CN117071072A - High-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material and preparation method and application thereof - Google Patents
High-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 112
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 118
- 239000013078 crystal Substances 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000011572 manganese Substances 0.000 claims abstract description 40
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 37
- 238000001816 cooling Methods 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000010406 cathode material Substances 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 238000010583 slow cooling Methods 0.000 claims description 18
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 13
- 230000000630 rising effect Effects 0.000 claims description 12
- 239000010405 anode material Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 150000004679 hydroxides Chemical class 0.000 claims description 6
- 238000005056 compaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 238000000137 annealing Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000006911 nucleation Effects 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001000 micrograph Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010280 constant potential charging Methods 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035772 mutation Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001778 solid-state sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material, and a preparation method and application thereof, wherein the general formula of the high-nickel monocrystal ternary positive electrode material is LiNi x Co y Mn 1‑x‑y M b O 2 Wherein x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2,0.001 and b is more than or equal to 0.02. The invention adopts multiple variable-temperature sintering technology, integrates the advantages of three methods of high-temperature sintering, ultra-fast sintering and annealing sintering, utilizes short-time high-temperature regulation and control of crystal nucleation and long-time proper temperature to ensure the crystallinity of a single crystal structure, reduces collapse and lithium loss of a high-nickel single crystal structure when obtaining a large-size single crystal, obviously reduces lithium nickel mixed discharge and lattice stress, and ensures high capacity and simultaneously improves structural stability and cycling stability. The lithium ion battery assembled by the ternary positive electrode material prepared by the invention has high specific capacity, high rate performance, good high-temperature cycle performance and good low-temperature discharge performance.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries with high energy density have gradually become a main power source for electric automobiles and consumer electronics, and positive electrode materials are a particularly important component in lithium ion batteries, which largely determine the energy density of lithium batteries and affect the battery cost. Ternary cathode materials are one of the main cathode materials, and as high nickel technology tends to mature, ultra-high nickel becomes a necessary place for ternary materials in the future, the battery energy density ceiling will be further improved, and an effective way to reduce the cost. However, conventional polycrystalline high nickel materials generally exhibit irreversible structure and electrochemical losses at high pressures, and a large number of secondary particles exacerbate side reactions between the positive electrode material and the electrolyte during electrochemical cycling and promote volume changes and crack generation. The monocrystal appearance has excellent high voltage stability, high mechanical strength and stable structure, so that the problems of structural damage, poor cycle performance and the like of the traditional polycrystalline high-nickel material under high voltage can be effectively solved. The single crystal high nickel material has the advantages of ensuring structural stability, simultaneously having high specific capacity and high energy density, and being more outstanding as the nickel content is higher, so that the single crystal ultrahigh nickel ternary material is considered as an ideal positive electrode material of a high energy density lithium ion battery.
However, the high nickel material still has some difficulties at present, such as high stress of the high nickel material, and the high nickel material cannot prepare large-size single crystals with high capacity and low mixed discharge rate. Because the high nickel monocrystal ternary material has high nickel content, more Li is generated in the charging and discharging process of the lithium battery + Takes part in electrochemical reaction, with more Li + The problems of capacity loss, gas expansion, cycle performance reduction and the like of the lithium battery are caused by the increase of lithium nickel mixed discharge rate, and the battery performance is seriously degraded.
In addition, the conditions for synthesizing the high-nickel single crystal positive electrode material are very severe, on the one hand, nickel in the ternary positive electrode material is Ni 3+ In the form of Ni 3+ Unstable Ni 2+ Is difficult to convert into Ni 3+ Therefore, it is required to perform at a high temperature. Ni in the high nickel material during the roasting reaction as the nickel content increases 2+ Difficult to be completely oxidized into Ni 3+ Thereby preventing the growth of single crystal size, leading the morphology of single crystal to be mostly agglomerated small single crystal, and hardly obtaining large-size high-nickel single crystal with good dispersibility. At the same time a large amount of residual Ni 2+ Will lead to Ni 2+ And Li (lithium) + Mixed row is generated, part of Ni 2+ Occupying Li + Thereby severely degrading the electrochemical properties of the material. On the other hand, higher sintering temperatures are relatively required for preparing high nickel single crystals, and the larger the single crystal grain size, the higher the sintering temperature, and the higher the high temperature further aggravates Ni 2+ And Li (lithium) + Kinetic activity, causing severe lithium nickel miscibility. At the same time, high temperature sintering can cause stress concentration in the single crystal, thereby triggering the sliding of the layer plane to nucleate cracks in the single crystal and form a layerDislocation and intragranular cracking produce irreversible losses to the capacity and structural stability of the material. Currently, solid state sintering is still the main method for preparing the positive electrode material in the industry, and based on A perspective on single-crystal layered oxide cathodes for lithium-ion batteries report, the document summarizes and reviews the various single crystal material synthesis processes which have been developed at present, mainly including single-step high-temperature, multi-step high-temperature and molten salt assisted methods, and the like, but all the methods have certain defects. The single-step high-temperature method requires higher temperature, so that the problems of particle agglomeration, high residual stress, lithium nickel mixed discharge and the like are easily caused; the multi-step high temperature method can reduce the sintering time of the material, but still needs to be carried out at high temperature and improves the material performance only to a certain extent; the molten salt method can regulate and control the morphology of the material through the selection of molten salt, and the large monocrystal with high crystallinity is obtained through sintering, but the capacity is generally lower, and meanwhile, the molten salt is difficult to completely remove, so that the performance of the material is affected. Therefore, how to change the sintering process to prepare the low-stress high-nickel monocrystal with high capacity, large size and low lithium nickel mixed discharge rate is still a technical problem to be solved.
