CN112573585A - High-voltage lithium cobalt oxide cathode material and preparation method thereof - Google Patents
High-voltage lithium cobalt oxide cathode material and preparation method thereof Download PDFInfo
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- CN112573585A CN112573585A CN201910936927.9A CN201910936927A CN112573585A CN 112573585 A CN112573585 A CN 112573585A CN 201910936927 A CN201910936927 A CN 201910936927A CN 112573585 A CN112573585 A CN 112573585A
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- lithium cobaltate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010406 cathode material Substances 0.000 title claims abstract description 15
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title description 14
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 176
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 176
- 239000000463 material Substances 0.000 claims abstract description 84
- 238000005245 sintering Methods 0.000 claims abstract description 68
- 239000011159 matrix material Substances 0.000 claims abstract description 66
- 238000002156 mixing Methods 0.000 claims abstract description 62
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 39
- 239000010941 cobalt Substances 0.000 claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000007873 sieving Methods 0.000 claims abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002019 doping agent Substances 0.000 claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims description 44
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 40
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 21
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 8
- 150000004679 hydroxides Chemical class 0.000 claims description 8
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- -1 phosphate compound Chemical class 0.000 claims description 8
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 8
- 150000003841 chloride salts Chemical class 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 6
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 6
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 6
- 150000002823 nitrates Chemical class 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 5
- 150000004673 fluoride salts Chemical class 0.000 claims description 5
- 150000003891 oxalate salts Chemical class 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229940071264 lithium citrate Drugs 0.000 claims description 4
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 2
- 229940097267 cobaltous chloride Drugs 0.000 claims description 2
- 229940045032 cobaltous nitrate Drugs 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 description 24
- 238000001816 cooling Methods 0.000 description 17
- 238000010298 pulverizing process Methods 0.000 description 12
- 238000011068 loading method Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000010405 anode material Substances 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- 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
- H01M4/36—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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2006/40—Electric properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-voltage lithium cobaltate cathode material and a preparation method thereof, wherein the method comprises the following steps: step 1, mixing, sintering, crushing and sieving a first cobalt source, a first lithium source and a dopant M to obtain a lithium cobaltate material matrix A; step 2, mixing, sintering, crushing and sieving a second cobalt source, a second lithium source and an additive N to obtain a lithium cobaltate material matrix B; and 3, mixing the lithium cobaltate material matrix A and the lithium cobaltate material matrix B, adding the additive L, sintering, crushing and sieving to obtain the high-voltage lithium cobaltate cathode material. According to the invention, different elements are respectively doped on two different lithium cobaltate material matrixes, and then the two lithium cobaltate material matrixes are mixed and sintered to obtain the high-voltage lithium cobaltate cathode material with high voltage resistance, high specific capacity and excellent cycle performance. The preparation method has the advantages of simple process, environmental protection, no pollution and low manufacturing cost, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of preparation of a lithium ion battery anode material, in particular to a high-voltage lithium cobalt oxide anode material and a preparation method thereof.
Background
Currently, the applied positive electrode materials of lithium ion batteries mainly include lithium cobaltate, lithium nickelate, lithium phosphate, lithium iron phosphate, spinel lithium manganate and lithium nickel cobalt manganate ternary positive electrode materials. The lithium cobaltate cathode material has been commercialized and widely applied to 3C electronic products after years of development, and occupies most market shares of lithium ion battery markets at home and abroad.
The lithium cobaltate positive electrode material has the advantages of outstanding compaction density, high capacity, high voltage and the like, can be flexibly modified according to the performance requirements of products, but with the continuous improvement of the requirements of domestic 3C products on the performance of batteries, higher requirements on the performance of the lithium cobaltate positive electrode material, such as energy density and the like, are provided, so that the lithium cobaltate positive electrode material is also developed towards the direction of high voltage.
At present, main high-voltage products on the market are 4.35V and 4.4V, the capacity is improved to 155mAh/g and 160mAh/g from 140mAh/g of a conventional 4.2V product, for example, Chinese patent CN103618080A provides a preparation method of high-voltage lithium cobaltate, the prepared lithium cobaltate-based lithium ion battery is in the range of 2.8V-4.35V, the 1C first-time discharge gram capacity reaches over 164mAh/g, and the cycle capacity retention rate of 300 weeks is over 89%. However, the theoretical gram capacity of lithium cobaltate is 274mAh/g, which is quite different from that of lithium cobaltate, and the preparation method of high-voltage lithium cobaltate needs to be further improved.
Therefore, it is urgently needed to develop a high-voltage lithium cobalt oxide cathode material with high energy density, stable structure, simple preparation method and excellent cycle performance and a preparation method thereof.
