CN112174221A - Reagent for wet coating of high-nickel ternary cathode material and preparation method and application thereof - Google Patents
Reagent for wet coating of high-nickel ternary cathode material and preparation method and application thereof Download PDFInfo
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- CN112174221A CN112174221A CN202010880743.8A CN202010880743A CN112174221A CN 112174221 A CN112174221 A CN 112174221A CN 202010880743 A CN202010880743 A CN 202010880743A CN 112174221 A CN112174221 A CN 112174221A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 239000010406 cathode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title description 8
- 239000000463 material Substances 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims abstract description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [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 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 2
- -1 aluminum ions Chemical class 0.000 description 23
- 239000002243 precursor Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 239000002131 composite material Substances 0.000 description 13
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 12
- 229910044991 metal oxide Inorganic materials 0.000 description 12
- 150000004706 metal oxides Chemical class 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 230000002572 peristaltic effect Effects 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 6
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910011011 Ti(OH)4 Inorganic materials 0.000 description 1
- 229910011006 Ti(SO4)2 Inorganic materials 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- XNQULTQRGBXLIA-UHFFFAOYSA-O phosphonic anhydride Chemical compound O[P+](O)=O XNQULTQRGBXLIA-UHFFFAOYSA-O 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 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
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- 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
- H01M4/50—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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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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
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a reagent for wet coating of a high-nickel ternary positive electrode material, and belongs to the technical field of lithium ion power batteries for new energy automobiles. A reagent for wet coating of a high-nickel ternary cathode material comprises the following raw materials: metal source and/or complexing agent, solvent; the metal source is at least one of a lithium source, an aluminum source, a magnesium source, a titanium source, a manganese source, a nickel source and a phosphorus source; the complexing agent is at least one of CTAB, citric acid and ammonium citrate; the solvent is at least one of deionized water, ethanol, absolute ethanol and acetone. The reagent for wet coating is coated on the surface of the material through liquid phase reaction, so that the surface of the material is uniformly coated, the cyclicity is good, and the residual alkali level is low.
Description
Technical Field
The invention belongs to the technical field of lithium ion power batteries for new energy automobiles, and particularly relates to a reagent for wet coating of a high-nickel ternary positive electrode material, and a preparation method and application thereof.
Background
The ternary cathode material is one of the most promising cathode materials with the largest using amount in the current market, and the current market mainstream ternary cathode material comprises NCM, NCA and LiCoO2、LiNiO2And LiMnO2Compared with the three anode materials, the NCM or NCA integrates the advantages of the three materials, realizes the ternary synergistic effect, and has the advantages of high energy density, low cost and good market prospect.
The influence mechanism of three elements in NCM and NCA on the electrochemical performance of the material is different, wherein Ni is mainly used for improving the battery capacity; co mainly has the functions of stabilizing the layered structure of the ternary material, inhibiting mixed cation discharge, improving the electronic conductivity of the material and improving the cycle performance; the main functions of Mn or Al are to improve the structural stability and safety of the material and to reduce the synthesis cost of the material.
With social development, endurance mileage and cost gradually become an important index for consumers to select new energy automobiles, so that the development of the anode material is gradually pushed to the direction of underestimation (cost reduction) of high nickel (capacity improvement and endurance increase), but with the increase of the content of Ni, the higher the surface residual alkali level of the material is, the more serious lithium-nickel mixed discharge is, and the cycle performance is deteriorated, the gas expansion is serious, and the safety performance is reduced.
At present, high nickel (n)NiNot less than 0.80) is mainly used for reducing the residual alkali on the surface of the material through processes such as washing and coating, but the performance of the material after washing is greatly reduced, and the internal resistance is increased, so that the cycle life and the safety performance of the material are influenced.
Patent CN201910041610.9 discloses a method for preparing a carbon-coated high-nickel ternary cathode material by a dry method and a wet method, the cycle performance and the rate capability of the material prepared by the method are improved, but SEM images provided by the patent show that the surface coating of the material is not uniform, which easily causes poor batch stability and the risk of cycle water-jumping; patent 201811522126.X discloses a preparation method of lithium iron manganese phosphate and a method for coating a ternary material by the method, the method prepares a nanometer-level high-capacity cathode material by a wet fusion method, the cycle performance and the safety performance of the ternary material prepared by the method are improved, but the method designs a hydrothermal synthesis reaction and is not suitable for industrial mass production. Therefore, the wet coating process of the high-nickel cathode material and the selection of the coating agent need to be optimized.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a reagent for wet coating of a high-nickel ternary cathode material, and a preparation method and application thereof.