With the application of Tesla 4680 large cylindrical battery cells, the application prospect of the high-nickel and ultra-high-nickel ternary cathode material in the power market is further expanded, and the battery performances such as gas production, cycle performance and the like are improved by improving the particle size and dispersibility of the high-nickel single crystal ternary cathode material and reducing the lithium nickel mixed discharge and lattice stress, so that the problem that research and development personnel need to overcome is still solved.
Disclosure of Invention
Aiming at the defects and the defects existing in the prior art, the invention aims to provide a high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material and a preparation method thereof. The ternary positive electrode material prepared by the invention is a lithium ion battery assembled by electrodes, and has high specific capacity, high rate performance, good high-temperature cycle performance and good low-temperature discharge performance.
In order to achieve the above object, the present invention is as follows:
the first aspect of the invention provides a high-nickel single crystal nickel-cobalt-manganese ternary positive electrode material, which has the general formula ofLiNi x Co y Mn 1-x-y M b O 2 Wherein 0.8.ltoreq.x < 1, e.g. 0.80, 0.85, 0.90, 0.95, 0.99,0 < y < 0.2, e.g. 0.01, 0.05, 0.10, 0.15, 0.199,0.001 < b.ltoreq.0.02, e.g. 0.0011, 0.005, 0.010, 0.015, 0.020, M being selected from one or more of Zr, al, ce, sr, mg, ti, si, la, ba, ta, W, co, nb, cr, mo, ca, Y, in, sn, F, P.
In the invention, the lithium nickel mixed discharge rate of the high nickel single crystal nickel cobalt manganese ternary positive electrode material is 1.90-2.10%, such as 1.90%, 2.00%, 2.05% and 2.10%;
in the invention, the lattice stress of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is 0.02-0.07, such as 0.02, 0.03, 0.04, 0.05, 0.06 and 0.07;
the lattice stress and the lithium nickel mixed discharge rate are obtained through XRD ray diffraction method test and fine modification, wherein the scanning range of the XRD test is 15 degrees-2 theta-80 degrees, and the scanning speed is 1.5 degrees/min. The lattice stress is calculated by utilizing the Highscore software through a Scherrer formula; the lithium nickel mixed discharge rate is finished by using Fullprof software and a Rietveld full spectrum fitting finishing method, the Rwp value after finishing is controlled below 10%, and the Ni atom occupation rate is calculated.
In the invention, the specific surface area of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is 0.4-0.8m 2 /g, e.g. 0.4m 2 /g、0.5m 2 /g、0.6m 2 /g、0.7m 2 /g、0.8m 2 /g。
In the invention, the compaction density of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is more than or equal to 3.35g/cm 3 For example 3.35g/cm 3 、3.40g/cm 3 、3.45g/cm 3 、3.50g/cm 3 、3.55g/cm 3 、3.60g/cm 3 、3.65g/cm 3 、3.70g/cm 3 。
In the invention, the granularity D50 of the high-nickel single crystal nickel cobalt manganese ternary positive electrode material is 3-6 mu m, such as3 mu m, 4 mu m, 5 mu m and 6 mu m.
In the invention, the granularity distribution (D90-D10)/D50 of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is 0.8-1.2, such as 0.8, 0.9, 1.0, 1.1 and 1.2.
In the present invention, the single crystal grain size of the high nickel single crystal nickel cobalt manganese ternary positive electrode material is 1.5 to 3 μm, for example, 1.5 μm, 1.7 μm, 1.9 μm, 2.1 μm, 2.3 μm, 2.5 μm, 2.7 μm, 3 μm.
In the invention, the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is also optionally introduced with a coating agent on the surface thereof; the coating agent is a compound containing one or more of Ti, mg, W, al, ce, co, F, P and B elements; the optional coating agent is introduced to the surface of the material, which is a routine choice in the field, the invention only guides the screening of the key element types in the coating agent, other characteristics such as the existence form, the dosage and the like are not particularly limited, and a technician can add the proper coating agent types and dosage according to the product requirement;
typically, the capping agent is introduced by a secondary sintering process, in the form of a compound of the capping agent precursor after sintering, the capping agent precursor being of a variety including, but not limited to, oxides, hydroxides, salts, and the like; the coating agent precursor is usually an oxygen-containing compound after sintering, but also exists in the form of an unconverted precursor or a compound with a complex structure formed with other elements during sintering, for example, when cobalt hydroxide is used as a precursor, active substance lithium cobaltate is more easily generated with surface residual lithium at high temperature than cobalt oxide.
Preferably, the coating agent is used in an amount of 0.01 to 1wt%, for example, 0.01wt%, 0.05wt%, 0.1wt%, 0.3wt%, 0.5wt%, 0.7wt%, 0.9wt%, 1.0wt%, based on the coating agent precursor, of the high nickel single crystal nickel cobalt manganese ternary cathode material.
The lithium nickel mixed discharge rate of the high nickel monocrystal nickel cobalt manganese ternary positive electrode material is 1.90-2.10%, the lattice stress is 0.02-0.07, the D50 is 3-6 mu m, the granularity distribution is 0.8-1.2, and the monocrystal grain size is 1.5-3 mu m. The cathode material according to the present invention has high dispersibility of large-sized single crystals, and realizes both low mixed discharge rate, and high capacity and low stress while having large single crystal size, as compared with conventionally used high nickel ternary cathode materials having the same content. The high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material within the specification range can effectively inhibit poor multiplying power performance and capacity loss of the high-nickel monocrystal positive electrode material caused by high lithium-nickel mixing rate, reduce continuous deterioration of cycle performance caused by large lattice stress in the monocrystal, greatly improve the structural stability and intra-crystal cracking problem of the monocrystal, and improve the safety of the material.