Disclosure of Invention
In order to solve the above problems, the present inventors have made intensive studies to provide a high voltage lithium cobaltate positive electrode material and a method for preparing the same, the method comprising mixing, sintering, crushing and sieving a first cobalt source, a first lithium source and a dopant M to obtain a lithium cobaltate material matrix a; mixing, sintering, crushing and sieving a second cobalt source, a second lithium source and an additive N to obtain a lithium cobaltate material matrix B; and mixing the lithium cobaltate material matrix A and the lithium cobaltate material matrix B, adding the additive L, sintering, crushing and sieving to obtain the high-voltage lithium cobaltate positive electrode material. According to the invention, different elements are respectively doped on two different lithium cobaltate material matrixes, and then the two lithium cobaltate material matrixes are mixed and sintered to obtain the high-voltage lithium cobaltate cathode material with high voltage resistance, high specific capacity and excellent cycle performance. The preparation method has the advantages of simple process, environmental protection, no pollution and low manufacturing cost, and is suitable for large-scale industrial production, thereby completing the invention.
The first aspect of the present invention provides a method for preparing a high-voltage lithium cobaltate positive electrode material, which includes the steps of:
step 1, mixing, sintering, crushing and sieving a first cobalt source, a first lithium source and a dopant M to obtain a lithium cobaltate material matrix A;
step 2, mixing, sintering, crushing and sieving a second cobalt source, a second lithium source and an additive N to obtain a lithium cobaltate material matrix B;
step 3, mixing the lithium cobaltate material matrix A and the lithium cobaltate material matrix B, adding the additive L, sintering, crushing and sieving to obtain the high-voltage lithium cobaltate positive electrode material,
wherein, the doping agent M is a compound or a composition containing an element M, and the element M is selected from one or more of metal elements or nonmetal elements with the atomic number of more than 6 except Co.
In the step 1, the element M is selected from one or more of Al, Zr, Mg, Ti, Mn, Ni, Sn, Zn, Zr, Ca, Sr, Ba, Y, Sm, V, Nb, Ta, Si, Ce, Ge and Pb; and/or
The doping agent M is selected from one or more of oxide, hydroxide, carbonate, nitrate, sulfate, oxalate, acetate, fluoride, chloride and ester containing the element M.
In the step 2, the additive N is a compound or a composition containing an element N, the element N is selected from metal elements with the atomic number of more than 6 except Co, and preferably one or more of Mg, Ni, Zn, Ca, Sr, Ba and Cu;
the additive N is selected from one or more of oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, acetates, fluorides and chlorides containing element N.
In step 3, the additive L is phosphoric acid or a phosphate compound.
Wherein the first cobalt source and the second cobalt source are both compounds or compositions containing cobalt element,
preferably, it is selected from one or more of cobaltosic oxide, cobaltous oxide, cobalt acetate, cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt carbonate, cobalt oxalate, cobalt hydroxide and cobalt oxyhydroxide,
the first lithium source and the second lithium source are both lithium-containing compounds or compositions, preferably each of the first lithium source and the second lithium source is independently selected from one or more of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium fluoride, lithium bromide, lithium chloride, lithium acetate, lithium oxide, lithium citrate, lithium dihydrogen phosphate and lithium phosphate,
the molar ratio of the lithium element in the first lithium source to the cobalt element in the first cobalt source is (1.0-1.2): 1, preferably, Li/Co ═ (1.01 to 1.1): 1.
wherein, in the step 1,
the dopant M is added in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 1.0 part by weight, based on 100 parts by weight of the first cobalt source, and/or
The sintering temperature is 600-1300 ℃, and the sintering time is 4-18 h; preferably, the sintering temperature is 750-1200 ℃, and the sintering time is 5-14 h;
in the step 3, the weight ratio of the lithium cobaltate material matrix A to the lithium cobaltate material matrix B is 1: 1-1: 10, preferably 1: 1-1: 8, and more preferably 1:1 to 1: 5.
In step 3, the additive L is added in an amount of 0.05 to 5.0 parts by weight, preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the total weight of the lithium cobaltate material substrate a and the lithium cobaltate material substrate B.
In the step 3, the sintering temperature is 400-1000 ℃, and more preferably 400-900 ℃; and/or the sintering time is 2-24 h, preferably 3-18 h.
A second aspect of the present invention provides a high voltage lithium cobalt oxide positive electrode material prepared by the method of the first aspect of the present invention.
