CN116443946A - Positive electrode material, preparation method thereof and battery - Google Patents
Positive electrode material, preparation method thereof and battery Download PDFInfo
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- CN116443946A CN116443946A CN202310288144.0A CN202310288144A CN116443946A CN 116443946 A CN116443946 A CN 116443946A CN 202310288144 A CN202310288144 A CN 202310288144A CN 116443946 A CN116443946 A CN 116443946A
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- metal oxide
- layered metal
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- electrode material
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 68
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 68
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000010405 anode material Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 26
- 239000011734 sodium Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000011572 manganese Substances 0.000 description 21
- 239000010949 copper Substances 0.000 description 16
- 239000002002 slurry Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 235000015110 jellies Nutrition 0.000 description 4
- 239000008274 jelly Substances 0.000 description 4
- 238000010902 jet-milling Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- -1 metal element Sn Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- OANFWJQPUHQWDL-UHFFFAOYSA-N copper iron manganese nickel Chemical compound [Mn].[Fe].[Ni].[Cu] OANFWJQPUHQWDL-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/628—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
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode materialPreparation method, positive electrode material and battery. Comprising a coating step of a layered metal oxide. The coating step of the layered metal oxide includes: layered metal oxide Na x M1 a Ni b Fe c Mn d O 2 Mixing with a precursor solution containing M2, and then sintering to obtain the positive electrode material. Wherein, the definitions of M1, x, a, b, c, d and M2 are described in the specification. The anode material prepared by the method has the advantages of less residual alkali on the surface, stable crystal structure and capability of improving gram capacity of the anode material and cycle performance of a battery.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a battery anode material, a preparation method thereof and a battery.
Background
In recent years, with the development of new energy technologies, the lithium ion battery technology faces challenges from various aspects such as high energy density requirements, cost and performance, and the source of positive and negative electrode raw materials in the sodium ion battery is rich, besides the remarkable characteristic of low cost, the sodium ion battery also has the advantages of excellent multiplying power performance, quick charge performance, low temperature performance, environmental protection, high safety and the like, and becomes an important choice of low-speed vehicles, power vehicles and large-scale energy storage technologies, so that the sodium ion battery has been widely paid attention to the scientific research and the commercial industry in recent years.
Currently, three types of sodium-ion battery cathode materials mainly exist, including layered metal oxides, prussian blue and polyanions. Among them, layered metal oxides are receiving a great deal of attention because of their excellent processability, outstanding compact density, and extremely high industrial matching with material manufacturers and battery manufacturers. The existing layered oxides of sodium ion batteries mainly comprise a copper-nickel-iron-manganese system and a nickel-iron-manganese system, wherein the surface alkalinity of the layered oxides of the two systems is relatively strong, and hydroxyl groups in the alkali can easily react with adjacent-F groups and-H groups in a common binder PVDF, so that the PVDF is invalid, and the concrete manifestation is that the slurry is in a jelly state in the homogenizing process and during storage, the slurry cannot be coated at all, and qualified batteries cannot be made. Therefore, in order to process smoothly, the problem of surface alkalinity of the positive electrode material of the sodium ion battery must be emphasized. In addition, the range of the charge-discharge interval of the sodium ion battery made by using the layered metal oxide as the positive electrode is usually between 1.5V and 4.0V, and when the voltage is more than 4.0V, a great amount of sodium ions in the layered metal oxide are extracted, so that the crystal structure of the material is converted from a hexagonal system to a monoclinic system, and the irreversible phase change process can lead to the sodium ions not being extracted and intercalated completely reversibly, thereby leading to the rapid degradation of the cycle performance of the sodium ion battery. Therefore, how to overcome the degradation problem of the sodium-electric layered oxide at high voltage and thereby greatly improve the energy density of the sodium-ion battery has become an urgent problem to be solved in the industry.
Disclosure of Invention
The invention provides a preparation method of a positive electrode material and the positive electrode material, wherein the residual alkali on the surface of the positive electrode material prepared by the method is less, the crystal structure is stable, and the cycle performance of a battery under high voltage and the gram capacity of the positive electrode material can be improved.
According to a first aspect, in one embodiment, a method for preparing a positive electrode material of a sodium ion battery is provided, including the steps of:
coating step of layered metal oxide: layered metal oxide Na x M1 a Ni b Fe c Mn d O 2 Mixing with a precursor solution containing M2, and then sintering to obtain a positive electrode material; wherein M2 is selected from at least one of Sn, ti and Zr; m1 is selected from at least one of Cu, zn, al and Ti, and x, a, b, c and d satisfy x: a: b: c: d= (0.8-1): (0-0.4): (0-0.4): (0.3-0.4): (0.3-0.4).