The invention provides a preparation method of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material, which comprises the following steps of:
(1) Uniformly mixing a nickel-cobalt-manganese ternary positive electrode material precursor, a lithium source and a compound containing an element M;
(2) Sintering the mixture obtained in the step (1) for one time in an oxygen-containing atmosphere; the primary sintering is multiple variable-temperature sintering, which sequentially comprises a rapid heating section I (heating rate V1 and final temperature T1), a slow heating sintering section II (heating rate V2 and final temperature T2), a rapid heating section III (heating rate V3 and final temperature T3), a rapid cooling section IV (cooling rate V4 and final temperature T4), a slow cooling sintering section V (cooling rate V5 and final temperature T5) and a cooling section VI (cooling rate V6 and final temperature T6);
wherein the final temperature (T2) of the slow temperature rise sintering section II is 50-150 ℃ higher than the final temperature (T1) of the fast temperature rise sintering section I, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, the final temperature (T3) of the fast temperature rise sintering section III is 50-100 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, the final temperature (T4) of the fast temperature reduction sintering section IV is the same as the final temperature (T2) of the slow temperature rise sintering section II, the final temperature (T5) of the slow temperature reduction sintering section V is 100-200 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ lower than the final temperature (T2) of the slow temperature rise sintering section II;
(3) Crushing the material subjected to the primary sintering in the step (2), sieving, and performing secondary sintering to obtain the high-nickel monocrystal nickel-cobalt-manganese ternary anode material.
The preparation method of the invention, wherein the structural formula of the nickel-cobalt-manganese ternary positive electrode material precursor in the step (1) is Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.8 and less than 1, and y is more than or equal to 0 and less than 0.2; the x and y in the precursor correspond to the x and y in the general formula of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material, the general formula of the ternary positive electrode material is used for continuing the proportion of nickel-cobalt-manganese in the precursor according to the current experimental result and naming habit, no loss or increase is caused basically in the sintering process, and the proportion of nickel-cobalt-manganese in the final product is not changed if nickel-cobalt-manganese is not added in the doping and cladding processes; the subsequent nickel, cobalt and manganese introduced by doping element M, coating agent and other means are calculated separately in the general formula.
The nickel-cobalt-manganese ternary positive electrode material precursor is an existing product, can be directly purchased or can be prepared by any method, has no special requirement on the source, and can be a commercial product Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 、Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 、Ni 0.92 Co 0.04 Mn 0.04 (OH) 2 、Ni 0.92 Co 0.06 Mn 0.02 (OH) 2 Etc.
The preparation method according to the present invention, wherein the lithium source in step (1) is selected from one or more of lithium salts, lithium oxygen-containing compounds, preferably one or more of lithium carbonate, lithium nitrate, lithium hydroxide, lithium oxide, lithium acetate, lithium oxalate.
The production method according to the present invention, wherein the compound containing the element M in the step (1) is selected from one or more of organic and inorganic compounds such as oxides, hydroxides, sulfates, carbonates of the element M (Zr, al, ce, sr, mg, ti, si, la, ba, ta, W, co, nb, cr, mo, ca, Y, in, sn, F, P), preferably one or more of oxides, hydroxides of the element M, such as ZrO 2 、Co(OH) 2 、Al 2 O 3 。
According to the preparation method provided by the invention, in the step (1), the nickel-cobalt-manganese ternary positive electrode material precursor, a lithium source and a compound containing an element M are mixed according to the total amount of Ni, co and Mn, the lithium element and the element M, wherein the mixing molar ratio is 1:0.9-1.1:0.001-0.02, e.g. 1: (0.90, 0.95, 1.00, 1.05 or 1.10): (0.001, 0.005, 0.010, 0.015 or 0.020), preferably 1:1.0-1.05:0.001-0.003.
The preparation method according to the present invention, wherein the mixing process of step (1) comprises mixing at 200-500rpm (e.g. 200, 300, 400, 500 rpm) for 5-10min, e.g. 5, 8, 10min, and then mixing at 1000-1200rpm (e.g. 1000, 1100, 1200 rpm) for 20-40min, e.g. 20, 30, 40min;
the mixing process is preferably carried out using a high-speed mixer.
The preparation method according to the invention, wherein, in the step (2), the final temperature (T1) of the rapid heating section I is 700-830 ℃, such as 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 830 ℃, the final temperature (T2) of the slow heating sintering section II is 750-880 ℃, such as 750 ℃, 770 ℃, 790 ℃, 810 ℃, 830 ℃, 850 ℃, 870 ℃, 880 ℃, and the final temperature (T3) of the rapid heating section III is 850-980 ℃, for example 850 ℃, 870 ℃, 890 ℃, 910 ℃, 930 ℃, 950 ℃, 970 ℃, 980 ℃, the final temperature (T4) of the rapid cooling stage IV is the same as the final temperature (T2) of the slow heating sintering stage II, the final temperature (T5) of the slow cooling sintering stage V is 800-600 ℃, for example 800 ℃, 780 ℃, 760 ℃, 740 ℃, 720 ℃, 700 ℃, 680 ℃, 660 ℃, 640 ℃, 620 ℃, 600 ℃, the final temperature (T6) of the cooling stage VI is 25-150 ℃, for example 25 ℃, 30 ℃, 50 ℃, 70 ℃, 90 ℃, 110 ℃, 130 ℃, 150 ℃;
preferably, the temperature rising rate (V1) of the rapid temperature rising section I is 3-5 ℃/min, such as3 ℃/min, 4 ℃/min and 5 ℃/min, the temperature rising rate (V2) of the slow temperature rising sintering section II is 0.3-0.5 ℃/min, such as 0.3 ℃/min, 0.4 ℃/min and 0.5 ℃/min, the temperature rising rate (V3) of the rapid temperature rising section III is 5-8 ℃/min, such as 5 ℃/min, 6 ℃/min, 7 ℃/min and 8 ℃/min, the temperature falling rate (V4) of the rapid temperature falling section IV is 5-8 ℃/min, such as 5 ℃/min, 6 ℃/min, 7 ℃/min and 8 ℃/min, the temperature falling rate (V5) of the slow temperature falling sintering section V is 0.1-0.5 ℃/min, such as 0.1 ℃/min, 0.2 ℃/min, 0.3 ℃/min, 0.4 ℃/min and 0.5 ℃/min, and the temperature falling rate (V6) of the cooling section VI is 3-5 ℃/min, such as3 ℃/min, 4 min and 5 ℃/min.