The invention has the following beneficial effects:
(1) according to the preparation method of the high-voltage lithium cobalt oxide cathode material, different elements are adopted to dope different lithium cobalt oxide material matrixes, the advantages of each doping element are exerted, the lattice stability of the finally obtained lithium cobalt oxide cathode material can be improved, and the electrochemical performance of the cathode material is improved;
(2) according to the preparation method provided by the invention, two lithium cobaltate material matrix particles are mixed, so that the compacted density of the final lithium cobaltate positive electrode material can be improved, and further, the energy density and the specific capacity of the lithium cobaltate positive electrode material are improved;
(3) the lithium cobaltate positive electrode material prepared by the method provided by the invention has high voltage resistance, higher specific capacity and excellent cycle performance. And (3) carrying out cycle performance test at 25 ℃ and 0.5C rate and under the voltage of 4.6V, wherein the cycle retention rate of the obtained lithium cobaltate positive electrode material for 50 weeks is more than 95%.
(4) The preparation method provided by the invention has the advantages of simple process, no pollution, rich raw material sources and low manufacturing cost, and is suitable for large-scale industrial production.
Drawings
FIG. 1 shows a scanning electron microscope image of a high voltage lithium cobaltate positive electrode material obtained in example 1 of the present invention;
fig. 2 shows a cycle curve of the high voltage lithium cobaltate positive electrode material obtained in example 1 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
According to a first aspect of the present invention, there is provided a high voltage lithium cobaltate positive electrode material and a method for preparing the same, the method comprising the steps of:
step 1, mixing, sintering, crushing and sieving a first cobalt source, a first lithium source and a doping agent M to obtain a lithium cobaltate material matrix A.
According to the present invention, in step 1, the first cobalt source is a compound containing cobalt element and a composition thereof, and is preferably one or more selected from cobaltosic oxide, cobaltous oxide, cobalt acetate, cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt carbonate, cobalt oxalate, cobalt hydroxide and cobalt oxyhydroxide, more preferably one or two selected from cobaltosic oxide, cobalt carbonate, cobalt oxalate and cobalt hydroxide, such as cobaltosic oxide.
According to the present invention, in step 1, the first lithium source is selected from lithium-containing compounds and compositions thereof, preferably from one or more of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium fluoride, lithium bromide, lithium chloride, lithium acetate, lithium oxide, lithium citrate, lithium dihydrogen phosphate and lithium phosphate; more preferably one or two selected from lithium carbonate, lithium nitrate, lithium hydroxide. For example, the high purity of the battery-grade lithium carbonate is beneficial to reducing the impurity content of the product and improving the performance, and the fine granularity of the lithium carbonate can improve the uniformity of material mixing, so that the performance of the later-stage product is ensured.
According to the present invention, in step 1, the molar ratio of the lithium element in the first lithium source to the cobalt element in the first cobalt source is Li/Co ═ 1.0 to 1.2: 1, preferably, Li/Co ═ (1.01 to 1.1): 1, more preferably, Li/Co ═ 1.04 to 1.08: 1.
according to the invention, in step 1, the dopant M is a compound comprising an element M, wherein the element M is selected from one or more of metallic elements or non-metallic elements having an atomic number of 6 or more other than Co, preferably from one or more of Al, Zr, Mg, Ti, Mn, Ni, Sn, Zn, Zr, Ca, Sr, Ba, Y, Sm, V, Nb, Ta, Si, Ce, Ge, Pb, more preferably from one or more of Zr, Si, Ti, Sn, Ce, Ge, Pb.
According to a preferred embodiment of the invention, the element M is selected from one or several of Zr, Si, Ti, Ge.
According to the invention, in step 1, the dopant M is selected from one or more of oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, acetates, fluorides, chlorides and esters containing the element M, preferably from one or more of oxides, hydroxides, carbonates, nitrates and esters containing the element M, and more preferably from oxides or hydroxides containing the element M, such as oxides containing the element M.
According to a preferred embodiment of the invention, the dopant M is selected from ZrO2(zirconium oxide), TiO2(titanium oxide) GeO2(germanium oxide), SiO2(silicon dioxide) or a plurality of (silicon dioxide) compounds. The addition amount of the doping agent M needs to be controlled within a certain range, so that the performances of the product such as gram volume, circulation, storage and the like can be ensured simultaneously, and the optimization of the product performance is realized.
According to the present invention, the dopant M is added in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 1.0 part by weight, more preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the first cobalt source, and the prepared lithium cobaltate positive electrode material has excellent electrochemical properties
According to the invention, in step 1, first mixing a first cobalt source and a first lithium source, then adding a dopant M, and mixing to obtain a mixture of the three, wherein the mixing manner is ball milling mixing, the mixing speed is 200-500r/min, the mixing time is 1-6h, preferably, the mixing speed is 300-400 r/min, and the mixing time is 2-5 h.