The solution for solving the technical problem is as follows:
a reagent for wet coating of a high-nickel ternary cathode material comprises the following raw materials: metal source and/or complexing agent, solvent; the metal source is at least one of a lithium source, an aluminum source, a magnesium source, a titanium source, a manganese source, a nickel source and a phosphorus source; the complexing agent is at least one of CTAB, citric acid and ammonium citrate; the solvent is at least one of deionized water, ethanol, absolute ethanol and acetone.
Preferably, the lithium source is LiOH, Li2CO3、LiNO3、CH3At least one of COOLi.
Preferably, the aluminum source is Al2(SO4)3、Al(NO3)3、Al[OCH(CH3)2]3、AlCl3At least one of (1).
Preferably, the magnesium source is MgSO4、Mg(NO3)2、MgCl2At least one of (1).
Preferably, the titanium source is Ti (SO)4)2、C16H36O4At least one of Ti.
Preferably, the manganese source is Mn (CH)3COO)2、MnSO4At least one of (1).
Preferably, the nickel source is Ni (CH)3COO)2、NiSO4At least one of (1).
Preferably, the phosphorus source is NH4H2PO4、(NH4)2HPO4、H3PO3At least one of (1).
A preparation method of a reagent for wet coating of a high-nickel ternary cathode material comprises the following specific steps: and (2) selecting a metal source and/or a complexing agent, dissolving in a solvent, reacting for 2-10h at 20-60 ℃, and standing to obtain the wet-process coating reagent.
A reagent for wet coating of a high-nickel ternary cathode material is used for preparing the ternary cathode material, and specifically comprises the following steps:
s1, adding a primary calcined high-nickel ternary cathode material and water into a reaction kettle according to a water-material ratio of 0.5:1-5:1 for wet mixing; then adding a wet coating reagent, finishing dripping within 5-30min, reacting at 25-80 ℃ for 0.5-3h, and drying at 80-350 ℃ for 1-10h to obtain a wet coating mixed material;
s2, placing the wet-process coating mixed material and the coating agent in the S2 in an atmosphere furnace for aerobic calcination at the temperature of 250 ℃ and 750 ℃ for 2-15h, and then crushing, sieving and demagnetizing to obtain the ternary cathode material.
Specifically, the preparation of the once-calcined high-nickel ternary cathode material comprises the following steps: placing the high-nickel ternary precursor in an atmosphere furnace, calcining at 300-700 ℃ for 2-10h, and pre-oxidizing; then adding lithium hydroxide to mix according to the molar ratio of lithium to metal being 1.01-1.15:1, adding a doping agent, and calcining for 6-15h in an oxygen atmosphere at 650-850 ℃ to obtain the primary calcined high-nickel ternary cathode material.
Specifically, the adding amount of the wet coating reagent is 1-15% of the mass of the reaction material.
Specifically, the coating agent is Al (OH)3、Mg(OH)2、Ti(OH)4、AlOOH、Al2O3、ZrO、MgO、V2O5、SiO2、Y2O3、Rb2O、WO3、TiO2、SrO、H3BO3、B2O3The addition amount of the coating agent is 0.18-1.0% of the mass of the wet coating mixed material.
Specifically, the preparation method of the reagent for the wet coating of the high-nickel ternary material can be used for coating modification of the high-nickel ternary material, but is not limited to the high-nickel ternary material, and can be doped with other metal or nonmetal elements except nickel, cobalt, manganese and aluminum according to the needs, and the proportion of various elements in the elements can be adjusted at will.
Specifically, the atmosphere of the aerobic calcination is air or oxygen.
The invention has the beneficial effects that:
(1) compared with the traditional solid-phase coating, the invention adopts the addition of the reagent for wet coating, the reagent for wet coating generates a wet coating mixed material on the surface of the material through liquid-phase reaction, then the wet coating mixed material is mixed with the coating agent for calcination, and a more uniform coating layer can be observed to coat the surface of the material through SEM after calcination, so that the corrosion of electrolyte to the interior of the material can be more effectively blocked.
(2) Compared with the traditional solid phase coating, the wet reagent coating can control the thickness of a coating layer on the surface of the material, further balance the electrochemical performances of the material in various aspects such as capacity, circulation, safety and the like, and leave a space for improving the performance of the dried composite coating.
