WO2022201609A1 - 全固体リチウムイオン電池用正極活物質、全固体リチウムイオン電池用正極、全固体リチウムイオン電池及び全固体リチウムイオン電池用正極活物質の製造方法 - Google Patents
全固体リチウムイオン電池用正極活物質、全固体リチウムイオン電池用正極、全固体リチウムイオン電池及び全固体リチウムイオン電池用正極活物質の製造方法 Download PDFInfo
- Publication number
- WO2022201609A1 WO2022201609A1 PCT/JP2021/037628 JP2021037628W WO2022201609A1 WO 2022201609 A1 WO2022201609 A1 WO 2022201609A1 JP 2021037628 W JP2021037628 W JP 2021037628W WO 2022201609 A1 WO2022201609 A1 WO 2022201609A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- active material
- electrode active
- solid
- lithium ion
- Prior art date
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 156
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 94
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000002245 particle Substances 0.000 claims abstract description 79
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000011247 coating layer Substances 0.000 claims abstract description 32
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 24
- 239000010410 layer Substances 0.000 claims description 51
- 239000007784 solid electrolyte Substances 0.000 claims description 39
- 239000010955 niobium Substances 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 150000004703 alkoxides Chemical class 0.000 claims description 20
- 230000001186 cumulative effect Effects 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 4
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910003327 LiNbO3 Inorganic materials 0.000 claims description 3
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 3
- HAUKUGBTJXWQMF-UHFFFAOYSA-N lithium;propan-2-olate Chemical compound [Li+].CC(C)[O-] HAUKUGBTJXWQMF-UHFFFAOYSA-N 0.000 claims description 3
- IJCCNPITMWRYRC-UHFFFAOYSA-N methanolate;niobium(5+) Chemical compound [Nb+5].[O-]C.[O-]C.[O-]C.[O-]C.[O-]C IJCCNPITMWRYRC-UHFFFAOYSA-N 0.000 claims description 3
- LZRGWUCHXWALGY-UHFFFAOYSA-N niobium(5+);propan-2-olate Chemical compound [Nb+5].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] LZRGWUCHXWALGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052759 nickel Inorganic materials 0.000 abstract description 15
- 229910006025 NiCoMn Inorganic materials 0.000 abstract description 8
- 229910014638 LiaNib Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 24
- 238000000034 method Methods 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- -1 flame-retardant compound Chemical class 0.000 description 11
- 239000002131 composite material Substances 0.000 description 9
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011163 secondary particle Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000005001 laminate film Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002203 sulfidic glass Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 229910008029 Li-In Inorganic materials 0.000 description 3
- 229910006670 Li—In Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 239000007771 core particle Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910008523 Li2O-B2O3-ZnO Inorganic materials 0.000 description 2
- 229910008627 Li2O—B2O3—ZnO Inorganic materials 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920003026 Acene Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000003109 Karl Fischer titration Methods 0.000 description 1
- 229910003548 Li(Ni,Co,Mn)O2 Inorganic materials 0.000 description 1
- 229910009147 Li1.3Al0.3Ti0.7(PO4)3 Inorganic materials 0.000 description 1
- 229910008745 Li2O-B2O3-P2O5 Inorganic materials 0.000 description 1
- 229910008590 Li2O—B2O3—P2O5 Inorganic materials 0.000 description 1
- 229910012316 Li3.6Si0.6P0.4O4 Inorganic materials 0.000 description 1
- 229910012722 Li3N-LiI-LiOH Inorganic materials 0.000 description 1
- 229910012716 Li3N-LiI—LiOH Inorganic materials 0.000 description 1
- 229910012734 Li3N—LiI—LiOH Inorganic materials 0.000 description 1
- 229910012605 Li3PO(4-3/2w)Nw Inorganic materials 0.000 description 1
- 229910012606 Li3PO(4−3/2w)Nw Inorganic materials 0.000 description 1
- 229910013043 Li3PO4-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910013035 Li3PO4-Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910012810 Li3PO4—Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910012804 Li3PO4—Li2S—Si2S Inorganic materials 0.000 description 1
- 229910012797 Li3PO4—Li2S—SiS2 Inorganic materials 0.000 description 1
- 239000002225 Li5La3Ta2O12 Substances 0.000 description 1
- 229910010712 Li5La3Ta2O12 Inorganic materials 0.000 description 1
- 229910010640 Li6BaLa2Ta2O12 Inorganic materials 0.000 description 1
- 229910010823 LiI—Li2S—B2S3 Inorganic materials 0.000 description 1
- 229910010847 LiI—Li3PO4-P2S5 Inorganic materials 0.000 description 1
- 229910010864 LiI—Li3PO4—P2S5 Inorganic materials 0.000 description 1
- 229910012254 LiPO4—Li2S—SiS Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 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
-
- 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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M4/04—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
- H01M4/13—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
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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
- 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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—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
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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
- H01M4/36—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
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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- 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
- C01P2006/12—Surface area
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- 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
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a positive electrode active material for all-solid-state lithium ion batteries, a positive electrode for all-solid-state lithium-ion batteries, an all-solid-state lithium-ion battery, and a method for producing a positive electrode active material for all-solid-state lithium-ion batteries.
- lithium ion batteries are attracting attention because of their high energy density.