According to the invention, after mixing, the obtained mixture needs to be sintered, the sintering temperature is 600-1300 ℃, and the sintering time is 4-18 h; preferably, the sintering temperature is 750-1200 ℃, and the sintering time is 5-14 h; more preferably, the sintering temperature is 900-1100 ℃, and the sintering time is 6-10 h. Under the sintering temperature and the sintering time, the product granularity, the morphology and the electrical property of the obtained lithium cobaltate material matrix A reach ideal levels, so that the final lithium cobaltate positive electrode material has excellent electrochemical properties.
According to the invention, in the step 1, after sintering, crushing and sieving are carried out to obtain the lithium cobaltate material matrix A, wherein the median particle size of the lithium cobaltate material matrix A is 10-30 μm, preferably 13-25 μm, and more preferably 16-20 μm.
In the invention, in the step 1, the doping agent M is added, the element M is adopted to dope the lithium cobaltate material matrix A, and the element M can replace a small amount of cobalt ions, so that the structural stability of the lithium cobaltate material matrix A is improved, the structural stability of the final lithium cobaltate anode material is further improved, and the cycle performance of the final high-voltage lithium cobaltate anode material is further improved.
Step 2, mixing, sintering, crushing and sieving a second cobalt source, a second lithium source and an additive N to obtain a lithium cobaltate material matrix B;
according to the present invention, in step 2, the second cobalt source is selected from the same range as the first cobalt source in step 1, and may be the same as or different from the first cobalt source, and the second cobalt source is preferably selected from one or more of cobaltosic oxide, cobaltous acetate, cobaltous sulfate, cobaltous nitrate, cobaltous chloride, cobaltous carbonate, cobaltous oxalate, cobaltous hydroxide, and cobaltous oxyhydroxide, and more preferably selected from one or two of cobaltosic oxide, cobaltous carbonate, cobaltous oxalate, and cobaltous hydroxide, such as cobaltosic oxide.
According to the invention, in step 2, the second lithium source is selected from the same range as the first lithium source in step 1, can be the same as or different from the first lithium source, and is preferably selected from one or more of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium fluoride, lithium bromide, lithium chloride, lithium acetate, lithium oxide, lithium citrate, lithium dihydrogen phosphate and lithium phosphate; more preferably one or two selected from lithium carbonate, lithium nitrate, lithium hydroxide, for example battery grade lithium carbonate.
According to the invention, in step 2, the molar ratio of the lithium element in the second lithium source to the cobalt element in the second cobalt source is (1.0-1.2): 1, preferably, Li/Co ═ (1.01 to 1.1): 1, more preferably, Li/Co ═ 1.04 to 1.08: 1.
according to the invention, in step 2, the additive N is selected from compounds comprising the element N, wherein the element N is selected from one or more of metal elements with an atomic number of 6 or more other than Co, preferably from one or more of Mg, Ni, Zn, Ca, Sr, Ba, Cu, more preferably from one or more of Mg, Zn, Ni, Cu, most preferably Mg.
According to the invention, in step 2, the additive N is selected from one or more of oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, acetates, fluorides and chlorides containing element N, preferably from one or more of oxides, hydroxides, carbonates, sulfates and chlorides containing element N, and more preferably from one or more of oxides, carbonates, chlorides and sulfates containing element N.
According to a preferred embodiment of the invention, the additive N is chosen from MgO, MgCO3、MgCl2、MgSO4At least one of (1). The addition amount of the additive N needs to be controlled within a certain range, so that the performances of the product such as gram volume, circulation, storage and the like can be ensured simultaneously, and the optimization of the product performance is realized. If the doping amount is too small, the ideal effects such as improving the cycle performance and the like may not be achieved; if the amount of the dopant is too large, the gram volume of the product is reduced.
According to the present invention, in step 2, the additive N is added in an amount of 0.01 to 2.0 parts by weight, preferably 0.05 to 1.0 part by weight, more preferably 0.08 to 0.5 part by weight, for example 0.08 to 0.3 part by weight, based on 100 parts by weight of the second cobalt source.
According to the invention, in step 2, the second cobalt source and the second lithium source are firstly mixed, and then the additive N is added and mixed to obtain a mixture of the three, wherein the mixing mode is preferably a mixing mode commonly used in the field, such as ball milling mixing, wherein the mixing speed of the ball milling mixing is 200-500r/min, and the mixing time is 1-6 h.
