CN116947123A - Modified positive electrode material and preparation method and application thereof - Google Patents
Modified positive electrode material and preparation method and application thereof Download PDFInfo
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- CN116947123A CN116947123A CN202311200544.8A CN202311200544A CN116947123A CN 116947123 A CN116947123 A CN 116947123A CN 202311200544 A CN202311200544 A CN 202311200544A CN 116947123 A CN116947123 A CN 116947123A
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- positive electrode
- electrode material
- cobalt
- aluminum
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 54
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 48
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 aluminum compound Chemical class 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 59
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 239000010406 cathode material Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 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 8
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 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
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 0.000 claims 1
- 239000003759 ester based solvent Substances 0.000 claims 1
- 239000005453 ketone based solvent Substances 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 21
- 239000007787 solid Substances 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 17
- 238000007086 side reaction Methods 0.000 description 16
- 239000002203 sulfidic glass Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 238000005245 sintering Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000002356 single layer Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000009501 film coating Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000007888 film coating Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910008029 Li-In Inorganic materials 0.000 description 2
- 229910006670 Li—In Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052755 nonmetal Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical class [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical class [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- C01P2006/80—Compositional purity
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application belongs to the technical field of lithium battery anode materials, and particularly relates to a modified anode material, a preparation method and application thereof. The method comprises the following steps: firstly, adding a certain amount of cobalt source and aluminum source into a solvent, and fully stirring, wherein the solvent dissolves the aluminum source and does not dissolve the cobalt source to obtain an aluminum source solution with the cobalt source dispersed therein; then adding the positive electrode material into the solution, stirring fully, and then stirring and evaporating at a certain temperature to dryness to obtain a precursor; finally, the precursor is subjected to heat treatment in an oxygen-containing atmosphere to form a modified positive electrode material with a coating layer, wherein the coating layer contains a cobalt compound and an aluminum compound. The method provided by the application can improve the mechanical strength of the modified anode material particles, can also improve the capacity, multiplying power performance and cycle performance of the solid anode, and has the advantages of simple process, low equipment requirement, low cost and the like.
Description
Technical Field
The application belongs to the technical field of all-solid-state lithium battery anode materials, and particularly relates to a modified anode material, a preparation method and application thereof.
Background
In recent years, the traditional liquid lithium ion battery has a plurality of challenges such as poor safety and limited energy density, and the all-solid-state battery adopts solid electrolyte to replace liquid electrolyte, so that the safety and the energy density of the battery can be remarkably improved. Among them, sulfide solid-state electrolytes having high ionic conductivity and excellent mechanical properties are considered as solid-state electrolytes most likely to be used in large-scale applications. In addition, the selection of the positive electrode material is also one of key factors for improving the energy density of the all-solid-state lithium battery, and the layered oxide positive electrode material (particularly the high-nickel positive electrode material with the nickel content of more than 80%) which is concerned has the advantages of high capacity, high theoretical energy density and the like, and is one of excellent all-solid-state lithium battery candidate positive electrode materials.
However, after the high-nickel positive electrode material is directly contacted with the sulfide solid electrolyte, serious interface side reaction is generated to form an insulating decomposition product, and secondly, due to mismatching of electrochemical potentials of the high-nickel positive electrode material and the sulfide solid electrolyte, a space charge layer is generated, li+ near the interface is redistributed, and a high-resistance layer of a few nanometers is formed on the sulfide solid electrolyte side, wherein both phenomena can influence the capacity performance and the safety performance of the solid battery. In addition, as the surface of the high-nickel positive electrode material is provided with a layer of surface residual alkali (mainly comprising lithium hydroxide, lithium carbonate and lithium oxide) with the thickness of about 2-15 nm, the electron conductivity of the surface residual alkali is extremely low, and the multiplying power performance of the positive electrode material can be influenced.