(3) Compared with the traditional water washing process (at present)Commercial high nickel material with the same specification and proportion), the anode material prepared by the invention adopts the wet mixing process and adds the reagent for wet coating to react, so that Li remained on the surface of the prepared material2CO3And the LiOH content is at a lower level.
The traditional solid phase coating method means that a ternary cathode material and a solid coating agent are mechanically mixed.
Drawings
FIG. 1 is a high power scanning electron microscope image of a lithium nickel cobalt manganese oxide positive electrode material according to a second embodiment of the present invention;
FIG. 2 is a second high power scanning electron microscope image of the lithium nickel cobalt manganese oxide positive electrode material of the second embodiment of the present invention;
Detailed Description
The conception, specific structure, and technical effects of the present application will be described clearly and completely with reference to the following embodiments, so that the purpose, features, and effects of the present application can be fully understood. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
Example 1:
preferably Al2(SO4)3、MgSO4、Mn(CH3COO)2、MnSO4And Li2CO3Respectively weighing the mass of metal ions, namely aluminum ions, magnesium ions, manganese ions and lithium ions according to the molar ratio of 1:1:0.5:0.5:1, respectively dissolving the metal ions in 1L of deionized water, stirring the solution at the temperature of 30 ℃ in a reaction kettle for 2 hours, and standing the solution to obtain a mixed salt solution with the total metal molar mass of 0.25mol/L, which is marked as a wet-process coating reagent 1.
The application comprises the following steps:
s1, adding Ni0.83Co0.12Mn0.05(OH)2Loading the ternary precursor into a pot, and carrying out preoxidation at 400 ℃ in an oxygen atmosphere furnace for 2h to obtain a composite metal oxide; the average particle diameter of the nickel-cobalt-containing ternary precursor is 10.0um, and the specific surface area is 5m2(g) apparent density of 1.72g/cm3Tap density of 2.05g/cm3；
S2, mixing the composite metal oxide with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.08:1, and adding Sr (OH) with the mass being 1% of that of the nickel-cobalt-containing ternary precursor2·8H2O and 0.05% of V2O5Then, the mixture is calcined for 8 hours at the temperature of 770 ℃ in the oxygen atmosphere to obtain a primary calcined material;
s3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 2:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 45 ℃, then dripping a reagent 1 with the addition amount of 15 percent of the mass of the reaction material into the reaction kettle at a constant speed through a peristaltic pump, controlling the dripping to be finished within 30min, continuously stirring the reaction kettle for reaction for 45min, then carrying out filter pressing, and then putting the reaction kettle into a drying oven for drying for 4h at 150 ℃ to obtain a mixed material;
s4, mixing the mixed material with ZrO in an addition amount of 0.1% of the mixed material mass20.05% of AlOOH and 0.05% of Al2O3Uniformly mixing, then placing the mixture in an oxygen atmosphere furnace for calcining at 650 ℃ for 4h, and then crushing, sieving and demagnetizing the mixture to obtain the ternary cathode material.
Example 2:
al (NO) is preferred3)3、Ti(SO4)2、NH4H2PO4And LiNO3Respectively weighing the mass of aluminum ions, titanium ions, phosphorus ions and lithium ions, dissolving the aluminum ions, the titanium ions, the phosphorus ions and the lithium ions in 1L of deionized water, stirring the mixture for 5 hours at the temperature of 20 ℃ in a reaction kettle, standing the mixture to obtain a mixed salt solution with the molar mass (the sum of the molar mass of the metal ions and the molar mass of the phosphorus ions) of 0.20mol/L, and marking the mixed salt solution as a wet-method coating reagent 2.
The application comprises the following steps:
s1, adding Ni0.80Co0.10Mn0.10(OH)2Loading the ternary precursor into a pot, and carrying out preoxidation at 450 ℃ in an air atmosphere furnace for 6h to obtain a composite metal oxide; the average grain diameter of the nickel-cobalt-containing ternary precursor is 10.5um, and the specific surface area is 8m2(g) apparent density of 1.75g/cm3Tap density of 2.10g/cm3；
S2, mixing the composite metal oxide with battery-grade lithium hydroxide monohydrate, lithium and metalMixing at a molar ratio of 1.06:1, and adding ZrO with a mass of 0.3% of that of the nickel-cobalt-containing ternary precursor2And 0.05 percent of MgO, and then calcining at 800 ℃ for 12 hours in an oxygen atmosphere to obtain a primary calcined material;
s3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 1:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 30 ℃, then dripping a reagent 2 with the addition amount of 8 percent of the mass of the reaction material into the reaction kettle at a constant speed through a peristaltic pump, controlling the dripping to be finished within 5min, continuously stirring the reaction kettle for reaction for 60min, then carrying out filter pressing, and then drying the reaction kettle in a drying oven for 10h at 120 ℃ to obtain a mixed material;
s4, mixing the materials with Y in an amount of 0.05% of the mass of the materials2O30.10% of Al (OH)30.03% of Rb2And mixing the materials evenly, then placing the mixture in an air atmosphere furnace for calcining for 6h at 450 ℃, and then crushing, sieving and demagnetizing the mixture to obtain the ternary cathode material.