According to the invention, in the step 2, the mixture is required to be sintered after mixing, the sintering temperature is 600-1300 ℃, and the sintering time is 4-18 h; preferably, the sintering temperature is 750-1200 ℃, and the sintering time is 5-14 h; more preferably, the sintering temperature is 900-1100 ℃, and the sintering time is 6-10 h. At the sintering temperature, the granularity, the appearance and the electrical property of the product all reach ideal levels.
According to the invention, in the step 2, after sintering, crushing and sieving are carried out to obtain the lithium cobaltate material matrix B, wherein the median particle size of the lithium cobaltate material matrix B is 10-30 μm, preferably 13-25 μm, and more preferably 16-20 μm.
According to the invention, the lithium cobaltate material matrix B is doped with the metal element N (such as Mg), and then mixed and sintered with the lithium cobaltate material matrix A, so that the conductivity of the lithium cobaltate positive electrode material can be improved, the internal resistance of the positive electrode material is reduced, the voltage resistance and low temperature resistance are improved, the thermal stability of the positive electrode material can be enhanced, and the cycle performance of the positive electrode material is further improved.
And 3, mixing the lithium cobaltate material matrix A and the lithium cobaltate material matrix B, adding the additive L, sintering, crushing and sieving to obtain the high-voltage lithium cobaltate cathode material.
According to the invention, in step 3, the lithium cobaltate material matrix A and the lithium cobaltate material matrix B are mixed in a mixing mode commonly used in the field, such as ball milling mixing, wherein the mixing speed is 200-500r/min, the mixing time is 1-6h, and then the additive L is added and mixed to obtain a mixture.
The inventor finds that the particle size distribution of the finally obtained high-voltage lithium cobalt oxide anode material is uniform by mixing and sintering two lithium cobalt oxide material matrixes A and B with medium particle sizes which are not different from each other, and the obtained anode material is high-voltage resistant and excellent in cycle performance.
According to the invention, in step 3, the additive L is phosphoric acid or a phosphate-based compound.
According to a preferred embodiment of the present invention, the additive L is selected from one or more of lithium iron phosphate, lithium vanadium phosphate, phosphoric acid, lithium phosphate, aluminum phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and the like.
According to a further preferred embodiment of the present invention, the additive L is selected from at least one of lithium iron phosphate, lithium vanadium phosphate and lithium phosphate.
The inventor finds that the cycle stability of the finally obtained high-voltage lithium cobaltate cathode material can be improved by adding the additive L (such as phosphate) after the lithium cobaltate material matrix A and the lithium cobaltate material matrix B are mixed and then performing mixed sintering. On the one hand, the phosphate compound is coated, so that a stable phosphate coating layer can be formed on the surface of the particles, the direct contact between the lithium cobaltate particles and the electrolyte can be effectively isolated, the occurrence of side reactions is inhibited, the consumption of the electrolyte is reduced, and the circulation stability of the material is effectively improved. On the other hand, the covalent bond between O and P ions in phosphate radical is stronger, and can play an effective stabilizing role in the crystal structure of the material.
According to the invention, in the step 3, the mass ratio of the lithium cobaltate material matrix A to the lithium cobaltate material matrix B is 1: 1-1: 10, preferably 1: 1-1: 8, and more preferably 1:1 to 1: 5.
According to the present invention, in step 3, the additive L is added in an amount of 0.05 to 5.0 parts by weight, preferably 0.1 to 2.5 parts by weight, more preferably 0.2 to 1.0 part by weight, for example 0.2 to 0.5 part by weight, based on 100 parts by weight of the total weight of the lithium cobaltate material matrix a and the lithium cobaltate material matrix B.
According to the invention, after the mixture is obtained in the step 3, the mixture is sintered, wherein the sintering temperature is 400-1000 ℃, preferably 400-900 ℃, more preferably 400-800 ℃, for example 400-600 ℃; and/or
The sintering time is 2-24 h, preferably 3-18 h, more preferably 4-10 h, for example 4-8 h. At the sintering temperature, the granularity, the appearance and the electrical property of the product all reach ideal levels.
According to the invention, in the step 3, the median particle diameter of the obtained high-voltage lithium cobaltate positive electrode material is 15-25 μm, preferably 16-22 μm, and more preferably 17-19 μm.
The inventor finds that different doping elements are added into the lithium cobaltate positive electrode material at the same time, so that the finally obtained lithium cobaltate positive electrode material is low in specific capacity and poor in cycle performance.
The high-voltage lithium cobaltate positive electrode material prepared by the preparation method provided by the invention has excellent cycle performance under the high voltage of 4.6V, for example, the cycle retention rate of the lithium cobaltate positive electrode material in 50 weeks is up to 95% or more when a cycle performance test is carried out under the voltage of 4.6V at the temperature of 25 ℃ and the multiplying power of 0.5C.