At present, the literature reports that the conventional means for solving the interface side reaction is to carry out surface coating modification on the positive electrode material so as to prevent the positive electrode material from directly contacting with the sulfide solid electrolyte, and the interface side reaction and the generation of a space charge layer can be reduced. Common coating modification methods mainly comprise Atomic Layer Deposition (ALD), pulse Laser Deposition (PLD), chemical Vapor Deposition (CVD) and the like, but the methods have the problems of high process difficulty, high equipment requirement, high manufacturing cost and the like, and are unfavorable for mass production, so that a surface coating modification method with simple process, low equipment requirement and low cost needs to be developed.
In addition, according to the literature report, the interface side reaction of the high-nickel cathode material and the sulfide solid electrolyte is due to the fact that the cathode material has strong oxidizing property, the sulfide solid electrolyte is easily oxidized and decomposed, and the interface side reaction increases with the increase of the nickel content, but the reduction of the nickel content of the cathode material inevitably leads to the loss of the material capacity.
Regarding the problem of poor multiplying power of the positive electrode material, the conventional solution is to wash out residual alkali on the surface of the material by adopting a water washing mode, but the ternary positive electrode material (particularly the high-nickel positive electrode material) can damage the surface bulk phase structure in the water washing process to form a rock salt structure, thereby affecting the capacity of the material and the exertion of circulation, and recovering part of the surface bulk phase structure by adopting a heat treatment mode, but still has certain defects.
Disclosure of Invention
In order to solve the defects in the prior art, the application provides a modified anode material, and a preparation method and application thereof. The method for modifying the surface of the positive electrode material can improve the mechanical strength of the positive electrode material particles, can improve the capacity, the multiplying power performance and the cycle performance of the solid positive electrode, and has the advantages of simple process, low equipment requirement, low cost and the like.
The technical scheme provided by the application is as follows:
a preparation method of a modified cathode material comprises the following steps: firstly, adding a certain amount of cobalt source and aluminum source into a solvent, and fully stirring, wherein the solvent dissolves the aluminum source and does not dissolve the cobalt source to obtain an aluminum source solution with the cobalt source dispersed therein; then adding the granular positive electrode material into the solution, stirring fully, and then stirring and evaporating at a certain temperature to obtain a precursor; finally, the precursor is subjected to heat treatment in an oxygen-containing atmosphere to form a modified positive electrode material with a coating layer, wherein the coating layer contains a cobalt compound and an aluminum compound. The amount of the solvent is not limited here as long as the solvent can completely dissolve the aluminum source.
The technical scheme adopts a one-step method to carry out modified coating on the surface of the positive electrode material, and the method can form a cobalt compound island-shaped coating layer and an aluminum compound membranous coating layer on the surface of the positive electrode material, especially the surface of a high-nickel positive electrode material. The island-shaped coating layer has the effects of improving electronic conductivity and reducing nickel content on the surface of the material, can improve the multiplying power and the cycling stability of the material, and the film coating can fill the exposed area outside the island-shaped coating, so that the anode material and the sulfide solid electrolyte are completely isolated, the interface side reaction is reduced, the effect of improving the cycling stability of the solid anode is achieved, and meanwhile, the mechanical strength of anode material particles can be increased.
Furthermore, there are two risks of peeling or cracking of the coating layer present in the existing laminate film coating: firstly, the coating layer is easy to fall off in the process of mixing materials or manufacturing the battery, so that the coating effect is unstable, and the first effect and the cycle performance of the battery are further affected; and secondly, the coating layer is broken due to volume expansion of the positive electrode material in charge and discharge cycles, so that the cycle performance of the battery is affected. After the method provided by the application is adopted, island-shaped cobalt salt can be tightly attached to the surface of the positive electrode material in the forming process because the island-shaped cobalt salt contains cobalt which is the same as cobalt in the positive electrode material, so that a crystalline island-shaped coating layer is formed. The cobalt salt is firmly embedded into the aluminum salt coating layer, so that the cobalt salt has a good anchoring effect on the aluminum salt coating layer, the stability of the coating layer is greatly improved, and the mechanical strength of the modified positive electrode material is improved.