- improvements in energy density and battery characteristics are required for lithium secondary batteries used in large-scale applications such as power sources for vehicles and load leveling.
- All-solid-state lithium-ion batteries using a sulfide-based solid electrolyte have a problem in that the reaction between the positive electrode active material and the solid electrolyte forms a high-resistance layer, resulting in a decrease in output.
- a method of coating the surface of the positive electrode active material with a Li composite oxide is known.
- LiNbO 3 which exhibits high ionic conductivity, is a typical Li composite oxide for coating the surface of the positive electrode active material.
- Patent Document 1 discloses a positive electrode active material having an oxide positive electrode active material and a coating portion made of a lithium niobate-based compound formed on the surface of the oxide positive electrode active material, and a sulfide solid electrolyte material.
- Patent Document 2 discloses an active material and lithium niobate attached to the surface of the active material, and has a BET specific surface area S [m 2 /g] greater than 0.93 and 1 Active material composite powders are disclosed that are less than 0.44.
- Patent Document 3 discloses an all-solid lithium battery using a lithium ion conductive solid electrolyte as an electrolyte, in which the lithium ion conductive solid electrolyte is mainly composed of sulfide, and the surface of the positive electrode active material is lithium ion conductive.
- An all-solid-state lithium battery is disclosed, characterized in that it is coated with a reactive oxide. LiCoO is used as core particles of the positive electrode active material, and the core particles are coated with LiNbO 3 with an alkoxide solution.
- Patent Documents 1 to 3 materials such as LiCoO, NiCoMn with a molar ratio of 1:1:1, or LiNiO 2 are used as the core particles of the positive electrode active material. These documents do not describe a technique for producing a so-called high-nickel product, which is a positive electrode active material of a ternary system (Li(Ni, Co, Mn)O 2 ) with a Ni ratio exceeding 80 mol %.
- NiCoMn - based positive electrode active material having a so-called high-nickel composition in which the Ni ratio is 80 mol% or more, there is a problem that the resistance increases when an oxide of Li and Nb such as LiNbO3 is coated. .
- the present invention has been made to solve the above problems, and is a positive electrode active material for an all-solid lithium ion battery, which has a so-called high-nickel composition in which the Ni ratio is 80 mol% or more.
- An object of the present invention is to provide a resistive NiCoMn-based positive electrode active material.
- the present invention provides a positive electrode for an all-solid lithium ion battery using the positive electrode active material for an all-solid lithium ion battery, an all-solid lithium ion battery, and a method for producing a positive electrode active material for an all-solid lithium ion battery. for another purpose.
- a positive electrode active material for an all-solid-state lithium ion battery comprising core positive electrode active material particles and a coating layer
- the coating layer is an oxide of Li and Nb
- a positive electrode active material for an all-solid-state lithium-ion battery wherein the specific surface area X (m 2 /g) of the positive electrode active material and the Nb content Y (mass%) in the positive electrode active material satisfy the following formula (2): material.
- An all-solid lithium ion battery comprising a positive electrode layer composed of the positive electrode for an all-solid lithium ion battery according to 4 above, a negative electrode layer, and a solid electrolyte layer. 6.
- a step of preparing core positive electrode active material particles represented by the composition shown in the following formula (1); LiaNibCocMndOe ( 1 ) _ (In the formula (1), 1.0 ⁇ a ⁇ 1.05, 0.8 ⁇ b ⁇ 0.9, 1.8 ⁇ e ⁇ 2.2, and b+c+d 1.) forming a coating layer made of an oxide of Li and Nb on the surface of the core positive electrode active material particles by means of a tumbling fluidized bed apparatus using an alkoxide solution containing Li and Nb;
- the alkoxide solution contains (1) any one of methoxylithium, ethoxylithium, and isopropoxylithium as a solute lithium source, and (2) any one of pentamethoxyniobium, pentaethoxyniobium, and pentaisopropoxyniobium as a niobium source.
- a low-resistance NiCoMn-based positive electrode active material for an all-solid-state lithium-ion battery which has a so-called high-nickel composition with a Ni ratio of 80 mol% or more.
- a positive electrode for an all-solid lithium ion battery using the positive electrode active material for an all-solid lithium ion battery, an all-solid lithium ion battery, and a method for producing a positive electrode active material for an all-solid lithium ion battery are provided. can provide.
- FIG. 1 is a schematic diagram of an all-solid-state lithium-ion battery according to an embodiment of the present invention
- a positive electrode active material for an all-solid-state lithium ion battery according to an embodiment of the present invention includes core positive electrode active material particles and a coating layer.
- a which indicates the lithium composition
- a is controlled to 1.0 ⁇ a ⁇ 1.05 in the above formula (1). Since a, which indicates the lithium composition, is 1.0 or more, reduction of nickel due to lithium deficiency can be suppressed. In addition, since a, which indicates the lithium composition, is 1.05 or less, residual alkaline components such as lithium carbonate and lithium hydroxide, which are present on the surface of the core positive electrode active material particles and can become resistance components when used as a battery, are suppressed. can do.
- b which indicates the nickel composition
- b is controlled to 0.8 ⁇ b ⁇ 0.9, which is a so-called high-nickel composition. Since b, which indicates the nickel composition, is 0.8 or more, a good battery capacity of the all-solid lithium ion battery can be obtained.