According to a second aspect, in one embodiment, there is provided a positive electrode material, the positive electrode material including a layered metal oxide having a molecular formula shown in formula I below and a doped coating layer coated on a surface of the layered metal oxide, the coating layer including an oxide containing M2, M2 being at least one selected from Sn, ti, and Zr;
Na x M1 a Ni b Fe c Mn d O 2 i type
Wherein M1 is selected from at least one of Cu, zn, al and Ti, and x, a, b, c and d satisfy x: a: b: c: d= (0.8-1): (0-0.4): (0-0.4): (0.3-0.4): (0.3-0.4).
According to a third aspect, there is provided in one embodiment a battery comprising the positive electrode material of the second aspect.
The invention provides a preparation method of a positive electrode material, which is prepared by the preparation method and contains Sn, ti and Zr compounds, and can reduce sodium ions in layered metal oxide, water and CO in the external environment 2 The residual alkali on the surface is less, the processing performance of the slurry is improved, and the gram capacity of the anode material is finally improved. In addition, the inventors of the present invention have found that the metal element Sn, ti or Zr in the positive electrode material can enhance the interaction force of transition metal (such as Cu, fe, mn or Ni) and oxygen, and can effectively suppress the irreversible phase transition of the crystal structure in the high voltage section, thereby improving the cycle performance of the battery.
Drawings
FIG. 1 is a graph showing the relationship between the capacity retention rate and the cycle curve of the present invention in example 1 and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only a part of the invention and not all. All technical solutions obtained by conventional modifications or variations of the present invention by a person skilled in the art based on the embodiments of the present invention fall within the protection scope of the present invention.
Alkane alcohol: at least one hydrogen atom on the alkane is substituted with a hydroxyl group.
In an embodiment of the present invention, a method for preparing a positive electrode material is provided, including the steps of:
coating step of layered metal oxide: layered metal oxide Na x M1 a Ni b Fe c Mn d O 2 Mixing with a precursor solution containing M2, and then sintering to obtain a positive electrode material; wherein M2 is selected from at least one of Sn, ti and Zr; m1 is selected from at least one of Cu, zn, al and Ti, and x, a, b, c and d satisfy x: a: b: c: d= (0.8-1): (0-0.4): (0-0.4): (0.3-0.4): (0.3-0.4).
The sintering temperature in the coating step of the layered metal oxide is 600-900 ℃.
The positive electrode material in the embodiment of the invention is a positive electrode material of a sodium ion battery.
In the examples of the present invention, layered metal oxide Na x M1 a Ni b Fe c Mn d O 2 As the main body part of the positive electrode material, the surface of the layered metal oxide is coated with a compound containing M2 element, especially inactive element Zr, so that sodium ions in the layered metal oxide and water and CO in the external environment can be reduced 2 The residual alkali on the surface of the layered oxide is less by contact, the processing performance of the slurry is better, namely the slurry is not easy to form jelly, and the gram capacity of the active material is finally improved.
In addition, the inventors of the present invention found that doping of a specific metal element into a layered metal oxide, such as metal element Sn, ti or Zr, can enhance interaction force of a transition metal (such as Cu, fe, mn or Ni) with oxygen, and can effectively suppress irreversible phase transition of a crystal structure of a positive electrode material in a high voltage section (above 4.0V), so that the crystal structure of the positive electrode material is more stable, and especially, containing 5 or more metals can improve entropy value of the material, further improve stability of the material, and further improve cycle performance of a battery.
In some embodiments of the present invention, the step of coating the layered metal oxide specifically includes: adding the precursor containing M2 into a dispersing agent, mixing to form a precursor solution containing M2, and then adding the layered metal oxide Na x M1 a Ni b Fe c Mn d O 2 And adding the mixture into the precursor solution, mixing, and then sintering to obtain the positive electrode material.
The dispersant comprises at least one of water, an alkane alcohol, methyl pyrrolidone or a solvent oil, preferably the solvent oil may be a solvent oil boiling in the range 130 ℃ to 150 ℃ and having the trade name dayer, and the alkane alcohol comprises methanol or ethanol.
In some embodiments of the invention, the surface of the positive electrode material is coated with a layered metal oxide of element M2; or, a region close to the surface in the layered metal oxide is doped with a layered metal oxide of M2 element.