In the preparation method, the sintering process is optimized, and a multiple variable temperature sintering process is adopted, wherein the variable temperature sintering section can effectively reduce oxygen vacancies of the high-nickel single crystal nickel-cobalt-manganese ternary cathode material, so that lattice oxygen is stabilized, and the structural stability and electrochemical performance of the material are improved; the rapid heating and rapid cooling sections are arranged, the growth of single crystals can be greatly promoted by high-temperature abrupt sintering, meanwhile, the sintering time in the process is shortened, the high lithium nickel mixed discharge rate caused by long-time high-temperature sintering can be avoided, and the large-size single crystal morphology is obtained; the long-time slow cooling sintering process arranged after the process can perfect the crystal structure, improve the single crystal crystallinity, and the better crystal structure is beneficial to more release and intercalation of lithium ions, so that the capacity performance of the material is improved. Meanwhile, the crystal internal lattice stress can be released in the long-time slow cooling sintering process, so that the internal gaps and crystal boundaries of the positive electrode particles can be eliminated, the generation of intragranular cracks can be reduced, and the cycling stability and the safety performance of the battery can be improved.
The preparation method provided by the invention comprises the following steps that the oxygen-containing atmosphere in the step (2) is one or more of an air atmosphere, an oxygen atmosphere or an ozone atmosphere;
preferably, the slow cooling sintering section V adopts ozone atmosphere for sintering;
preferably, the primary sintering adopts different oxygen-containing atmospheres at different stages, wherein the slow cooling sintering section V adopts ozone atmosphere sintering, and the other sections adopt air atmosphere sintering. In the preferred scheme, the slow temperature rise sintering section II, the rapid temperature rise section III and the rapid temperature reduction section IV are sintered in an air atmosphere, the layered structure crystallinity of the material is reduced through a low oxygen concentration atmosphere, other heterogeneous phases such as spinel are generated, the multi-phase coexistence in the crystal can reduce the melting point of the material, the crystal growth is promoted, and the large-size single crystal is formed. Ozone atmosphere is changed in the subsequent slow cooling sintering section, so that ozone has stronger oxidizing property and can promote Ni 2+ Conversion to Ni 3+ Promote the transformation of spinel and other hetero-phases into a layered structure, reduce the concentration of oxygen vacancies and reduce lithiumNickel is mixed and arranged, the crystallinity of single crystals is improved, and the crystal structure is perfected.
The preparation method according to the present invention, wherein the crushing and sieving operation of step (3) has a mesh size of 200 to 500 mesh, for example 200 mesh, 300 mesh, 400 mesh, 500 mesh, preferably 200 to 400 mesh.
The preparation method according to the present invention, wherein the secondary sintering in step (3) is performed at a temperature of 300-700 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, for a time of 8-12 hours, such as 8.0 hours, 8.5 hours, 9.0 hours, 9.5 hours, 10.0 hours, 10.5 hours, 11.0 hours, 11.5 hours, 12.0 hours;
preferably, the secondary sintering is performed in an oxygen-containing atmosphere, wherein the oxygen-containing atmosphere is one or more of an air atmosphere, an oxygen atmosphere or an ozone atmosphere.
The preparation method according to the invention, wherein step (3) optionally carries out coating treatment after crushing and sieving the material, comprises adding a coating agent precursor after sieving, mixing uniformly, and carrying out the secondary sintering;
preferably, the coating agent precursor is selected from compounds containing one or more of Ti, mg, W, al, ce, co, F, P and B elements, and the types of the compounds are not limited to oxides, hydroxides, salts and the like;
preferably, the usage amount of the coating agent precursor accounts for 0.01-1wt% of the mass of the high nickel single crystal nickel cobalt manganese ternary positive electrode material, such as 0.01wt%, 0.05wt%, 0.1wt%, 0.3wt%, 0.5wt%, 0.7wt%, 0.9wt% and 1.0wt%;
preferably, the mixing process comprises mixing at 200-500rpm, such as 200, 300, 400, 500rpm, for 5-10min, such as 5, 8, 10min, and then at 800-1000rpm, such as 800, 900, 1000rpm, for 10-20min, such as 10, 15, 20min;
the mixing process is preferably carried out using a high-speed mixer.