- the core positive electrode active material particles mostly have the form of secondary particles in which a plurality of primary particles are aggregated, and may partially contain primary particles that are not aggregated as secondary particles. .
- the shape of the primary particles that constitute the secondary particles and the primary particles that exist alone are not particularly limited. good too.
- the form in which a plurality of primary particles are aggregated is not particularly limited. For example, a form in which a plurality of primary particles are aggregated in a random direction, or a form in which the secondary particles are aggregated in a substantially uniform radial direction from the center to form a substantially spherical or substantially elliptical secondary particle. Various forms such as a forming form may be used.
- the content of the lithium hydroxide is preferably 1.5% by mass or less, and 1.0% by mass. More preferably: When the lithium hydroxide content in the core positive electrode active material particles exceeds 1.5% by mass, lithium hydroxide is oxidatively decomposed and gas is likely to be generated when the positive electrode active material is charged in a high-temperature environment.
- the content of the lithium carbonate is preferably 1.5% by mass or less, and 1.0% by mass or less. It is more preferable to have If the lithium carbonate content in the core positive electrode active material particles exceeds 1.5% by mass, lithium carbonate is oxidatively decomposed and gas is likely to be generated when the positive electrode active material is charged in a high-temperature environment.
- the contents of lithium hydroxide and lithium carbonate contained in the above core positive electrode active material particles can be obtained by a neutralization titration method.
- Lithium hydroxide and lithium carbonate as excess lithium existing on the surfaces of the lithium metal composite oxide particles and the like are dissolved in water, whereby hydroxide ions and carbonate ions are ionized from lithium ions, respectively.
- These ionized anions can be titrated with an inorganic acid or the like, thereby making it possible to separate and quantify lithium hydroxide and lithium carbonate.
- the water content in the core positive electrode active material particles is preferably 0.10% by mass or less, more preferably 0.05% by mass or less. If the moisture contained in the core positive electrode active material particles exceeds 0.10% by mass, the metal elements forming the positive electrode may be damaged, degrading various battery characteristics. Dry weight method, Karl Fischer titration method, distillation method, or the like can be used as a method for measuring the moisture contained in the core positive electrode active material particles.
- the coating layer is an oxide of Li and Nb.
- the specific surface area X (m 2 /g) of the positive electrode active material and the Nb content Y (% by mass) in the positive electrode active material are expressed by the following formula The relationship of (2) is satisfied. 0.65 ⁇ Y/X ⁇ 1.20 (2)
- the resistance component of the battery can be reduced and the output characteristics can be improved. can. More specifically, if the surface of the core positive electrode active material particles can be covered as entirely as possible with a coating layer that is an oxide of Li and Nb, the solid electrolyte and the positive electrode active material when exposed to a high potential during charging. An increase in resistance due to interfacial reaction with a substance is suppressed.
- the coating layer which is an oxide of Li and Nb
- the coating layer which is an oxide of Li and Nb
- the movement of Li ions in the coating layer during charging and discharging is shortened, and the diffusion transfer resistance is reduced. can be reduced.
- the resistance is particularly problematic in a positive electrode active material having a so-called high-nickel composition in which the Ni ratio is 80 mol % or more.
- the Nb content Y (% by mass) in the positive electrode active material with respect to the specific surface area X (m 2 /g) of the positive electrode active material By controlling the ratio Y/X to 0.65 ⁇ Y/X ⁇ 1.20, a low-resistance NiCoMn-based positive electrode active material can be obtained. If the Y/X ratio is less than 0.65, there will be many uncovered portions, which may cause direct contact between the solid electrolyte and the positive electrode active material, resulting in the formation of a high resistance layer.
- Y/X which is the ratio of the Nb content Y (% by mass) in the positive electrode active material to the specific surface area X (m 2 /g) of the positive electrode active material, is 0.65 ⁇ Y/X ⁇ 1.0.
- 0.65 ⁇ Y/X ⁇ 0.75 is more preferable.
- the 50% cumulative volume particle size D50 of the positive electrode active material for all-solid-state lithium ion batteries is preferably 3 to 7 ⁇ m.
- the 50% cumulative volume particle size D50 is the volume particle size at the time of 50% accumulation in the volume-based cumulative particle size distribution curve.
- the 50% cumulative volume particle size D50 of the positive electrode active material for all-solid-state lithium ion batteries is 3 ⁇ m or more, the specific surface area can be suppressed, and the coating amount of oxides of Li and Nb can be suppressed.
- the 50% cumulative volume particle size D50 of the positive electrode active material for an all-solid-state lithium ion battery is 7 ⁇ m or less, it is possible to suppress an excessive decrease in the specific surface area.
- the 50% cumulative volume particle size D50 of the positive electrode active material for all-solid-state lithium ion batteries is more preferably 3 to 6 ⁇ m, and even more preferably 4 to 5 ⁇ m.
- the 50% cumulative volume particle size D50 can be measured with a Microtrac laser diffraction particle size distribution analyzer "MT3300EXII".