The invention also provides a high-voltage lithium cobalt oxide positive electrode material which is prepared by the preparation method of the first aspect of the invention. The obtained high-voltage lithium cobalt oxide positive electrode material is high-voltage resistant, high in specific capacity and excellent in cycle performance.
Examples
Example 1
Preparation of a lithium cobaltate material matrix A: 150g of cobaltosic oxide and 72g of lithium carbonate were mixed by grinding, and 0.15g of ZrO was added2Mixing, loading into crucible, sintering at 1000 deg.C in muffle furnace for 10 hr, cooling, pulverizing, and sieving to obtain D5016 μm lithium cobaltate base material a;
preparation of lithium cobaltate matrix B: grinding and mixing 150g of cobaltosic oxide and 72g of lithium carbonate, adding 0.12g of MgO, mixing, putting into a crucible, sintering at 1000 ℃ in a muffle furnace for 10 hours, cooling, crushing and sieving to obtain D5017 μm lithium cobaltate base material B;
preparing a high-voltage lithium cobaltate positive electrode material: grinding and mixing 75g of lithium cobaltate matrix A and 75g of lithium cobaltate matrix B, adding 0.3g of lithium vanadium phosphate, grinding and mixing, then putting into a crucible, sintering at 400 ℃ in a muffle furnace for 8 hours, and finishing sinteringCooling, pulverizing and sieving to obtain D5018 μm high voltage lithium cobaltate positive electrode material.
Scanning electron microscope test is carried out on the obtained high-voltage lithium cobaltate cathode material, and the obtained SEM image is shown in figure 1. As can be seen from fig. 1, there are more protrusions on the surface of lithium cobaltate due to the interference of phosphate with the growth of lithium cobaltate crystals.
Example 2
Preparation of a lithium cobaltate material matrix A: 150g of cobaltosic oxide and 72g of lithium carbonate were mixed by grinding, and 0.15g of TiO was added2Mixing, loading into crucible, sintering at 1000 deg.C in muffle furnace for 10 hr, cooling, pulverizing, and sieving to obtain D5017.5 μm lithium cobaltate base material a;
preparation of lithium cobaltate matrix B: 150g of cobaltosic oxide was mixed with 72g of lithium carbonate by grinding, and 0.12g of MgCl was added2Mixing, loading into crucible, sintering at 1000 deg.C in muffle furnace for 10 hr, cooling, pulverizing, and sieving to obtain D5016.5 μm lithium cobaltate base material B;
preparing a high-voltage lithium cobaltate positive electrode material: grinding and mixing 50g of lithium cobaltate matrix A and 100g of lithium cobaltate matrix B, adding 0.45g of lithium phosphate, grinding and mixing, then putting into a crucible, sintering at 600 ℃ in a muffle furnace for 4 hours, cooling, then crushing and sieving to finally obtain D5017.5 μm high voltage lithium cobaltate material.
Example 3
Preparation of a lithium cobaltate material matrix A: 150g of cobaltosic oxide was mixed with 50g of lithium carbonate by grinding, and 0.15g of GeO was added2Mixing, loading into crucible, sintering at 1000 deg.C in muffle furnace for 10 hr, cooling, pulverizing, and sieving to obtain D5018.5 μm lithium cobaltate base material a;
preparation of lithium cobaltate matrix B: 150g of cobaltosic oxide and 72g of lithium carbonate were mixed by grinding, and 0.12g of MgCO was added3Mixing, loading into crucible, sintering at 1000 deg.C in muffle furnace for 10 hr, cooling, pulverizing, and sieving to obtain D50Cobalt acid 16.5 μmA lithium base material B;
preparing a high-voltage lithium cobaltate positive electrode material: grinding and mixing 50g of lithium cobaltate matrix A and 100g of lithium cobaltate matrix B, adding 0.45g of lithium vanadium phosphate, grinding and mixing, then putting into a crucible, sintering at 600 ℃ in a muffle furnace for 4 hours, completing sintering, cooling, crushing and sieving to finally obtain D5017.5 μm high voltage lithium cobaltate material.
