に記載の方法。
- 工程(b)と工程(c)との間においてパージ工程が行われる、請求項1~4のいずれか一項に記載の方法。
- TMが、一般式(I):
(NiaCobMnc)1-dMd(I)
(式中、aが0.6~0.9の範囲であり、bが0.05~0.2の範囲であり、cが0~0.2の範囲であり、dが0~0.1の範囲であり、MがTi、Zr、およびAlから選択され、そして、a+b+c=1)
で表される遷移金属の組み合わせである、請求項1~5のいずれか一項に記載の方法。 - TMが、Ni0.85Co0.1Al0.05、Ni0.6Co0.2Mn0.2、Ni0.7Co0.2Mn0.1、Ni0.8Co0.1Mn0.1、Ni0.85Co0.1Mn0.05、および(Ni0.6Co0.2Mn0.2)1-dAld (式中、dは0~0.1の範囲である)から選択される、請求項1~6のいずれか一項に記載の方法。
- 前記方法が更なるコーティング工程(f)を含み、Al、Zn、Ti、Si、P、Zr、Hf、Ni、Li、またはCoの少なくとも1種の酸化物およびこれらの少なくとも2種の組み合わせが請求項1~7のいずれか一項に記載の方法から得られた物質上にコーティングされる、請求項1~7のいずれか一項に記載の方法。
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