- the manufacturing method of the core positive electrode active material particles is not particularly limited, and can be appropriately adjusted based on a known manufacturing method. For example, first, a NiCoMn-based composite hydroxide having a Ni composition of 0.8 to 0.9 in molar ratio is prepared. Next, a Li source (Li carbonate, Li hydroxide, etc.) is added to the composite hydroxide by adjusting the mixing ratio of each raw material and dry-mixing with a Henschel mixer or the like. A sintered body is obtained by sintering for 24 hours. Thereafter, if necessary, the fired body can be pulverized using, for example, a pulverizer or the like to obtain core positive electrode active material particles.
- a Li source Li carbonate, Li hydroxide, etc.
- a coating liquid used for coating the surface of the core positive electrode active material particles by a tumbling fluidized bed apparatus is prepared.
- An alkoxide solution containing Li and Nb is used as the coating liquid.
- a coating layer made of an oxide of Li and Nb is formed on the surface of the core positive electrode active material particles by a wet method using a tumbling fluidized bed apparatus. .
- the particles constituting the coating layer are coated as thinly as possible over the entire surface of the core positive electrode active material particles, so that the positive electrode active material-solid electrolyte It is possible to suppress the reaction between the layers and reduce the diffusion transfer resistance in the coating layer.
- the covering state of the covering layer changes from partial covering to complete covering at a certain film thickness, the output of the all-solid-state battery is further improved by performing complete covering targeting near this critical point as much as possible.
- the present inventors also found that when an alkoxide solution was used as the coating liquid, a gel was formed due to partial hydrolysis immediately after coating, making it easier to cover the surface, resulting in the coating layer described above.
- the alkoxide solution used as the coating liquid contains (1) any one of methoxylithium, ethoxylithium, and isopropoxylithium as a solute lithium source, and (2) pentamethoxyniobium, pentaethoxyniobium, and pentaisopropoxyniobium as a niobium source. and (3) any one of ethanol, methanol, and isopropanol as a solvent.
- the coating layer formed on the surface of the core positive electrode active material particles by the tumbling fluidized bed apparatus can be formed as thin as possible over the entire surface more satisfactorily.
- the LiNbO 3 concentration of the alkoxide solution is preferably 5% by mass or less. According to such a configuration, the coating layer is formed gently, and it is possible to form the coating layer as thin as possible over the entire surface more satisfactorily.
- a tumbling fluidized bed device has a rotor at the bottom, and the particles in the device can be brought into a fluid state by sucking in a supply gas.
- the core positive electrode active material particles are fluidized in a tumbling fluidized bed apparatus, the alkoxide solution of the coating raw material is sprayed onto the core positive electrode active material particles, and the granules are formed by drying. Next, the resulting granules are fired in the air or in an inert atmosphere to form a coating layer on the surfaces of the core positive electrode active material particles.
- the ratio of the coating raw material alkoxide solution to the core positive electrode active material particles is such that the mass ratio of the coating raw material (solute component): core positive electrode active material particles is 2:1000 to 1:1. A range of 100 is preferred. In the above method, it is preferable that the amount of intake air for making the core positive electrode active material particles in a fluid state is about 0.15 to 0.3 m 3 /min.
- the temperature of the intake air in the tumbling fluidized bed apparatus is set to, for example, at least room temperature or higher and 80° C. or lower, so that the alkoxide containing the coating raw material is coated on the surface of the core positive electrode active material particles.
- the solution is coated.
- firing is performed by heating at 200 to 350° C. for about 1 to 5 hours in an oxygen atmosphere or air.
- a positive electrode active material for an all-solid-state lithium ion battery according to an embodiment of the present invention which has core positive electrode active material particles and a coating layer formed on the surface of the core positive electrode active material particles, is obtained.
- a positive electrode is formed from the positive electrode active material for an all-solid lithium ion battery according to an embodiment of the present invention, the positive electrode is used as a positive electrode layer, and an all-solid lithium ion battery including the positive electrode layer, a solid electrolyte layer, and a negative electrode layer can be made.
- the solid electrolyte layer and the negative electrode layer that constitute the all-solid-state lithium ion battery according to the embodiment of the present invention are not particularly limited, and can be formed of known materials and have a known configuration as shown in FIG. can be done.
- a layered positive electrode mixture obtained by mixing the positive electrode active material for an all-solid-state lithium-ion battery according to the embodiment of the present invention and a solid electrolyte can be used.
- the content of the positive electrode active material in the positive electrode layer is, for example, preferably 50% by mass or more and 99% by mass or less, and more preferably 60% by mass or more and 90% by mass or less.
- the positive electrode mixture may further contain a conductive aid.
- a carbon material, a metal material, or a mixture thereof can be used as the conductive aid.
- Conductive agents include, for example, carbon, nickel, copper, aluminum, indium, silver, cobalt, magnesium, lithium, chromium, gold, ruthenium, platinum, beryllium, iridium, molybdenum, niobium, osnium, rhodium, tungsten and zinc. It may contain at least one element selected from the group.
- the conductive aid is preferably a highly conductive carbon single substance, carbon, nickel, copper, silver, cobalt, magnesium, lithium, ruthenium, gold, platinum, niobium, osnium or rhodium containing metal simple substance, mixture or compound.
- carbon material for example, carbon black such as ketjen black, acetylene black, denka black, thermal black and channel black, graphite, carbon fiber, activated carbon and the like can be used.