Example 4
Preparation of a lithium cobaltate material matrix A: 150g of cobaltosic oxide was mixed with 50g of lithium carbonate by grinding, and 0.15g of SiO was added2Mixing, loading into crucible, sintering at 900 deg.C in muffle furnace for 10 hr, cooling, pulverizing, and sieving to obtain D5018.5 μm lithium cobaltate base material a;
preparation of lithium cobaltate matrix B: 150g of cobaltosic oxide and 72g of lithium carbonate were mixed by grinding, and 0.12g of MgCO was added3Mixing, loading into crucible, sintering at 950 deg.C in muffle furnace for 8 hr, cooling, pulverizing, and sieving to obtain D5016.5 μm lithium cobaltate base material B;
preparing a high-voltage lithium cobaltate positive electrode material: grinding and mixing 50g of lithium cobaltate matrix A and 100g of lithium cobaltate material matrix B, adding 0.45g of lithium iron phosphate, grinding and mixing, then putting into a crucible, sintering at 800 ℃ in a muffle furnace for 4 hours, cooling, crushing and sieving to finally obtain D5017.5 μm high voltage lithium cobaltate material.
Example 5
Preparation of a lithium cobaltate material matrix A: 150g of cobaltosic oxide was mixed with 50g of lithium carbonate by grinding, and 0.15g of TiO was added2Mixing, loading into crucible, sintering at 900 deg.C in muffle furnace for 12 hr, cooling, pulverizing, and sieving to obtain D5018.5 μm lithium cobaltate base material a;
preparation of lithium cobaltate matrix B: 150g of cobaltosic oxide and 72g of lithium carbonate were mixed by grinding, and 0.12g of MgCO was added3Mixing, loading into crucible, sintering at 950 deg.C in muffle furnace for 15 hr, cooling, pulverizing, and sieving to obtain D50＝16.5μmThe lithium cobaltate base material B;
preparing a high-voltage lithium cobaltate positive electrode material: grinding and mixing 50g of lithium cobaltate matrix A and 100g of lithium cobaltate material matrix B, adding 0.45g of lithium iron phosphate, grinding and mixing, then putting into a crucible, sintering at 800 ℃ in a muffle furnace for 4 hours, cooling, crushing and sieving to finally obtain D5017.5 μm high voltage lithium cobaltate material.
Example 6
Preparation of a lithium cobaltate material matrix A: 150g of cobaltosic oxide was mixed with 50g of lithium carbonate by grinding, and 0.15g of ZrO was added2Mixing, loading into crucible, sintering at 1050 deg.C in muffle furnace for 9 hr, cooling, pulverizing, and sieving to obtain D5018.5 μm lithium cobaltate base material a;
preparation of lithium cobaltate matrix B: 150g of cobaltosic oxide and 72g of lithium carbonate were mixed by grinding, and 0.12g of MgCO was added3Mixing, loading into crucible, sintering at 1050 deg.C in muffle furnace for 12 hr, cooling, pulverizing, and sieving to obtain D5016.5 μm lithium cobaltate base material B;
preparing a high-voltage lithium cobaltate positive electrode material: grinding and mixing 50g of lithium cobaltate material matrix A and 100g of lithium cobaltate material matrix B, adding 0.5g of lithium iron phosphate, grinding and mixing, then putting into a crucible, sintering at 700 ℃ in a muffle furnace for 7h, cooling, crushing and sieving to finally obtain D5017.5 μm high voltage lithium cobaltate material.
Examples of the experiments
A button cell was assembled by using a conventional commercial lithium cobalt oxide positive electrode material (sample 1) and the high-voltage lithium cobalt oxide positive electrode material (sample 2) obtained in example 1 as positive electrode active materials, and a lithium plate as a negative electrode, and the button cell was subjected to a test using a blue-electricity system, wherein the charge-discharge voltage was 3.0 to 4.6V and the charge-discharge rate was 0.5C, and the charge-discharge test was performed at normal temperature (e.g., 25 ℃), and a cycle curve, which is a relationship curve between the number of charge-discharge cycles and the battery capacity, of the obtained battery was shown in fig. 2.
As can be seen from fig. 2, the capacity retention of sample 1 after 50 weeks of cycling was 90.1%, while the capacity retention of sample 2 was as high as 95% or more. The phosphate compound is coated, so that a stable phosphate coating layer can be formed on the surface of the positive electrode material particles, the direct contact between the lithium cobaltate positive electrode material particles and the electrolyte can be effectively isolated, the occurrence of side reactions is inhibited, and the consumption of the electrolyte is reduced; in addition, the covalent bond between O and P ions in phosphate radical is strong, and can play an effective stabilizing role in the crystal structure of the material, thereby effectively improving the cycling stability of the material.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A preparation method of a high-voltage lithium cobaltate positive electrode material is characterized by comprising the following steps of:
step 1, mixing, sintering, crushing and sieving a first cobalt source, a first lithium source and a dopant M to obtain a lithium cobaltate material matrix A;
step 2, mixing, sintering, crushing and sieving a second cobalt source, a second lithium source and an additive N to obtain a lithium cobaltate material matrix B;
and 3, mixing the lithium cobaltate material matrix A and the lithium cobaltate material matrix B, adding the additive L, sintering, crushing and sieving to obtain the high-voltage lithium cobaltate cathode material.