The preparation method of the layered metal oxide comprises the following steps: adding Na source, M1 source, ni source, fe source and Mn source into solvent, mixing, and sintering to obtain layered metal oxide Na x M1 a Ni b Fe c Mn d O 2 . The solvent in the preparation method of the layered metal oxide is selected from at least one of water, alkane alcohol, methyl pyrrolidone or solvent oil, preferably, the solvent oil can be solvent oil with a boiling point of 130-150 ℃ and a trade name of dadar, and the alkane alcohol comprises methanol or ethanol. The sintering temperature in the preparation method of the layered metal oxide is 600-1000 ℃.
Wherein the sodium source comprises at least one of sodium carbonate, sodium bicarbonate and sodium hydroxide; the nickel source comprises at least one of nickel oxide, nickel hydroxide and nickel carbonate; the iron source comprises at least one of ferric oxide, ferric hydroxide and ferric carbonate; the manganese source includes at least one of manganese oxide, manganese hydroxide, and manganese carbonate. In some embodiments of the invention, when M1 is Cu, the M1 source comprises at least one of an oxide, hydroxide, and nitrate of Cu. When M1 is Zn, the M1 source includes at least one of an oxide, hydroxide, and nitrate of Zn. When M1 is Ti, the M1 source comprises at least one of an oxide, hydroxide, and nitrate of Ti. When M1 is Al, the M1 source comprises at least one of an oxide, hydroxide, and nitrate of Al.
In some embodiments of the invention, when M2 is Sn, the M2-containing precursor comprises SnO 2 、Sn(OH) 4 、Sn(NO 3 ) 4 And SnC (SnC) 2 O 4 At least one of (a) and (b); when the M2 is Ti, the precursor containing M2 comprises TiO 2 、Ti(OH) 4 、Ti(NO3) 4 And TiC 2 O 4 At least one of (a) and (b); when the M2 is Zr, the M2-containing precursor comprises ZrO 2 、Zr(OH) 4 、Zr(NO3) 4 And ZrC 2 O 4 At least one of them.
The anode material prepared by the embodiment of the invention comprises a layered metal oxide and a coating layer coated on the surface of the layered metal oxide, wherein the layered metal oxide has a molecular formula shown in the following formula I, the coating layer comprises an oxide containing M2, and M2 is selected from one of Sn, ti and Zr;
Na x M1 a Ni b Fe c Mn d O 2 i type
Wherein M1 is selected from at least one of Cu, zn, al and Ti, and x, a, b, c and d satisfy x: a: b: c: d= (0.8-1): (0-0.4): (0-0.4): (0.3-0.4): (0.3-0.4).
Preferably, the oxide containing M2 is present in an amount of 0.1 to 5wt% of the positive electrode material.
In other embodiments, the layered metal oxide has a region of the layered metal oxide near the surface doped with an M2 element.
Example 1
Preparation of layered metal oxide: according to Na: cu: ni: fe: the atomic molar ratio of mn=9:1:2:3:3 was weighed for sodium source Na, respectively 2 CO 3 805g, copper source CuO 134g, nickel source Ni (OH) 2 313g of Fe as iron source 2 O 3 404g and Mn source 3 O 4 386g, adding the powder into 1200g of NMP to obtain a mixed solution, ball-milling the mixed solution for 12h by using a ball-milling method, drying the ball-milled mixed solution in an environment of 150 ℃ to obtain a solid, sieving the solid with a 80-mesh sieve, placing the sieved powder into a muffle furnace to sinter for 12h at 900 ℃, cooling, carrying out jet milling on the cooled powder, and then passing through a 150-mesh vibrating screen to obtain the quaternary sodium ion battery O3-phase layered metal oxide Na 0.98 Cu 0.11 Ni 0.20 Fe 0.30 Mn 0.31 O 2 。
Coating of layered metal oxide: 20g of Zr (NO) 3 ) 4 Adding into 400g of water, dispersing and mixing to form Zr (NO) 3 ) 4 Solution and then the layered metal oxide Na 0.98 Cu 0.11 Ni 0.20 Fe 0.30 Mn 0.31 O 2 To be matched with Zr (NO) 3 ) 4 The mass ratio of (2) is 100:1 to Zr (NO) 3 ) 4 Mixing the solutions by ball milling, and mixing the mixed solutions to obtain a mixture containing Na 0.98 Cu 0.11 Ni 0.20 Fe 0.30 Mn 0.31 O 2 Zr (NO) 3 ) 4 The solution is dried and sieved at 150 ℃, then is sintered for the second time, the sintering temperature is 700 ℃ and the sintering time is 10 hours, and finally, the sintered product is crushed by air flow and is sieved by a vibrating screen to obtain the O3 phase layered metal oxide of the sodium ion battery, namely the anode material.