- the average thickness of the positive electrode layer of the lithium-ion battery is not particularly limited, and can be appropriately designed according to the purpose.
- the average thickness of the positive electrode layer of the lithium ion battery may be, for example, 1 ⁇ m to 100 ⁇ m, or 1 ⁇ m to 10 ⁇ m.
- the method for forming the positive electrode layer of the lithium ion battery is not particularly limited, and can be appropriately selected according to the purpose.
- a method for forming the positive electrode layer of the lithium ion battery for example, a method of compression-molding positive electrode active material particles can be used.
- the negative electrode layer of the lithium ion battery may be formed by layering a known negative electrode active material for all-solid lithium ion batteries. Further, the negative electrode layer may be formed by layering a negative electrode composite material obtained by mixing a known negative electrode active material for a lithium ion battery and a solid electrolyte.
- the content of the negative electrode active material in the negative electrode layer is, for example, preferably 10% by mass or more and 99% by mass or less, and more preferably 20% by mass or more and 90% by mass or less.
- the negative electrode layer may contain a conductive aid.
- the same material as the material described for the positive electrode layer can be used for the conductive aid.
- negative electrode active materials include carbon materials such as artificial graphite, graphite carbon fiber, resin baked carbon, pyrolytic vapor growth carbon, coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin baked carbon. , polyacene, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite, non-graphitizable carbon, etc., or a mixture thereof.
- metals such as metallic lithium, metallic indium, metallic aluminum, and metallic silicon, or alloys in which they are combined with other elements or compounds can be used.
- the average thickness of the negative electrode layer of the lithium ion battery is not particularly limited, and can be appropriately selected according to the purpose.
- the average thickness of the negative electrode layer of the lithium ion battery may be, for example, 1 ⁇ m to 100 ⁇ m, or 1 ⁇ m to 10 ⁇ m.
- the method for forming the negative electrode layer of the lithium ion battery is not particularly limited, and can be appropriately selected according to the purpose.
- Methods for forming the negative electrode layer of the lithium ion battery include, for example, a method of compression-molding negative electrode active material particles, a method of vapor-depositing a negative electrode active material, and the like.
- a known solid electrolyte for all-solid lithium ion batteries can be used as the solid electrolyte. Even if an oxide-based solid electrolyte is used as the solid electrolyte, it is possible to reduce the resistance in the all-solid lithium ion battery using the positive electrode active material according to the embodiment of the present invention. In particular, when a sulfide-based solid electrolyte is used as the solid electrolyte, there has conventionally been the problem of formation of a high-resistance layer due to the reaction between the positive electrode active material and the solid electrolyte, resulting in a decrease in output.
- the positive electrode active material since the entire positive electrode active material is covered as much as possible, formation of a high resistance layer can be favorably suppressed even in an all-solid lithium ion battery having a sulfide-based solid electrolyte.
- the coating layer by forming the coating layer as thin as possible, the migration of Li ions in the coating layer during charging and discharging is shortened, so that the diffusion migration resistance can also be reduced. These two effects can reduce resistance.
- a lithium-containing compound containing lithium and at least one element selected from niobium, tantalum, silicon, phosphorus and boron may be used as the solid electrolyte.
- oxide-based solid electrolytes examples include LiTi 2 (PO 4 ) 3 , Li 2 O—B 2 O 3 —P 2 O 5 , Li 2 O—SiO 2 , Li 2 O—B 2 O 3 , and Li 2O—B 2 O 3 —ZnO and the like.
- Examples of sulfide solid electrolytes include LiI-Li 2 SP 2 S 5 , LiI-Li 2 S-B 2 S 3 , Li 3 PO 4 -Li 2 S-Si 2 S, Li 3 PO 4 - Li 2 S—SiS 2 , LiPO 4 —Li 2 S—SiS, LiI—Li 2 SP 2 O 5 , LiI—Li 3 PO 4 —P 2 S 5 , Li 3 PS 4 , and Li 2 SP 4 . 2S5 and the like .
- the average thickness of the solid electrolyte layer of the lithium-ion battery is not particularly limited, and can be appropriately designed according to the purpose.
- the average thickness of the solid electrolyte layer of the lithium ion battery may be, for example, 50 ⁇ m to 500 ⁇ m, or 50 ⁇ m to 100 ⁇ m.
- the method for forming the solid electrolyte layer of the lithium ion battery is not particularly limited, and can be appropriately selected according to the purpose.
- Methods for forming the solid electrolyte layer of the lithium ion battery include, for example, sputtering using a solid electrolyte target material and compression molding of the solid electrolyte.
- Other members constituting the lithium-ion battery are not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include a positive electrode current collector, a negative electrode current collector, and a battery case.
- the size and structure of the positive electrode current collector are not particularly limited, and can be appropriately selected according to the purpose.
- materials for the positive electrode current collector include die steel, stainless steel, aluminum, aluminum alloys, titanium alloys, copper, gold, and nickel.
- examples of the shape of the positive electrode current collector include a foil shape, a plate shape, and a mesh shape.
- the average thickness of the positive electrode current collector may be, for example, 10 ⁇ m to 500 ⁇ m, or may be 50 ⁇ m to 100 ⁇ m.