The application carries out island coating of cobalt compound on the positive electrode material, and forms a membranous coating layer of aluminum compound on the surface, thereby being capable of repairing the remained exposed area when the cobalt is coated. More importantly, when the coating is carried out by adopting a one-step method, as cobalt salt and aluminum salt exist simultaneously, the aluminum source is dissolved and then subjected to precipitation and low-temperature treatment, the obtained coating layer belongs to an amorphous state, the amorphous coating layer has good flexibility and is not easy to crack, various stresses generated in the charging and discharging processes of the anode material can be absorbed, the generation of cracks of the modified anode material particles is relieved, and the mechanical strength of the modified anode particles is improved. In addition, because aluminum is very stable, the compatibility with sulfide solid electrolyte is better than Co, and the aluminum hardly reacts with sulfide solid electrolyte, so that the generation of interface side reaction can be further reduced, and the cycle performance of the solid-state battery is improved.
Specifically, the cobalt source is cobalt salt or cobalt oxide.
Specifically, the cobalt source is selected from any one or more of cobalt nitrate, cobalt sulfate, cobalt hydroxide, cobalt acetate, cobalt oxide, cobaltosic oxide and cobaltosic oxide.
The cobalt source is insoluble in a solvent, and after the surface is coated, the electron conductivity can be improved, and the nickel content of the surface of the positive electrode material can be reduced. Other transition metal compounds having the same function, such as titanium, zirconium, niobium metal compounds, may also be selected.
Specifically, the aluminum source is aluminum salt or aluminum oxide for forming the amorphous coating layer.
Specifically, the aluminum source is selected from any one or more of aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum silicate, aluminum n-propoxide, aluminum isopropoxide, aluminum hydroxide and aluminum oxide.
The aluminum source is dissolved in a solvent, has good compatibility with sulfide solid electrolyte and can generate an amorphous coating. Other transition metal compounds having the same function, such as metal compounds of niobium, tantalum, zirconium, or non-metal compounds, such as non-metal compounds of boron, silicon, phosphorus, sulfur, may also be selected.
Specifically, the solvent is at least one of water, an alcohol solvent, an ester solvent and a ketone solvent.
The alcohol solvent can be ethanol, isopropanol, ethylene glycol, etc. The ester solvent can be ethyl acetate, butyl acetate, dimethyl carbonate, etc. The ketones are acetone, methyl ethyl ketone, cyclohexanone, etc.
Specifically, the evaporating temperature is 50-150 ℃, and the specific temperature can be adjusted according to the type of the solvent.
Specifically, the heat treatment temperature is 200-700 ℃, and the specific temperature can be adjusted according to the type of the coating layer material.
Specifically, the weight percentage of cobalt in the obtained coating layer and the weight percentage of the positive electrode material are 0.2-5.0%.
Specifically, the weight percentage of the aluminum in the obtained coating layer and the weight percentage of the positive electrode material are 0.2-5.0%.
Specifically, the positive electrode material contains nickel, cobalt and manganese elements, and the percentage of nickel in the positive electrode material to the total molar weight of nickel cobalt manganese transition metal is more than 60%. Preferably, greater than 80%.
The method for modifying the surface of the positive electrode material provided by the application can be used for ternary positive electrode materials with low nickel content, medium nickel content or high nickel content, and is preferably used for high nickel positive electrode materials.
The application also provides a modified positive electrode material prepared by the preparation method of the modified positive electrode material.
Specific:
the cobalt compounds are distributed on the surface of the positive electrode material in an island shape;
the aluminum compound is coated on the surface of the positive electrode material in a layered manner;
the cobalt compound is embedded in the aluminum compound and is connected to the positive electrode material.
Based on the technical proposal, a cobalt compound island coating layer and an aluminum compound membranous coating layer are formed on the surface of the positive electrode material. The island-shaped coating layer has the effects of improving electronic conductivity and reducing nickel content on the surface of the material, can improve the multiplying power and the cycling stability of the material, and the film coating can fill the exposed area outside the island-shaped coating, so that the anode material and the sulfide solid electrolyte are completely isolated, the interface side reaction is reduced, the effect of improving the cycling stability of the solid anode is achieved, and meanwhile, the mechanical strength of anode material particles can be increased.