It should be noted that the above method disclosed in the present invention is only used to illustrate one method adopted to realize the high nickel single crystal nickel cobalt manganese ternary positive electrode material according to the present invention, and the high nickel single crystal nickel cobalt manganese ternary positive electrode material according to the present invention should not be limited by the steps and parameters in the above method. In practical operation, other auxiliary agents and additives may be added during the preparation process, and the operation parameters such as the types and proportion of the precursor of the positive electrode material, the doping element and the coating agent, the temperature time and the like are not limited to the above-mentioned cases, and a person skilled in the art can make corresponding insubstantial adjustments according to requirements.
The third aspect of the invention provides a positive electrode of a lithium ion battery, which comprises the high-nickel single crystal nickel-cobalt-manganese ternary positive electrode material.
A fourth aspect of the invention provides a lithium ion battery comprising a positive electrode according to the invention.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) The high-nickel monocrystal nickel cobalt manganese ternary positive electrode material has the advantages that the lattice stress is 0.02-0.07, the lithium nickel mixed discharge rate is 1.90-2.10%, the D50 is 3-6 mu m, the granularity distribution is 0.8-1.2, meanwhile, the high-dispersity large monocrystal with the granularity of 1.5-3 mu m is provided, in the specification range, the poor multiplying power performance and the capacity loss of the high-nickel monocrystal positive electrode material caused by the high lithium nickel mixed discharge rate can be effectively restrained, the continuous deterioration of the circulation performance caused by the large lattice stress in the monocrystal is reduced, the structural stability and the intra-crystal cracking of the monocrystal are greatly improved, and the safety of the material is improved.
(2) The invention combines the high-temperature sintering, variable-temperature sintering and annealing processes in the sintering process, breaks through the concept that the traditional solid-phase sintering heat preservation section is constant temperature, adopts multi-step variable-temperature sintering, introduces rapid heating and rapid cooling sections in the process, prepares large single crystals by high-temperature sintering in a short time through high-temperature mutation, introduces a slow cooling sintering method more conforming to the annealing definition after the high-temperature mutation, and achieves the purpose of more complete annealing by adopting slow cooling to lower temperature. In addition, considering that 2-valence nickel is difficult to oxidize into 3-valence nickel, in the multi-step variable-temperature sintering process, the crystal perfecting stage of the sintering section is slowly cooled, and in the preferred scheme, the sintering is performed by adopting ozone atmosphere with stronger oxidability, so that the crystallinity of the material is further improved, and the crystal structure is perfected.
(3) The preparation process of the high-nickel monocrystal nickel-cobalt-manganese ternary material provided by the invention is simple, is convenient to operate, and is suitable for large-scale industrial production. In the preparation method, the sintering process is improved, so that lithium-nickel mixed discharge and lattice stress can be effectively reduced, a high-dispersity large-size monocrystal can be obtained, the phenomena of serious volume expansion and shrinkage and intra-crystal crack generation of the existing high-nickel monocrystal material are effectively relieved, and the problems of capacity loss, flatulence, cycle performance reduction, battery performance degradation and the like of a lithium battery caused by the increase of the high-lithium-nickel mixed discharge rate are solved. The lithium ion battery assembled by the ternary positive electrode material prepared by the invention has high specific capacity, high rate performance, good high-temperature cycle performance and good low-temperature discharge performance.
Drawings
FIG. 1 is a scanning electron microscope image of the high nickel single crystal nickel cobalt manganese ternary positive electrode material prepared in example 1;
FIG. 2 is a scanning electron microscope image of the high nickel single crystal nickel cobalt manganese ternary positive electrode material prepared in example 2;
FIG. 3 is a scanning electron microscope image of the high nickel single crystal nickel cobalt manganese ternary positive electrode material prepared in example 3;
FIG. 4 is a scanning electron microscope image of the high nickel single crystal nickel cobalt manganese ternary positive electrode material prepared in example 4;
FIG. 5 is a scanning electron microscope image of the high nickel single crystal nickel cobalt manganese ternary positive electrode material prepared in example 5;
FIG. 6 is a scanning electron microscope image of the high nickel single crystal nickel cobalt manganese ternary positive electrode material prepared in comparative example 1;
FIG. 7 is a scanning electron microscope image of the high nickel single crystal nickel cobalt manganese ternary positive electrode material prepared in comparative example 2;
FIG. 8 is a scanning electron microscope image of the high nickel single crystal nickel cobalt manganese ternary positive electrode material prepared in comparative example 3;
FIG. 9 is a scanning electron microscope image of the high nickel single crystal nickel cobalt manganese ternary cathode material prepared in comparative example 4.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
1. The main raw material source information in the examples and comparative examples of the present invention are as follows:
Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 : hua Yougu, model: 9AS3X;
Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 : new energy source of Zhongwei, model: ZWN83066a;
Ni 0.92 Co 0.04 Mn 0.04 (OH) 2 : new energy source of Zhongwei, model: ZWN920911a;
Ni 0.96 Co 0.03 Mn 0.01 (OH) 2 : hua Yougu, model: 96CL2X;
lithium hydroxide: the elegance lithium industry;
ZrO 2 : beijing family;
Al 2 O 3 : jinghuang, JH-205-A-100 gamma;
Co(OH) 2 : hua Yougu;
WO 3 : deke;
B 2 O 3 : the delborium industry.
2. The main test method adopted by the embodiment and the comparative example of the invention comprises the following steps:
the lattice stress and the lithium nickel mixed discharge rate are obtained through XRD ray diffraction method test and refinement, wherein the scanning range of the XRD test is more than or equal to 10 degrees and less than or equal to 80 degrees, the scanning speed is 1.6 degrees/min, and the lattice stress is obtained through calculation by utilizing Highscore software through a Scherrer formula; the lithium nickel mixed discharge rate is refined by using Fullprof software and using a Rietveld full spectrum fitting refining method, the Rwp value after refining is controlled below 10%, the Ni atom occupation rate is calculated, and the XRD test adopts Markov Pasers.