- the size and structure of the negative electrode current collector are not particularly limited, and can be appropriately selected according to the purpose.
- materials for the negative electrode current collector include die steel, gold, indium, nickel, copper, and stainless steel.
- examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh shape.
- the average thickness of the negative electrode current collector may be, for example, 10 ⁇ m to 500 ⁇ m, or may be 50 ⁇ m to 100 ⁇ m.
- the battery case is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include known laminate films that can be used in conventional all-solid-state batteries. Examples of laminate films include resin laminate films and films obtained by vapor-depositing metal on resin laminate films.
- the shape of the battery is not particularly limited, and can be appropriately selected according to the purpose. Examples thereof include cylindrical, square, button, coin, and flat shapes.
- Examples 1 to 6, Comparative Examples 1 to 6) First, a NiCoMn-based composite hydroxide having a Ni composition of 0.82 to 0.9 in molar ratio was prepared. Next, after adjusting the mixing ratio of each raw material, Li hydroxide is dry-mixed with the composite hydroxide using a Henschel mixer, and then fired at a temperature of 700 to 780 ° C. for 12 to 24 hours to obtain a fired body. got After that, the fired body was pulverized by a pulverizer to obtain core positive electrode active material particles.
- a coating liquid was prepared to be used for coating the surface of the core positive electrode active material particles using a tumbling fluidized bed apparatus.
- An alkoxide solution which is an ethanol solution of ethoxylithium and pentaethoxyniobium, was used as the coating liquid.
- the core positive electrode active material particles were fluidized in a tumbling fluidized bed apparatus, and the alkoxide solution of the coating raw material was sprayed onto the core positive electrode active material particles, followed by drying to form granules.
- the resulting granules were fired in the air or in an inert atmosphere to form a coating layer on the surfaces of the core positive electrode active material particles.
- the concentration of the alkoxide solution, the ratio of the alkoxide solution and the core positive electrode active material particles, the intake air volume and the intake air temperature in the tumbling fluidized bed apparatus, respectively, are the targets of the coating amount of LiNbO3. It was adjusted as appropriate based on the value (Nb content Y in the positive electrode active material).
- the concentration of the alkoxide solution is 4.1 wt % in terms of LiNbO 3
- 125 g of the alkoxide solution is sprayed onto 800 g of core positive electrode active material particles at a rate of 2.0 g/min.
- the amount of intake air in the tumbling fluidized bed apparatus is set to 0.2 m 3 /min, and the intake air temperature is set to 90°C.
- composition of positive electrode active material, Nb content Y in positive electrode active material Weigh 0.2 g of the sample (powder) of each positive electrode active material obtained, decompose it by an alkali fusion method, and then use an inductively coupled plasma emission spectrometer (ICP-OES) "PS7800" manufactured by Hitachi High-Tech Co., Ltd. A compositional analysis was performed. Moreover, the Nb content Y in the positive electrode active material was also measured by the composition analysis.