The application also provides application of the modified positive electrode material prepared by the preparation method of the modified positive electrode material, which is used for preparing all-solid-state lithium batteries.
The preparation method of the modified cathode material provided by the application can reduce the Ni content on the surface of the material, reduce side reaction, improve the cycle performance of the solid-state battery and improve the doubling performance.
The modified anode material provided by the application is also suitable for lithium batteries of liquid systems, semi-solid systems and solid systems.
The beneficial effects of the application are as follows:
1. according to literature reports, in NCM ternary cathode materials, ni element has two valence states (Ni 2+ And Ni 3+ ) The divalent nickel is stable, the trivalent nickel is unstable and has oxidizing property, sulfide solid electrolyte can be oxidized and decomposed, and the products of the oxidized and decomposed products can cause impedance to be increased. While high nickel NCM positive electrode materials have more Ni 3+ Thus, the side reactions of the high nickel material with the sulfide solid state electrolyte are greater than those of the low nickel cathode material. Compared with nickel, cobalt has better compatibility with sulfide solid electrolyte, and the cobalt compound is coated on the surface of the high-nickel positive electrode material particles, so that the Ni content on the surface of the positive electrode material can be reduced, side reaction is reduced, and the cycle performance of the solid battery is improved.
2. In the heat treatment process, the cobalt source reacts with residual lithium salt (lithium carbonate, lithium hydroxide and lithium oxide) on the surface of the positive electrode material, an island-shaped coating layer of cobalt compound is formed on the surface of the material, and the cobalt compound of the island-shaped coating layer has good electron conductivity and forms a good electron channel, so that the effect of improving the capacity and the multiplying power performance of the positive electrode material is achieved. After the technical scheme of the application is adopted, the island-shaped cobalt compound has the functions of stabilizing the layered structure of the anode material, reducing impedance and improving ploidy.
3. The cobalt compound island coating is carried out on the positive electrode material, and meanwhile, a membranous coating layer of aluminum compound is formed on the surface, so that the exposed area remained in the cobalt coating process can be repaired, and more importantly, when the cobalt compound island coating is carried out on the positive electrode material by adopting the one-step coating method, the obtained coating layer belongs to an amorphous state due to the existence of cobalt salt and aluminum salt, has good flexibility and is not easy to break, various stresses generated in the charging and discharging processes of the positive electrode material can be absorbed, the generation of cracks of particles of the modified positive electrode material is relieved, and the mechanical strength of the modified positive electrode particles is improved. In addition, because aluminum is very stable, the compatibility with sulfide solid electrolyte is better than Co, and the aluminum hardly reacts with sulfide solid electrolyte, so that the generation of side reaction can be further reduced, and the cycle performance of the solid-state battery is improved.
4. The application adopts a one-step method to form two different types of coating layers (island shape and membranous shape) on the surface of the anode material, has simple process flow, low equipment requirement and low cost, and is convenient for mass production.
Drawings
Fig. 1 is a schematic structural diagram of a modified cathode material with a coating layer provided by the application.
Fig. 2 is a TEM image of one region of the modified cathode material with a coating layer provided by the present application.
Fig. 3 is a TEM image of another region of the modified cathode material with a coating layer provided by the present application.
Fig. 4 is a schematic diagram of the structure of an all-solid-state lithium battery in performance test.
Detailed Description
The principles and features of the present application are described below with examples only to illustrate the present application and not to limit the scope of the present application.
Example 1
Cladding experiments were performed using NCM811 cathode material (a ternary cathode material product purchased from beijing liter materials technologies, inc. Firstly, accurately weighing 0.15 g of nano cobalt hydroxide and 0.2 g of aluminum isopropoxide in 5mL of absolute ethyl alcohol, fully stirring for 30 minutes at 50 ℃, adding 3 g of positive electrode material, stirring and evaporating at 60 ℃ until evaporating, and finally transferring into a tube furnace, and sintering under the oxygen atmosphere, wherein the sintering conditions are as follows: 500-3 h, heating up at a rate of 5 ℃/min, obtaining the modified positive electrode material A with a composite coating layer (the coating amount is Co:2.0 wt% and Al:1.0 wt%).