Example 3:
mixing Al [ OCH (CH)3)2]3And CTAB (cetyl trimethyl ammonium bromide) is weighed according to the molar ratio of aluminum to bromide ions of 2:1, respectively dissolved in 1L of 75% ethanol solution, stirred at 60 ℃ for 3h, and C is weighed according to the molar ratio of aluminum to silicon ions of 1:18H20O4The Si solution was slowly dropped into the mixed solution and stirred for 7 hours, and after standing, a mixed salt solution having a total metal molar mass of 0.5mol/L was obtained and was designated as wet-process coating reagent 3.
The application comprises the following steps:
s1, adding Ni0.88Co0.09Al0.03(OH)2Loading the ternary precursor into a pot, and pre-oxidizing at 650 ℃ for 4h in an air atmosphere furnace to obtain a composite metal oxide; the average particle diameter of the nickel-cobalt-containing ternary precursor is 11.0um, and the specific surface area is 9m2(g) apparent density of 1.8g/cm3Tap density of 2.25g/cm3；
S2, mixing the composite metal oxide with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.02:1, and adding TiO with the mass of 0.15 percent of the mass of the nickel-cobalt-containing ternary precursor2、0.1％SrO、0.05％WO3Then, the reaction is carried out at 710 ℃ in an oxygen atmosphere,Calcining for 10 hours to obtain a primary calcined material;
s3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 1:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 50 ℃, then dripping a reagent 3 with the addition amount of 4 percent of the mass of the reaction material into the reaction kettle at a constant speed through a peristaltic pump, controlling the dripping to be finished within 5min, continuously stirring the reaction kettle for reaction for 10min, and then carrying out spray drying at the spray drying temperature of 250 ℃ to obtain a mixed material;
s4, mixing the materials and Ti (OH) with the addition amount of 0.12 percent of the mass of the materials40.10% SiO2And 0.12% Mg (OH)2Uniformly mixing, then placing the mixture into an air atmosphere furnace for calcining at 700 ℃ for 10h, and then crushing, sieving and demagnetizing to obtain the ternary cathode material.
Example 4:
mixing AlCl3、MgCl2、Ni(CH3COO)2、NiSO4And LiOH, weighing mass according to the molar ratio of aluminum ions to magnesium ions to nickel ions to lithium ions of 1:1:0.5:0.5:1, dissolving the mass in 1L of deionized water at 30 ℃, stirring for 2 hours and completely dissolving the solution to obtain solution A; and then weighing ammonium citrate according to the molar ratio of ammonium ions to aluminum ions of 1:1, dissolving the ammonium citrate in 1L of deionized water, stirring for 1h to completely dissolve the ammonium citrate to obtain a solution B, finally dropping the solution A into the solution B at a constant speed through a peristaltic pump, continuing stirring for 2h at 30 ℃ after complete dropping, standing to obtain a mixed salt solution with the total metal molar mass of 1.5mol/L, and marking the mixed salt solution as a wet coating reagent 4.