- ICP-OES inductively coupled plasma emission spectrometer
- the obtained composite material layer of the solid electrolyte layer and the positive electrode active material layer is turned over, and Li foil (10 mm diameter ⁇ thickness 0.1 mm) and In foil (9 mm diameter) are attached to the solid electrolyte layer side on the SUS plate. ⁇ thickness 0.1 mm) was provided and pressed at a pressure of 20 MPa to form a Li—In negative electrode layer.
- a laminate was produced in which the positive electrode active material layer, the solid electrolyte layer, and the Li—In negative electrode layer were laminated in this order.
- the laminate was placed in a battery test cell made of SUS304 and a confining pressure of 2.5 N ⁇ m was applied to obtain an all-solid secondary battery.
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Abstract
Description
1.コア正極活物質粒子と被覆層とを含む全固体リチウムイオン電池用正極活物質であり、
前記コア正極活物質粒子は下記式(1)に示す組成で表され、
LiaNibCocMndOe (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、1.8≦e≦2.2、及び、b+c+d=1である。)
前記被覆層は、LiとNbとの酸化物であり、
前記正極活物質の比表面積X(m2/g)と、前記正極活物質におけるNb含有量Y(質量%)とが、下記式(2)の関係を満たす、全固体リチウムイオン電池用正極活物質。
0.65≦Y/X≦1.20 (2)
2.前記全固体リチウムイオン電池用正極活物質の50%累積体積粒度D50が3~7μmである、前記1に記載の全固体リチウムイオン電池用正極活物質。
3.前記被覆層が、LiNbO3を含む、前記1または2に記載の全固体リチウムイオン電池用正極活物質。
4.前記1~3のいずれかに記載の全固体リチウムイオン電池用正極活物質を含む、全固体リチウムイオン電池用正極。
5.前記4に記載の全固体リチウムイオン電池用正極で構成された正極層と、負極層と、固体電解質層と、を含む、全固体リチウムイオン電池。
6.下記式(1)に示す組成で表されたコア正極活物質粒子を準備する工程と、
LiaNibCocMndOe (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、1.8≦e≦2.2、及び、b+c+d=1である。)
前記コア正極活物質粒子の表面に、LiとNbとを含むアルコキシド溶液を用いて、転動流動層装置によって、LiとNbとの酸化物からなる被覆層を形成する工程と、
を含む、全固体リチウムイオン電池用正極活物質の製造方法。
7.前記アルコキシド溶液が、(1)溶質のリチウム源としてメトキシリチウム、エトキシリチウム、及び、イソプロポキシリチウムのいずれか一種、(2)ニオブ源としてペンタメトキシニオブ、ペンタエトキシニオブ、ペンタイソプロポキシニオブのいずれか一種、及び、(3)溶媒としてエタノール、メタノール、イソプロパノールのいずれか一種、を含む溶液である、前記6に記載の全固体リチウムイオン電池用正極活物質の製造方法。
本発明の実施形態に係る全固体リチウムイオン電池用正極活物質は、コア正極活物質粒子と被覆層とを含む。コア正極活物質粒子は、下記式(1)に示す組成で表される。
LiaNibCocMndOe (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、1.8≦e≦2.2、及び、b+c+d=1である。)
0.65≦Y/X≦1.20 (2)
次に、本発明の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法について詳述する。本発明の実施形態に係る全固体リチウムイオン電池用正極活物質の製造方法は、まず、下記式(1)に示す組成で表されたコア正極活物質粒子を準備する。
LiaNibCocMndOe (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、1.8≦e≦2.2、及び、b+c+d=1である。)
本発明の実施形態に係る全固体リチウムイオン電池用正極活物質によって正極を形成し、当該正極を正極層とし、当該正極層と、固体電解質層と、負極層とを含む全固体リチウムイオン電池を作製することができる。本発明の実施形態に係る全固体リチウムイオン電池を構成する固体電解質層及び負極層は、特に限定されず、公知の材料で形成することができ、図1に示すような公知の構成とすることができる。
正極集電体の材質としては、例えば、ダイス鋼、ステンレス鋼、アルミニウム、アルミニウム合金、チタン合金、銅、金、ニッケルなどが挙げられる。
正極集電体の形状としては、例えば、箔状、板状、メッシュ状などが挙げられる。正極集電体の平均厚みとしては、例えば、10μm~500μmであってもよく、50μm~100μmであってもよい。
負極集電体の材質としては、例えば、ダイス鋼、金、インジウム、ニッケル、銅、ステンレス鋼などが挙げられる。
負極集電体の形状としては、例えば、箔状、板状、メッシュ状などが挙げられる。
負極集電体の平均厚みとしては、例えば、10μm~500μmであってもよく、50μm~100μmであってもよい。
電池の形状については特に限定されず、目的に応じて適宜選択することができ、例えば、円筒型、角型、ボタン型、コイン型、扁平型などが挙げられる。
まず、Ni組成がモル比で0.82~0.9であるNiCoMn系の複合水酸化物を準備した。次に、当該複合水酸化物に、水酸化Liを、各原料の混合割合を調整してヘンシェルミキサーで乾式混合した後、700~780℃の温度で12~24時間焼成することで、焼成体を得た。その後、焼成体をパルベライザーで解砕することによりコア正極活物質粒子を得た。
得られた各正極活物質のサンプル(粉末)を0.2gはかり取り、アルカリ溶融法で分解後、日立ハイテク社製の誘導結合プラズマ発光分光分析装置(ICP-OES)「PS7800」を用いて、組成分析を行った。また、当該組成分析により、正極活物質におけるNb含有量Yも測定した。