The high nickel single crystal nickel cobalt manganese ternary positive electrode material is used as an active material to prepare a battery positive electrode, and is assembled into a lithium ion battery to test the performance of the battery positive electrode, and the C2032 button cell is prepared by adopting a conventional method in the field without special limitation, specifically according to the method comprising the following steps: dispersing active substances, a conductive agent Super P and a binder PVDF in N-methyl pyrrole ketone (NMP) according to the mass ratio of 95:2:3, wherein the solid content is 70%, and ball milling to form uniform anode slurry; coating the positive electrode slurry on the rough surface of clean aluminum foil by using a coater, and then placing the aluminum foil into a vacuum oven to be dried for 12 hours at 120 ℃ in vacuum to obtain a pole piece with the compaction density of 3.45g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The prepared pole piece is adopted, a lithium piece is taken as a counter electrode, celgard2400 is taken as a diaphragm, and the pole piece is assembled into a 2032 button cell in an argon glove box; the electrolyte used in assembling 2032 button cell is LiPF 6 LiPF obtained by dissolving in a mixed solvent of Ethyl Carbonate (EC) and diethyl carbonate (DMC) (volume ratio EC: dmc=1:1) 6 Is 1 mol/L.
The button cell prepared by the method is tested on a new Wei blue electric tester (model: CT-4008Tn-5V20 mA-164), and specifically comprises the following steps:
1) Firstly, standing the prepared C2032 button battery for one night at room temperature, then carrying out constant-current charging to a charging cutoff voltage at a rate of 0.1C, then carrying out constant-current discharging to a discharging cutoff voltage at a rate of 0.1C after constant-voltage charging to 0.05mA, and obtaining a first-round discharge capacity of 0.1C after standing for 5 min;
2) Then constant-current and constant-voltage charging is carried out at 0.33C, constant-current discharging is carried out at 0.2C, 0.5C and 1C multiplying power respectively, 0.2C, 0.5C and 1C discharging capacities are obtained respectively,
1C/0.2C capacity retention = 1C discharge capacity/0.2C first turn discharge capacity 100%;
3) Finally, constant-current and constant-voltage charging is carried out at 0.33C, charge-discharge cycle test is carried out at 1C discharge rate,
capacity retention rate for 50 cycles = 1C discharge capacity after 50 cycles/1C first cycle discharge capacity 100%;
all tests were performed at room temperature, with a voltage range between 3-4.3V for the charge and discharge test.
Example 1
A high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material has a chemical formula of LiNi 0.9 Co 0.05 Mn 0.05 Zr 0.001 O 2 The median particle diameter D50 is 3.8 μm, the particle size distribution (D90-D10)/D50 is 0.8, the lattice stress is 0.04, the lithium nickel mixing rate is 2.01%, the single crystal particle size is 2.2 μm, and the specific surface area is 0.5m 2 Per gram, a compacted density of 3.4g/cm 3 . The surface of the ternary positive electrode material is introduced with a coating agent (precursor Al) 2 O 3 ) The mass ratio of the catalyst is 0.01wt%.
The preparation method of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material comprises the following steps:
(1) The molar ratio is 1:1.05:0.001 weight of Ni, a precursor of a ternary nickel-cobalt-manganese positive electrode material 0.9 Co 0.05 Mn 0.05 (OH) 2 (based on the total amount of Ni, co and Mn), lithium hydroxide (based on lithium element) and an additive ZrO 2 Adding the weighed materials into a small high-speed mixer (calculated by Zr element), mixing for 5min at a rotating speed of 200rpm, and mixing for 20min at a rotating speed of 1100 rpm;
(2) Sintering the mixture obtained in the step (1) for one time by using a box furnace at room temperature, and sequentially passing through the steps of
Quick heating section I: the temperature rise rate V1 (3 ℃/min) and the final temperature T1 (720 ℃),
slowly heating up a sintering section II: the temperature rise rate V2 (0.4 ℃/min), the final temperature T2 (840 ℃),
quick heating section III: the temperature rise rate V3 (6 ℃/min) and the final temperature T3 (920 ℃),
and (4) a rapid cooling section IV: the cooling rate v4=v3 (6 ℃/min), the final temperature t4=t2 (840 ℃),
slowly cooling and sintering a section V: the cooling rate V5 (0.2 ℃/min) and the final temperature T5 (640 ℃),
cooling section vi: cooling rate V6 (3 ℃/min), final temperature T6 (150 ℃);
wherein, the sintering section with slow cooling is replaced by ozone atmosphere sintering;
(3) Coarse crushing the sintered material obtained in the step (2) by a pair of rollers, crushing by an air flow mill, removing oversize materials by a 300-mesh screen, and adding 0.01wt% of coating agent precursor Al 2 O 3 Mixing, adding into a small high-speed mixer, mixing at 200rpm for 5min, mixing at 800rpm for 10min, and sintering at 450 deg.C for 8 hr. The obtained sintered material passes through a 300-mesh screen to remove oversize materials, and then the material with D50 of 3.8 mu m is obtained, namely the high nickel single crystal nickel cobalt manganese ternary cathode material LiNi 0.9 Co 0.05 Mn 0.05 Zr 0.001 O 2 The scanning image of the electron microscope is shown in figure 1.