Example 2
Coating experiments were performed using NCM811 positive electrode material. Firstly, accurately weighing 0.015 g of nano cobalt hydroxide and 0.04 g of aluminum isopropoxide in 5mL of absolute ethyl alcohol, fully stirring for 30 minutes at 50 ℃, adding 3 g of positive electrode material, stirring and evaporating at 60 ℃ until evaporating, and finally transferring into a tube furnace, and sintering under the oxygen atmosphere, wherein the sintering conditions are as follows: 200-3 h, heating up at a rate of 5 ℃/min, and obtaining the modified positive electrode material B with a composite coating layer (the coating amount is Co:0.2 wt% and Al:0.2 wt%).
Example 3
Coating experiments were performed using NCM811 positive electrode material. Firstly, accurately weighing 0.4 g of nano cobalt hydroxide and 1.0 g of aluminum isopropoxide in 5mL of absolute ethyl alcohol, fully stirring for 30 minutes at 50 ℃, adding 3 g of positive electrode material, stirring and evaporating at 60 ℃ until evaporating, and finally transferring into a tube furnace, and sintering under the oxygen atmosphere, wherein the sintering conditions are as follows: 700-3 h, heating up at a rate of 5 ℃/min, and obtaining the modified positive electrode material C with a composite coating layer (the coating amount is Co:5.0 wt% and Al:5.0 wt%).
Comparative example 1
A single layer coating experiment was performed using NCM811 positive electrode material with respect to example 1. Firstly, accurately weighing 0.15 g of nano cobalt hydroxide powder in 5mL of absolute ethyl alcohol, fully stirring for 30 minutes at 50 ℃, adding 3 g of positive electrode material, stirring at 60 ℃ and evaporating until the powder is evaporated, transferring the powder into a tube furnace, and sintering under the oxygen atmosphere, wherein the sintering conditions are as follows: 500-3 h, and heating up at a rate of 5 ℃/min, thus obtaining the anode material D with the Co coating amount of 2.0-wt%.
Comparative example 2
A single layer coating experiment was performed using NCM811 positive electrode material with respect to example 1. Accurately weighing 0.2 g of aluminum isopropoxide, dissolving in 5mL of absolute ethyl alcohol, fully stirring for 30 minutes at 50 ℃, adding 3 g of positive electrode material, evaporating at 60 ℃ while stirring until evaporating, and finally transferring into a tube furnace, and sintering under the oxygen atmosphere, wherein the sintering conditions are as follows: 500-3 h, and heating up at a rate of 5 ℃/min, thus obtaining the anode material E with the Al coating amount of 1.0 wt%.
Comparative example 3
In contrast to example 1, a heat treatment experiment was performed using NCM811 cathode material. Firstly, accurately measuring 5mL absolute ethyl alcohol, fully stirring for 30 minutes at 50 ℃, adding 3 g of positive electrode material, stirring and evaporating at 60 ℃ until evaporating, and finally sintering under the oxygen atmosphere, wherein the sintering conditions are as follows: 500-3 h, and heating up at a rate of 5 ℃/min to obtain the heat-treated positive electrode material F.
Comparative example 4
Untreated NCM811 positive electrode material was named positive electrode material G.
Performance test of each example and comparative example
Assembly structure of solid-state battery: the assembled all-solid-state lithium battery is a sulfide electrolyte all-solid-state lithium battery pressed by a pressure die. Each of the positive electrode material, sulfide electrolyte and conductive carbon was prepared in a ratio of 70:30: 3 mass ratio grinding and mixing as composite positive electrode, li 6 P 5 An all-solid-state lithium battery structure schematic diagram using SCl (LPSC) as a solid electrolyte, li-In alloy as a negative electrode, and stainless steel sheet as a current collector is shown In FIG. 4 below.
Test equipment: LAND battery test system of model CT-2001A of blue electric electronic Co Ltd in Wuhan, switzerland Ten thousand-pass EIS alternating current impedance tester (PGSTAT 204), and Shimazuwa island jin MCT series micro compression tester in Japan.