2. The method according to claim 1, wherein, in step 1,
the doping agent M is a compound or a composition containing an element M, and the element M is selected from one or more of metal elements or nonmetal elements with the atomic number of more than 6 except Co.
3. The method according to claim 2, wherein the element M is selected from one or more of Al, Zr, Mg, Ti, Mn, Ni, Sn, Zn, Ca, Sr, Ba, Y, Sm, V, Nb, Ta, Si, Ce, Ge, Pb; and/or
The doping agent M is selected from one or more of oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, acetates, fluorides, chlorides and esters containing the element M.
4. The method of claim 1,
in the step 2, the additive N is a compound or a composition containing element N, the element N is selected from metal elements with the atomic number of more than 6 except Co, preferably one or more of Mg, Ni, Zn, Ca, Sr, Ba and Cu,
the additive N is selected from one or more of oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, acetates, fluorides and chlorides containing element N;
in step 3, the additive L is phosphoric acid or a phosphate compound.
5. The method of claim 1, wherein the first cobalt source and the second cobalt source are both compounds or compositions comprising cobalt,
preferably, the first cobalt source and the second cobalt source are each independently selected from one or more of cobaltosic oxide, cobaltous acetate, cobaltous sulfate, cobaltous nitrate, cobaltous chloride, cobaltous carbonate, cobaltous oxalate, cobaltous hydroxide and cobaltous oxyhydroxide; and/or
The first lithium source and the second lithium source are each lithium-containing compounds or compositions,
preferably, the first lithium source and the second lithium source are each independently selected from one or more of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium fluoride, lithium bromide, lithium chloride, lithium acetate, lithium oxide, lithium citrate, lithium dihydrogen phosphate and lithium phosphate,
the molar ratio of the lithium element in the first lithium source to the cobalt element in the first cobalt source is (1.0-1.2): 1, preferably, Li/Co ═ (1.01 to 1.1): 1.
6. the method according to claim 1, wherein, in step 1,
the dopant M is added in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 1.0 part by weight, based on 100 parts by weight of the first cobalt source
The sintering temperature is 600-1300 ℃, and the sintering time is 4-18 h; preferably, the sintering temperature is 750-1200 ℃, and the sintering time is 5-14 h.
7. The method according to claim 1, wherein in step 3, the weight ratio of the lithium cobaltate material matrix A to the lithium cobaltate material matrix B is 1: 1-1: 10, preferably 1: 1-1: 8, and more preferably 1:1 to 1: 5.
8. The method according to claim 1, wherein, in step 3,
the additive L is added in an amount of 0.05 to 5.0 parts by weight, preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the total weight of the lithium cobaltate material substrate A and the lithium cobaltate material substrate B.
9. The method according to claim 1, wherein, in step 3,
the sintering temperature is 400-1000 ℃, and more preferably 400-900 ℃;
the sintering time is 2-24 h, preferably 3-18 h.
10. A high voltage lithium cobaltate positive electrode material prepared by the method of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114790012A (en) * | 2022-04-22 | 2022-07-26 | 格林美（无锡）能源材料有限公司 | Lithium cobaltate positive electrode material and preparation method and application thereof |
| CN115676905A (en) * | 2022-11-22 | 2023-02-03 | 天津巴莫科技有限责任公司 | High-voltage cobalt acid lithium battery cathode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682326A (en) * | 2013-12-13 | 2014-03-26 | 南通瑞翔新材料有限公司 | High-capacity lithium cobalt oxide-base lithium ion battery anode material and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682326A (en) * | 2013-12-13 | 2014-03-26 | 南通瑞翔新材料有限公司 | High-capacity lithium cobalt oxide-base lithium ion battery anode material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114790012A (en) * | 2022-04-22 | 2022-07-26 | 格林美（无锡）能源材料有限公司 | Lithium cobaltate positive electrode material and preparation method and application thereof |
| CN114790012B (en) * | 2022-04-22 | 2024-04-16 | 格林美（无锡）能源材料有限公司 | Lithium cobalt oxide positive electrode material and preparation method and application thereof |
| CN115676905A (en) * | 2022-11-22 | 2023-02-03 | 天津巴莫科技有限责任公司 | High-voltage cobalt acid lithium battery cathode material and preparation method thereof |
| CN115676905B (en) * | 2022-11-22 | 2024-04-09 | 天津巴莫科技有限责任公司 | High-voltage lithium cobalt oxide battery positive electrode material and preparation method thereof |
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Application publication date: 20210330 |