Example 2
A high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material has a chemical formula of LiNi 0.83 Co 0.11 Mn 0.06 W 0.01 O 2 The median particle diameter D50 is 5.5 μm, the particle size distribution (D90-D10)/D50 is 1.15, the lattice stress is 0.02, the lithium nickel mixing rate is 1.95%, the single crystal particle size is 2.8 μm, and the specific surface area is 0.4m 2 Per gram, a compacted density of 3.5g/cm 3 . The surface of the ternary positive electrode material is introduced with a coating agent (precursor Co (OH)) containing Co element 2 ) The mass ratio is 1wt%.
The preparation method of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material comprises the following steps:
(1) The molar ratio is 1:1.03:0.01 weight of Ni, a precursor of a ternary positive electrode material of nickel, cobalt and manganese 0.83 Co 0.11 Mn 0.06 (OH) 2 (based on the total amount of Ni, co and Mn), lithium hydroxide (based on the element lithium) and an additive WO 3 Adding the weighed materials into a small high-speed mixer (calculated by W element), mixing for 5min at a rotating speed of 300rpm, and mixing for 30min at a rotating speed of 1200 rpm;
(2) Sintering the mixture obtained in the step (1) for one time by using a box furnace at room temperature, and sequentially passing through the steps of
Quick heating section I: the temperature rise rate V1 (5 ℃/min) and the final temperature T1 (830 ℃),
slowly heating up a sintering section II: the temperature rise rate V2 (0.5 ℃/min) and the final temperature T2 (880 ℃),
quick heating section III: the temperature rise rate V3 (8 ℃/min) and the final temperature T3 (980 ℃),
and (4) a rapid cooling section IV: the cooling rate v4=v3 (8 ℃/min), the final temperature t4=t2 (880 ℃),
slowly cooling and sintering a section V: the cooling rate V5 (0.5 ℃/min) and the final temperature T5 (780 ℃),
cooling section vi: cooling rate V6 (5 ℃/min), final temperature T6 (50 ℃);
wherein, the sintering section with slow cooling is replaced by ozone atmosphere sintering;
(3) Coarse crushing the sintered material obtained in the step (2) through a roller, crushing through an air flow mill, removing oversize materials through a 300-mesh screen, and adding 1wt% of coating agent precursor Co (OH) into the crushed material 2 Mixing, adding into a small high-speed mixer, mixing at 200rpm for 5min, mixing at 800rpm for 10min, and sintering at 450 deg.C for 8 hr. The obtained sintered material passes through a 300-mesh screen to remove oversize materials, and then the material with the D50 of 5.5 mu m is obtained, namely the high nickel single crystal nickel cobalt manganese ternary cathode material LiNi 0.83 Co 0.11 Mn 0.06 W 0.01 O 2 The electron microscope scanning picture is shown in fig. 2.
Example 3
A high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material has a chemical formula of LiNi 0.96 Co 0.03 Mn 0.01 Co 0.02 O 2 The median particle diameter D50 is 3.1 μm, the particle size distribution (D90-D10)/D50 is 1.0, the lattice stress is 0.07, the lithium nickel mixing rate is 2.10%, the single crystal particle size is 1.5 μm, and the specific surface area is 0.8m 2 Per gram, a compacted density of 3.45g/cm 3 . The surface of the ternary positive electrode material is introduced with a coating agent (precursor Al) 2 O 3 ) Which is provided withThe mass ratio is 0.5wt%.
The preparation method of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material comprises the following steps:
(1) The molar ratio is 1:1.04:0.02 weighing Ni which is a precursor of the nickel-cobalt-manganese ternary cathode material 0.96 Co 0.03 Mn 0.01 (OH) 2 (based on the total amount of Ni, co and Mn), lithium hydroxide (based on lithium element) and additive Co (OH) 2 Adding the weighed materials into a small high-speed mixer (calculated by Co element), mixing for 5min at a rotating speed of 300rpm, and mixing for 30min at a rotating speed of 1200 rpm;
(2) Sintering the mixture obtained in the step (1) for one time by using a box furnace at room temperature, and sequentially passing through the steps of
Quick heating section I: the temperature rise rate V1 (3 ℃/min) and the final temperature T1 (700 ℃),
slowly heating up a sintering section II: the temperature rise rate V2 (0.3 ℃/min), the final temperature T2 (750 ℃),
quick heating section III: the temperature rise rate V3 (5 ℃/min) and the final temperature T3 (850 ℃),
and (4) a rapid cooling section IV: the cooling rate v4=v3 (5 ℃/min), the final temperature t4=t2 (750 ℃),
slowly cooling and sintering a section V: the cooling rate V5 (0.1 ℃/min) and the final temperature T5 (600 ℃),
cooling section vi: cooling rate V6 (3 ℃/min), final temperature T6 (150 ℃);
wherein, the sintering section with slow cooling is replaced by ozone atmosphere sintering;
(3) Coarse crushing the sintered material obtained in the step (2) through a pair of rollers, crushing through a jet mill, removing oversize materials through a 300-mesh screen, and adding 0.5wt% of coating agent precursor Al 2 O 3 Mixing, adding into a small high-speed mixer, mixing at 200rpm for 5min, mixing at 800rpm for 10min, and sintering at 450 deg.C for 8 hr. The obtained sintered material passes through a 300-mesh screen to remove oversize materials, and then the material with D50 of 3.1 mu m is obtained, namely the high nickel single crystal nickel cobalt manganese ternary cathode material LiNi 0.96 Co 0.03 Mn 0.01 Co 0.02 O 2 The electron microscope scanning picture is shown in fig. 3.