Preparing a positive electrode plate: mixing the O3 phase layered metal oxide, the conductive carbon material and the polyvinylidene fluoride glue solution together according to the mass ratio of 95:3:2, stirring for 2 hours at the speed of 3000rpm in a vacuum stirring tank to obtain slurry, uniformly coating the slurry on an aluminum foil with the thickness of 15 mu m, and drying, rolling and cutting to prepare the positive plate.
Preparing a negative electrode plate: stirring and mixing a hard carbon material and a conductive carbon material in a vacuum stirring tank at a speed of 1000rpm for 30min, adding sodium carboxymethyl cellulose emulsion, stirring at a speed of 1500rpm for 2h, adding styrene-butadiene rubber emulsion, stirring at a speed of 800rpm for 1h, uniformly coating the prepared slurry on an aluminum foil with a thickness of 15 mu m, drying, rolling, testing the maximum compaction density of the pole piece, and finally cutting to prepare the negative pole piece.
Preparation of sodium ion battery: the cylindrical sodium ion battery is prepared by winding a positive electrode, a diaphragm, a negative electrode and a diaphragm into a dry electrode in sequence, preparing 1mol/L sodium hexafluorophosphate by shell filling and spot welding, wherein solvents are EC (ethylene carbonate), EMC (methyl ethyl carbonate) and PC (propylene carbonate), additives are FEC, the mass ratio of the solvents to the additives is EC: EMC: PC: FEC=16:40:40:4, and the cylindrical sodium ion battery is prepared by conventional processes of liquid injection, component separation (constant current of 0.2C is used) and the like.
Example 2
The difference from example 1 is the coating step of the layered metal oxide, specifically: first 10g TiO 2 Adding into 100g of methyl pyrrolidone for dispersion and mixing to form the TiO-containing material 2 Then the layered metal oxide Na is added 0.98 Cu 0.1 1 Ni 0.20 Fe 0.30 Mn 0.31 O 2 To be combined with TiO 2 The mass ratio of (2) is 100:0.5 mass percent of the catalyst is added into the catalyst containing TiO 2 Is mixed by ball milling, and then the mixed solution containing Na 0.98 Cu 0.11 Ni 0.20 Fe 0.30 Mn 0.31 O 2 The mixed solution of the sodium ion battery O3 phase layered metal oxide is obtained by drying and sieving at 150 ℃, then sintering for the second time at 700 ℃ for 10 hours, and finally carrying out jet milling and vibrating sieving on the sintered product.
Example 3
Preparation of layered metal oxide: according to Na: ni: fe: the atomic molar ratio of mn=9:3:3:3 was weighed for sodium source Na, respectively 2 CO 3 805g of Ni source Ni (OH) 2 470g, fe source 2 O 3 404g and Mn source 3 O 4 386g and adding into 1200g NMP to obtain mixed solution, ball milling the mixed solution for 12h by ball milling, drying the ball milled mixed solution in 150 ℃ environment, sieving the solid with a 80-mesh sieve, sintering the sieved powder in a muffle furnace at 900 ℃ for 12h, cooling, jet milling the cooled powder, and passing through a 150-mesh vibrating screen to obtain the quaternary sodium ion battery O3-phase layered metal oxide Na 0.98 Ni 1/3 Fe 1/3 Mn 1/3 O 2 。
Coating of layered metal oxide: 20gZr (NO) 3 ) 4 Adding into 400g of water, dispersing and mixing to form Zr (NO) 3 ) 4 Solution and then the layered metal oxide Na 0.98 Ni 1/3 Fe 1/3 Mn 1/3 O 2 To be matched with Zr (NO) 3 ) 4 The mass ratio of (2) is 100:1 to Zr (NO) 3 ) 4 Mixing the solutions by ball milling, and mixing the mixed solutions to obtain a mixture containing Na 0.98 Ni 1/3 Fe 1/ 3 Mn 1/3 O 2 Zr (NO) 3 ) 4 The solution is dried and sieved at 150 ℃, then is sintered for the second time, the sintering temperature is 700 ℃ and the sintering time is 10 hours, and finally, the sintered product is crushed by air flow and is sieved by a vibrating screen to obtain the O3 phase layered metal oxide of the sodium ion battery, namely the anode material.