得られた各正極活物質のサンプル(粉末)100mgをMicrotrac製レーザー回折型粒度分布測定装置「MT3300EXII」を用いて、50%の流速中、40Wの超音波を60秒間照射して分散後、粒度分布を測定し、体積基準の累積粒度分布曲線を得た。得られた累積粒度分布曲線において、50%累積時の体積粒度を、正極活物質の粉末の50%累積体積粒度D50とした。
得られた各正極活物質のサンプル(粉末)1.5gをガラスセルに秤量し、脱気装置にセットし、窒素ガスでガラスセル内を充填した後、窒素ガス雰囲気中、150℃で1時間熱処理し、脱気した。その後、脱気後のサンプル(粉末)が入ったガラスセルをQuantachrome製比表面積測定装置「Monosorb」へセットし、吸着ガスとしてHe:70at%-N2:30at%混合ガスを流しながら、BET法(1点法)によって、比表面積Xを測定した。
正極活物質:75mgと硫化物固体電解質材料Li3PS4:25mgとを混合し、正極合材を得た。
また、硫化物固体電解質材料Li3PS4:80mgを、φ10mmの電池試験セル内部へ投入し、ペレット成形機を用いて37MPaの圧力でプレスし、固体電解質層を形成した。当該固体電解質層の上に正極合材10mgを投入し、330MPaの圧力でプレスして合材層を作製した。
次に、得られた固体電解質層と正極活物質層との合材層の上下を裏返し、固体電解質層側に、SUS板にLi箔(10mm径×厚み0.1mm)とIn箔(9mm径×厚み0.1mm)を貼り合わせたものを設け、20MPaの圧力でプレスしてLi-In負極層とした。これによって、正極活物質層、固体電解質層及びLi-In負極層がこの順で積層された積層体を作製した。
次に、当該積層体をSUS304製の電池試験セルに入れて2.5N・mの拘束圧をかけて全固体二次電池とした。
次に、全固体二次電池において、3.7V(vs.Li-In)まで充電し、充電後のセルにおいて交流インピーダンス測定を行った。そしてナイキストプロットから得られる円弧から初期抵抗を求めた。
上記製造条件及び試験結果を表1に示す。
実施例1~6の正極活物質は、いずれも、正極活物質の比表面積X(m2/g)と、正極活物質におけるNb含有量Y(質量%)とが、下記式(2)の関係を満たした。このため、全固体電池として評価した初期抵抗が低く抑えられていた。
0.65≦Y/X≦1.20 (2)
Claims (7)
- コア正極活物質粒子と被覆層とを含む全固体リチウムイオン電池用正極活物質であり、
前記コア正極活物質粒子は下記式(1)に示す組成で表され、
LiaNibCocMndOe (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、1.8≦e≦2.2、及び、b+c+d=1である。)
前記被覆層は、LiとNbとの酸化物であり、
前記正極活物質の比表面積X(m2/g)と、前記正極活物質におけるNb含有量Y(質量%)とが、下記式(2)の関係を満たす、全固体リチウムイオン電池用正極活物質。
0.65≦Y/X≦1.20 (2) - 前記全固体リチウムイオン電池用正極活物質の50%累積体積粒度D50が3~7μmである、請求項1に記載の全固体リチウムイオン電池用正極活物質。
- 前記被覆層が、LiNbO3を含む、請求項1または2に記載の全固体リチウムイオン電池用正極活物質。
- 請求項1~3のいずれか一項に記載の全固体リチウムイオン電池用正極活物質を含む、全固体リチウムイオン電池用正極。
- 請求項4に記載の全固体リチウムイオン電池用正極で構成された正極層と、負極層と、固体電解質層と、を含む、全固体リチウムイオン電池。
- 下記式(1)に示す組成で表されたコア正極活物質粒子を準備する工程と、
LiaNibCocMndOe (1)
(前記式(1)中、1.0≦a≦1.05、0.8≦b≦0.9、1.8≦e≦2.2、及び、b+c+d=1である。)
前記コア正極活物質粒子の表面に、LiとNbとを含むアルコキシド溶液を用いて、転動流動層装置によって、LiとNbとの酸化物からなる被覆層を形成する工程と、
を含む、全固体リチウムイオン電池用正極活物質の製造方法。 - 前記アルコキシド溶液が、(1)溶質のリチウム源としてメトキシリチウム、エトキシリチウム、及び、イソプロポキシリチウムのいずれか一種、(2)ニオブ源としてペンタメトキシニオブ、ペンタエトキシニオブ、ペンタイソプロポキシニオブのいずれか一種、及び、(3)溶媒としてエタノール、メタノール、イソプロパノールのいずれか一種、を含む溶液である、請求項6に記載の全固体リチウムイオン電池用正極活物質の製造方法。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010225309A (ja) | 2009-03-19 | 2010-10-07 | Toyota Motor Corp | 正極活物質材料の製造方法 |
JP4982866B2 (ja) | 2005-07-01 | 2012-07-25 | 独立行政法人物質・材料研究機構 | 全固体リチウム電池 |
JP2015056307A (ja) | 2013-09-12 | 2015-03-23 | トヨタ自動車株式会社 | 活物質複合粉体及びリチウム電池並びにその製造方法 |
JP2015201252A (ja) * | 2014-04-04 | 2015-11-12 | トヨタ自動車株式会社 | 活物質粉体及びその製造方法 |
JP2017084674A (ja) * | 2015-10-29 | 2017-05-18 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極及びリチウムイオン電池 |
JP2020047383A (ja) * | 2018-09-14 | 2020-03-26 | Jx金属株式会社 | 正極活物質、及び、その製造方法、並びに、正極、及びリチウムイオン電池 |
JP2020064799A (ja) * | 2018-10-18 | 2020-04-23 | Jx金属株式会社 | 全固体リチウムイオン電池用正極の製造方法及び全固体リチウムイオン電池の製造方法 |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4982866B2 (ja) | 2005-07-01 | 2012-07-25 | 独立行政法人物質・材料研究機構 | 全固体リチウム電池 |
JP2010225309A (ja) | 2009-03-19 | 2010-10-07 | Toyota Motor Corp | 正極活物質材料の製造方法 |
JP2015056307A (ja) | 2013-09-12 | 2015-03-23 | トヨタ自動車株式会社 | 活物質複合粉体及びリチウム電池並びにその製造方法 |
JP2015201252A (ja) * | 2014-04-04 | 2015-11-12 | トヨタ自動車株式会社 | 活物質粉体及びその製造方法 |
JP2017084674A (ja) * | 2015-10-29 | 2017-05-18 | Jx金属株式会社 | リチウムイオン電池用正極活物質、リチウムイオン電池用正極及びリチウムイオン電池 |
JP2020047383A (ja) * | 2018-09-14 | 2020-03-26 | Jx金属株式会社 | 正極活物質、及び、その製造方法、並びに、正極、及びリチウムイオン電池 |
JP2020064799A (ja) * | 2018-10-18 | 2020-04-23 | Jx金属株式会社 | 全固体リチウムイオン電池用正極の製造方法及び全固体リチウムイオン電池の製造方法 |
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