The application comprises the following steps:
s1, adding Ni0.83Co0.12Mn0.05(OH)2Loading the ternary precursor into a pot, and carrying out pre-oxidation in an air atmosphere furnace at 300 ℃ for 10h to obtain a composite metal oxide; the average particle diameter of the nickel-cobalt-containing ternary precursor is 10.0um, and the specific surface area is 5m2(g) apparent density of 1.72g/cm3Tap density of 2.05g/cm3；
S2, mixing the composite metal oxide with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.01:1, and adding Mg (OH) with the mass being 0.10% of that of the nickel-cobalt-containing ternary precursor2、0.1％Al(OH)3And 0.15% Ti (OH)4Then, calcining at 650 ℃ for 15 hours in an oxygen atmosphere to obtain a primary calcined material;
s3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 0.5:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 25 ℃, then dripping a reagent 4 with the addition amount of 1 percent of the mass of the reaction material into the reaction kettle at a constant speed through a peristaltic pump, controlling the dripping to be finished within 30min, continuously stirring the reaction kettle for reaction for 1h, then carrying out filter pressing, and then putting the reaction kettle into a drying oven for drying for 8h at the temperature of 80 ℃ to obtain a mixed material;
s4, mixing the mixed material with MgO in an amount of 0.12 percent and H in an amount of 0.30 percent of the mass of the mixed material3BO30.10% of B2O3Uniformly mixing, then placing in an air atmosphere furnace for calcining at 250 ℃ for 15h, and then crushing, sieving and demagnetizing to obtain the ternary cathode material.
Example 5:
will be (NH)4)2HPO4、H3PO3、C16H36O4Ti、LiNO3Dissolving phosphorus ions, titanium ions and lithium ions in a molar ratio of 0.5:0.5:1:1 in 1L of deionized water, stirring for 3 hours at 45 ℃ to completely dissolve the phosphorus ions, the titanium ions and the lithium ions and marking as A solution; and then weighing citric acid according to the molar ratio of 1:1 of the citric acid to the titanium ions, dissolving the citric acid in 1L of deionized water at 45 ℃, stirring for 1h to completely dissolve the citric acid and the titanium ions, marking as a solution B, finally dropping the solution A into the solution B at a constant speed through a peristaltic pump, continuing stirring for 4h at 45 ℃ after complete dropping, standing to obtain a mixed salt solution with the molar mass (the sum of the molar masses of the metal ions and the phosphorus ions) of 0.2mol/L, and marking as a wet coating reagent 5.
The application comprises the following steps:
s1, adding Ni0.80Co0.10Mn0.10(OH)2Loading the ternary precursor into a pot, and pre-oxidizing at 500 ℃ for 5h in an air atmosphere furnace to obtain a composite metal oxide; the average grain diameter of the nickel-cobalt-containing ternary precursor is 10.5um, and the specific surface area is 8m2(g) apparent density of 2.0g/cm2Tap density of 2.5g/cm2。
S2, mixing the composite metal oxide with battery-grade lithium hydroxide monohydrate in a molar ratio of lithium to metal of 1.08:1, andAlOOH with the mass of 0.65 percent of the mass of the nickel-cobalt-containing ternary precursor and Al with the mass of 0.10 percent are added2O3And 0.05% B2O3Then calcining at 800 ℃ for 8 hours in an oxygen atmosphere to obtain a primary calcined material;
s3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 3:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 60 ℃, then dripping a reagent 5 with the addition amount of 9 percent of the mass of the reaction material into the reaction kettle at a constant speed through a peristaltic pump, controlling the dripping to be finished within 5min, continuously stirring the reaction kettle for reaction for 2h, then carrying out filter pressing, and then putting the reaction kettle into a drying oven for drying for 5h at 200 ℃ to obtain a mixed material;
s4, mixing the mixed material with SrO and V, wherein the addition amount of the SrO is 0.05% of the mass of the mixed material, and the addition amount of the V is 0.10%2O5Uniformly mixing, then placing the mixture in an air atmosphere furnace for calcining for 6h at 450 ℃, and then crushing, sieving and demagnetizing to obtain the ternary cathode material.
Example 6:
will CH3COOLi、C16H36O4Ti、Mg(NO3)2、MnSO4、Al[OCH(CH3)2]3And NH4H2PO4Dissolving lithium ions, aluminum ions, titanium ions and phosphorus ions in a molar ratio of 3:1:1:1:3:6 in 1L of acetone solution respectively, stirring for 5 hours, uniformly mixing, and standing to obtain a mixed salt solution with the molar mass (sum of the molar masses of the metal ions and the phosphorus ions) of 1.0mol/L, which is marked as a reagent 6 for wet coating.