Preparing a positive electrode plate: mixing the O3 phase layered metal oxide, the conductive carbon material and the polyvinylidene fluoride glue solution together according to the mass ratio of 95:3:2, stirring for 2 hours at the speed of 3000rpm in a vacuum stirring tank to obtain slurry, uniformly coating the slurry on an aluminum foil with the thickness of 15 mu m, and drying, rolling and cutting to prepare the positive plate.
Preparing a negative electrode plate: stirring and mixing a hard carbon material and a conductive carbon material in a vacuum stirring tank at a speed of 1000rpm for 30min, adding sodium carboxymethyl cellulose emulsion, stirring at a speed of 1500rpm for 2h, adding styrene-butadiene rubber emulsion, stirring at a speed of 800rpm for 1h, uniformly coating the prepared slurry on an aluminum foil with a thickness of 15 mu m, drying, rolling, testing the maximum compaction density of the pole piece, and finally cutting to prepare the negative pole piece.
Preparation of sodium ion battery: the cylindrical sodium ion battery is prepared by winding a dry electrode in the sequence of anode/diaphragm/cathode/diaphragm, preparing 1mol/L sodium hexafluorophosphate by shell filling and spot welding, wherein the solvent is EC, EMC and PC, the additive is FEC, the mass ratio of the solvent to the additive is EC (ethylene carbonate): EMC (methyl ethyl carbonate): PC (propylene carbonate): FEC (fluoroethylene carbonate) =16:40:40:4, and the cylindrical sodium ion battery is prepared by conventional processes of liquid injection, component separation (using constant current of 0.2C) and the like.
Example 4
The difference from example 3 is in the preparation of layered metal oxides, in particular: according to Na: cu: fe: atomic molar ratio mn=9:3:3:3Respectively weighing Na source 2 CO 3 805g, copper source CuO 403g and iron source Fe 2 O 3 404g and Mn source 3 O 4 386g and adding into 1200g NMP to obtain mixed solution, ball milling the mixed solution for 12h by ball milling, drying the ball milled mixed solution in 150 ℃ environment, sieving the solid with a 80-mesh sieve, sintering the sieved powder in a muffle furnace at 900 ℃ for 12h, cooling, jet milling the cooled powder, and passing through a 150-mesh vibrating screen to obtain the quaternary sodium ion battery O3-phase layered metal oxide Na 0.98 Cu 1/3 Fe 1/3 Mn 1/3 O 2 。
Comparative example 1
The difference from example 1 is that the surface of the layered metal oxide in comparative example 1 is not coated with the M2 (Sn, ti or Zr) -containing compound, i.e., the coating step of the layered metal oxide is removed, and the other steps are identical to those of example 1.
The positive electrode materials of examples 1 to 4 and comparative example 1 were tested for PH; and (3) taking a proper amount of the slurry obtained in the preparation step of the positive electrode plate, sealing and preserving for 24 hours, and observing whether the slurry is in a jelly state.
The positive electrode materials of the sodium ion batteries of examples 1-4 and comparative example 1 were tested for gram capacity: the formation into components was performed using constant current 0.2C charge and discharge, and the discharge capacity was divided by the mass of the positive electrode active material to obtain the gram capacity of the positive electrode material.
The cycling performance of the sodium ion batteries of examples 1-4 and comparative example 1 were tested: the constant current 0.2C is used for formation of capacity, then the cyclic test is carried out in a mode of 0.5C charge/1C discharge in a voltage interval of 1.5-4.2V until the capacity is 80% of the initial capacity, and the number of cyclic turns is recorded. The results are shown in Table 1 below.
TABLE 1
As is clear from Table 1 and FIG. 1, in example 1, in comparison with comparative example 1, the layered metal oxide surface was not doped with M2 (Sn, ti or Zr) -containing compound, and the slurry of example 1 was not in a jelly state after sealed storage for 24 hours, and had a gram capacity of 145mAh/g, which was higher than 129mAh/g of comparative example 1. And the number of cycles (228 turns) of the battery of example 1 was significantly larger than that of comparative example 1 (25 turns) when the battery capacity was reduced to 80%. Comparative example 3 is available with examples 1-2, 4, and the gram capacity of the positive electrode material is better due to the increased nickel content in example 3, and the nickel content in examples 1-2 and 4 is even less than in examples 0, and the gram capacity of the positive electrode material is lower relative to example 3. In addition, the cycle data of examples 1-2 can be obtained, and the positive electrode material contains five metal elements, and the four metal elements are transition metal elements, so that the structure of the positive electrode material is more stable due to the addition of various transition metal elements, and the crystal structure is not easily damaged in the long-time sodium ion deintercalation process, so that the cycle performance of the battery prepared by the method is better. Therefore, the doping and coating of the compound containing M2 (Sn, ti or Zr) can obviously improve the gram capacity of the battery anode material, the cycle performance of the battery and the processing performance of the slurry.