The testing method comprises the following steps:
the charge and discharge test adopts a constant-current charge and constant-current discharge charge and discharge mode to characterize the capacity, the multiplying power performance and the cycle performance of the all-solid-state lithium battery, the test temperature is 45 ℃, the voltage range is 2.1-3.7V (corresponding to 2.72-4.32V vs. Li/Li+, because the potential of Li-In to Li/Li+ is 0.62V).
The electronic conductivity is tested by assembling ion blocking solid-state mould battery for direct current, and then the formula is passedWherein v=50 mV; i is steady-state current under 50 mV bias, L is the thickness of the composite anode; s is the cross-sectional area of the die; delta electron For electron conductivity) the electron conductivity was calculated and the test temperature was 45 ℃.
The particle strength of the positive electrode material was measured by using a Shimazuwa island MCT series micro compression tester.
The test data are as follows:
TABLE 1 comparison of solid State Positive electrode electric Properties (ASSB: 2.1-3.7V vs Li-In,45 ℃ C.)
Examples 1 to 3 (A to C) are samples coated with a coating layer, comparative example 1 (D) is a sample of a single layer of coated cobalt, comparative example 2 (E) is a sample of a single layer of coated aluminum, comparative example 3 (F) is a sample that is not coated but treated under the same conditions, and comparative example 4 (G) is a bare sample that is not treated at all. From the above table 1, the electrical performance data of the solid-state battery show that the capacity, the multiplying power and the cycle performance of the coating layer coating sample are far better than those of the bare sample and the single-layer coating sample, especially the a sample, and the 100-turn capacity retention rate at 0.5C reaches 98.9%, and almost no attenuation is achieved. The multiplying power performance of the sample (D) coated with cobalt by a single layer is far better than that of a bare sample, the cycle performance is also improved to a certain extent, the island-shaped coating layer of the cobalt compound has obvious improvement on the multiplying power performance, and the interface side reaction is reduced by reducing the nickel content on the surface of the positive electrode material, so that the effect of improving the cycle performance is achieved; the capacity and multiplying power of the sample (E) of the single-layer coated aluminum are lower than those of a bare sample, but the cycle performance is improved from 77.8% to 90.2%, which shows that the film-shaped coating layer of the aluminum isolates the positive electrode material and the solid electrolyte, and interface side reaction is reduced. The capacity and multiplying power of the F sample are better than those of the bare sample G, and the circulation is slightly worse, because the heat treatment leads to the surface residue of the positive electrode material partThe alkali volatilizes, the electronic conductivity of the material is increased, so that the capacity and multiplying power of the solid anode are improved, meanwhile, the anode material is directly contacted with sulfide solid electrolyte, the interface side reaction is correspondingly increased, and the capacity decay is faster. According to the electron conductivity data of the composite positive electrode, the electron conductivity of the solid positive electrode of the bare sample is only 1.2 x 10 -3 S/cm, and the single layer coating of cobalt compound is improved to 5.4x10 -3 S/cm, the corresponding solid-state positive electrode multiplying power performance is also obviously increased; whereas the electron conductivity of the individually coated aluminum compound was lower than that of the bare sample, only 0.8 x 10 -3 S/cm, the electron conductivity of the film coating layer is poor, and the electron conductivity of the A sample after being coated by the coating layer is 5.2 x 10 -3 S/cm, the comparison bare sample is obviously improved, which indicates that the solid anode electron conductivity of the coating layer coated sample is obviously increased. The mechanical strength of different coating materials shows that the mechanical strength of the coated modified positive electrode material is obviously higher than that of a bare sample, and the larger the coating amount of the aluminum compound is, the higher the mechanical strength is, so that the film coating layer of the aluminum compound has excellent anti-cracking capability. In summary, the capacity, multiplying power and cycle performance of the material can be improved by coating a layer of aluminum compound on the cobalt compound island-shaped coating layer at a proper coating amount and a proper heat treatment temperature, wherein the cobalt compound island-shaped coating layer has the effects of higher electronic conductivity and reduced surface nickel content, and mainly has the effects of improving the capacity, multiplying power and improving cycle, and the film-shaped coating layer of the aluminum compound can fill the exposed area, isolate the anode material from the solid electrolyte, reduce the interface side reaction, improve the mechanical strength of modified anode material particles, reduce the generation of cracks of the anode material, and further improve the cycle performance of the solid anode.