The application comprises the following steps:
s1, adding Ni0.88Co0.09Al0.03(OH)2Loading the ternary precursor into a pot, and carrying out pre-oxidation in an air atmosphere furnace at 700 ℃ for 2h to obtain a composite metal oxide; the average particle diameter of the nickel-cobalt-containing ternary precursor is 11.0um, and the specific surface area is 9m2(g) apparent density of 1.8g/cm2Tap density of 2.3g/cm2；
S2, mixing the composite metal oxide with the battery-grade lithium hydroxide monohydrate in a lithium-to-metal molar ratio of 1.15:1, and adding SiO (silicon dioxide) with the mass of 0.5% of that of the nickel-cobalt-containing ternary precursor20.10% of Y2O3、0.03％Rb2O and 0.05% B2O3Then calcining at 720 ℃ for 10 hours in an oxygen atmosphere to obtain a primary calcined material;
s3, adding the primary calcined material and water into a reaction kettle in a water-material ratio of 5:1 for wet mixing to obtain a reaction material; controlling the temperature of the reaction kettle to be 80 ℃, then dripping a reagent 6 with the addition amount of 1 percent of the mass of the reaction material into the reaction kettle at a constant speed through a peristaltic pump, controlling the dripping to be finished within 5min, continuously stirring the reaction kettle for reacting for 8min, and then carrying out spray drying at the spray drying temperature of 350 ℃ to obtain a mixed material;
s4, mixing the materials and WO with the addition amount of 0.20 percent of the mass of the materials3And 0.10% TiO2Uniformly mixing, then placing the mixture in an air atmosphere furnace for calcining at 650 ℃ for 2h, and then crushing, sieving and demagnetizing the mixture to obtain the ternary cathode material.
TABLE 1 statistical table of residual alkali on the surface of the material of the example
As can be seen from the table, the material obtained by adding the reagent in the wet mixing and coating and the wet method has low surface alkali residue.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited to the details of the embodiments, but is capable of various modifications and substitutions without departing from the spirit of the invention.
Claims (10)
1. The reagent for wet coating of the high-nickel ternary cathode material is characterized by comprising the following raw materials: metal source and/or complexing agent, solvent; the metal source is at least one of a lithium source, an aluminum source, a magnesium source, a titanium source, a manganese source, a nickel source and a phosphorus source; the complexing agent is at least one of CTAB, citric acid and ammonium citrate; the solvent is at least one of deionized water, ethanol, absolute ethanol and acetone.
2. The reagent for wet coating of the high-nickel ternary cathode material according to claim 1, wherein the lithium source is LiOH or Li2CO3、LiNO3、CH3At least one of COOLi.
3. The reagent for wet coating of the high-nickel ternary cathode material as claimed in claim 1, wherein the aluminum source is Al2(SO4)3、Al(NO3)3、Al[OCH(CH3)2]3、AlCl3At least one of (1).
4. The reagent for wet coating of the high-nickel ternary cathode material according to claim 1, wherein the magnesium source is MgSO4、Mg(NO3)2、MgCl2At least one of (1).
5. The wet coating agent for the high-nickel ternary positive electrode material, according to claim 1, wherein the titanium source is Ti (SO)4)2、C16H36O4At least one of Ti.
6. The reagent for wet coating of the high-nickel ternary positive electrode material as claimed in claim 1, wherein the manganese source is Mn (CH)3COO)2、MnSO4At least one of (1).
7. The reagent for wet coating of the high-nickel ternary cathode material as claimed in claim 1, wherein the nickel source is Ni (CH)3COO)2、NiSO4At least one of (1).
8. The reagent for wet coating of the high-nickel ternary cathode material according to claim 1, wherein the phosphorus source is NH4H2PO4、(NH4)2HPO4、H3PO3At least one of (1).
9. The method for preparing the reagent for wet coating the high-nickel ternary cathode material according to any one of claims 1 to 8, which comprises the following steps: and (2) selecting a metal source and/or a complexing agent, dissolving in a solvent, reacting for 2-10h at 20-60 ℃, and standing to obtain the wet-process coating reagent.
10. The reagent for wet coating of the high-nickel ternary cathode material as claimed in claim 9, which is used for preparing the ternary cathode material, and specifically comprises:
s1, adding a primary calcined high-nickel ternary cathode material and water into a reaction kettle according to a water-material ratio of 0.5:1-5:1 for wet mixing; then adding a wet coating reagent, finishing dripping within 5-30min, reacting at 25-80 ℃ for 0.5-3h, and drying at 80-350 ℃ for 1-10h to obtain a wet coating mixed material;
s2, mixing the wet coating mixed material and the coating agent in the step S1, placing the mixture in an atmosphere furnace for aerobic calcination at the temperature of 250-750 ℃ for 2-15h, and then crushing, sieving and demagnetizing the mixture to obtain the ternary cathode material.
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Application publication date: 20210105 |