The foregoing description of the invention has been presented for purposes of illustration and description, and is not intended to be limiting. Several simple deductions, modifications or substitutions may also be made by a person skilled in the art to which the invention pertains, based on the idea of the invention.
Claims (10)
1. The preparation method of the positive electrode material is characterized by comprising the following steps:
coating step of layered metal oxide: layered metal oxide Na x M1 a Ni b Fe c Mn d O 2 Mixing with a precursor solution containing M2, and then sintering to obtain a positive electrode material; wherein M2 is selected from at least one of Sn, ti and Zr; m1 is selected from at least one of Cu, zn, al and Ti, and x, a, b, c and d satisfy x: a: b: c: d= (0.8-1): (0-0.4): (0-0.4): (0.3-0.4): (0.3-0.4).
2. The method of claim 1, whereinThe step of coating the layered metal oxide specifically includes: firstly mixing a precursor containing M2 with a dispersing agent to form a precursor solution, and then mixing the layered metal oxide Na x M1 a Ni b Fe c Mn d O 2 Mixing with a precursor solution containing M2, and then sintering to obtain the positive electrode material.
3. The method of preparing according to claim 2, wherein the dispersant comprises at least one of water, an alkane alcohol, methyl pyrrolidone, or a solvent oil; preferably, the alkane alcohol comprises methanol or ethanol.
4. The method of claim 1, wherein the surface of the positive electrode material is coated with a layered metal oxide of M2 element;
or, a region close to the surface in the layered metal oxide is doped with a layered metal oxide of M2 element.
5. The method of producing according to claim 1, wherein the method of producing the layered metal oxide comprises: adding Na source, M1 source, ni source, fe source and Mn source into solvent, mixing, and sintering to obtain layered metal oxide Na x M1 a Ni b Fe c Mn d O 2 。
6. The method of any one of claims 1 to 5, wherein when M1 is Cu, the M1 source comprises at least one of an oxide, hydroxide, and nitrate of Cu; when the M1 is Zn, the M1 source includes at least one of an oxide, hydroxide, and nitrate of Zn; when the M1 is Al, the M1 source includes at least one of an oxide, hydroxide, and nitrate of Al; when the M1 is Zn, the M1 source includes at least one of an oxide, hydroxide, and nitrate of Zn; when the M1 is Ti, the M1 source comprises at least one of an oxide, hydroxide, and nitrate of Ti
Or, when the M2 is Sn, the precursor containing M2 comprises SnO 2 、Sn(OH) 4 、Sn(NO 3 ) 4 And SnC (SnC) 2 O 4 At least one of (a) and (b); when the M2 is Ti, the precursor containing M2 comprises TiO 2 、Ti(OH) 4 、Ti(NO3) 4 And TiC 2 O 4 At least one of (a) and (b); when the M2 is Zr, the M2-containing precursor comprises ZrO 2 、Zr(OH) 4 、Zr(NO3) 4 And ZrC 2 O 4 At least one of them.
7. The production method according to any one of claims 1 to 5, wherein in the production method of the layered metal oxide, the sintering temperature is 600 to 1000 ℃;
or, in the step of coating the layered metal oxide, the sintering temperature is 600-900 ℃.
8. The positive electrode material is characterized by comprising a layered metal oxide and a coating layer coated on the surface of the layered metal oxide, wherein the layered metal oxide has a molecular formula shown in the following formula I, the coating layer comprises an oxide containing M2, and the M2 is at least one of Sn, ti and Zr;
Na x M1 a Ni b Fe c Mn d O 2 i type
Wherein M1 is selected from at least one of Cu, zn, al and Ti, and x, a, b, c and d satisfy x: a: b: c: d= (0.8-1): (0-0.4): (0-0.4): (0.3-0.4): (0.3-0.4).
9. The positive electrode material according to claim 8, wherein the content of the oxide containing M2 is 0.1 to 5w t%;
or, the layered metal oxide is doped with M2 element in the area close to the surface
Or, the positive electrode material is prepared by the preparation method according to any one of claims 1 to 7.
10. A battery comprising the positive electrode material according to any one of claims 8 to 9.
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