Fig. 2 and 3 are TEM characterization diagrams of different areas of the sample coated by the coating layer, and it can be seen that a good island-shaped coating is formed after the coating layer is coated by the cobalt compound, and the coating substance belongs to a crystal (as shown in fig. 2), and after the coating layer is coated by the aluminum compound, the cobalt compound is well coated by the aluminum compound layer, and the exposed area is filled and is amorphous (as shown in fig. 3). Therefore, in combination with the electrical performance data, the multifunctional composite coating of the cobalt compound island-shaped coating layer and the aluminum compound film-shaped coating layer has the best coating effect, and can remarkably improve the mechanical strength, capacity, first effect, multiplying power and circulation of the modified cathode material.
Fig. 1 is a schematic structural diagram of a modified cathode material having a coating layer. The material core is a positive electrode material. The cobalt compound is distributed on the surface of the positive electrode material in an island shape. The aluminum compound is coated on the surface of the positive electrode material in a layered manner. The cobalt compound is intercalated into the aluminum compound and connected to the positive electrode material.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.
Claims (10)
1. The preparation method of the modified cathode material is characterized by comprising the following steps: firstly, adding a certain amount of cobalt source and aluminum source into a solvent, and fully stirring, wherein the solvent dissolves the aluminum source and does not dissolve the cobalt source to obtain an aluminum source solution with the cobalt source dispersed therein; then adding the positive electrode material into the solution, stirring fully, and then stirring and evaporating at a certain temperature to dryness to obtain a precursor; finally, the precursor is subjected to heat treatment in an oxygen-containing atmosphere to form a modified positive electrode material with a coating layer, wherein the coating layer contains a cobalt compound and an aluminum compound.
2. The method for producing a modified positive electrode material according to claim 1, characterized in that:
the cobalt source is selected from any one or more of cobalt nitrate, cobalt sulfate, cobalt hydroxide, cobalt acetate, cobalt oxide, cobaltosic oxide and cobaltosic oxide.
3. The method for producing a modified positive electrode material according to claim 1, characterized in that: the aluminum source is selected from any one or more of aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum silicate, aluminum n-propoxide, aluminum isopropoxide, aluminum hydroxide and aluminum oxide.
4. The method for producing a modified positive electrode material according to claim 1, characterized in that: the solvent is at least one of water, alcohol solvents, ester solvents and ketone solvents.
5. The method for producing a modified positive electrode material according to claim 1, characterized in that:
the evaporating temperature is 50-150 ℃;
the heat treatment temperature is 200-700 ℃.
6. The method for producing a modified positive electrode material according to claim 1, characterized in that:
the weight percentage of the cobalt in the obtained coating layer and the weight percentage of the positive electrode material are 0.2-5.0%;
the weight percentage of the aluminum in the obtained coating layer and the weight percentage of the positive electrode material are 0.2-5.0%.
7. The method for producing a modified positive electrode material according to any one of claims 1 to 6, characterized in that: the positive electrode material contains nickel, cobalt and manganese, and the percentage of nickel in the positive electrode material to the total molar quantity of nickel, cobalt and manganese is more than 60 percent.
8. A modified cathode material prepared according to the method of any one of claims 1 to 7.
9. The modified cathode material according to claim 8, wherein:
the cobalt compounds are distributed on the surface of the positive electrode material in an island shape;
the aluminum compound is coated on the surface of the positive electrode material in a layered manner;
the cobalt compound is embedded in the aluminum compound and is connected to the positive electrode material.
10. Use of a modified cathode material according to claim 8 or 9, characterized in that: is used for preparing all-solid-state lithium batteries.
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