Example 4
A high nickel single crystal nickel cobalt manganese ternary cathode material was prepared by the method of reference example 1, except that the precursor in step (1) was replaced with Ni 0.92 Co 0.04 Mn 0.04 (OH) 2 The slow cooling sintering section in the step (2) is not replaced by ozone atmosphere, and is sintered in oxygen atmosphere to prepare the high-nickel monocrystal nickel-cobalt-manganese ternary anode material LiNi 0.92 Co 0.04 Mn 0.04 Zr 0.001 O 2 The median particle diameter D50 is 3.6 μm, the particle size distribution (D90-D10)/D50 is 0.9, the lattice stress is 0.06, the lithium nickel mixing rate is 2.08%, the single crystal particle size is 2.0 μm, and the specific surface area is 0.6m 2 Per gram, a compacted density of 3.5g/cm 3 The electron microscope scanning picture is shown in fig. 4.
Example 5
The method of reference example 1 was used to prepare a high nickel single crystal nickel cobalt manganese ternary cathode material, except that in step (3), no cladding precursor Al was added during the secondary sintering 2 O 3 Secondary sintering is carried out to prepare the high-nickel monocrystal nickel cobalt manganese ternary anode material LiNi 0.9 Co 0.05 Mn 0.05 Zr 0.001 O 2 The median particle diameter D50 was 3.7. Mu.m, the particle size distribution (D90-D10)/D50 was 0.9, the lattice stress was 0.05, the lithium nickel mixed rate was 2.02%, the single crystal particle size was 2.1. Mu.m, and the specific surface area was 0.5m 2 Per gram, a compacted density of 3.4g/cm 3 The electron microscope scanning picture is shown in fig. 5.
Comparative example 1
The comparative example is a method for preparing a high nickel single crystal nickel cobalt manganese ternary cathode material according to the method of example 1, wherein the difference is that the primary sintering process of the step (2) is different, and the primary sintering process of the step (2) of the comparative example is conventional sintering, and comprises a heating section, a constant temperature sintering section and a natural cooling section: room temperature-940 ℃/6 h-915 ℃/8h, and sintering the sintering atmosphere by adopting oxygen. Preparing the high-nickel monocrystal nickel-cobalt-manganese ternary anode material LiNi 0.9 Co 0.05 Mn 0.05 Zr 0.001 O 2 The median particle diameter D50 is 3.8 μm, the particle size distribution (D90-D10)/D50 is 1.0, the lattice stress is 0.12, the lithium nickel mixing rate is 2.23%, the single crystal particle size is 2.0 μm, and the specific surface area is 0.8m 2 Per gram, a compacted density of 3.4g/cm 3 . The surface of the ternary positive electrode material is introduced with a coating agent (precursor Al) 2 O 3 ) The mass ratio is 0.01wt%, and the scanning image of the electron microscope is shown in figure 6.
Comparative example 2
A high nickel single crystal nickel cobalt manganese ternary cathode material was prepared with reference to the method of comparative example 1, except that: in the sintering process, an air atmosphere is adopted in the heating section, and an ozone atmosphere is adopted in the constant-temperature sintering section; other operations and conditions are kept unchanged, and the high-nickel monocrystal nickel-cobalt-manganese ternary anode material LiNi is prepared 0.9 Co 0.05 Mn 0.05 Zr 0.001 O 2 The median particle diameter D50 was 3.6. Mu.m, the particle size distribution (D90-D10)/D50 was 1.01, the lattice stress was 0.11, the lithium nickel mixed rate was 2.22%, and the single crystal particle size was 1.9. Mu.m. Specific surface area of 0.7m 2 Per gram, a compacted density of 3.4g/cm 3 The electron microscope scanning picture is shown in fig. 7.
Comparative example 3
A high nickel single crystal nickel cobalt manganese ternary cathode material was prepared by the method of reference example 1, except that: step (1) adding an additive ZrO 2 Replaced by B 2 O 3 Other operations and conditions are kept unchanged, and the high-nickel monocrystal nickel-cobalt-manganese ternary anode material LiNi is prepared 0.9 Co 0.05 Mn 0.05 B 0.001 O 2 The median particle diameter D50 is 3.5 μm, the particle size distribution (D90-D10)/D50 is 1.0, the lattice stress is 0.13, the lithium nickel mixing rate is 2.20%, the single crystal particle size is 1.7 μm, and the specific surface area is 0.9m 2 Per gram, a compaction density of 3.35g/cm 3 The electron microscope scanning picture is shown in fig. 8.
Comparative example 4
A high nickel single crystal nickel cobalt manganese ternary cathode material was prepared by the method of reference example 1, except that: step (2) omits a rapid heating section and a rapid cooling section; other operations and conditions are kept unchanged, and the high-nickel monocrystal nickel-cobalt-manganese ternary anode material LiNi is prepared 0.9 Co 0.05 Mn 0.05 Zr 0.001 O 2 The median particle diameter D50 is 3.2 μm, the particle size distribution (D90-D10)/D50 is 1.0, the lattice stress is 0.09, the lithium nickel mixing rate is 2.16%, the single crystal particle size is 1.2 μm, and the specific surface area is 0.3m 2 Per gram, a compaction density of 3.35g/cm 3 The electron microscope scanning picture is shown in fig. 9.
The high nickel single crystal nickel cobalt manganese ternary cathode materials prepared in examples 1 to 5 and comparative examples 1 to 4 were assembled into a C2032 type button cell, and performance tests were performed, and the results are shown in table 1:
table 1 lithium ion battery performance comparison
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As can be seen from the examples and comparative examples in Table 1, the single crystal ternary cathode material prepared by the invention can control the lattice stress of the material within the range of 0.02-0.07, and the lithium nickel mixed discharge rate within the range of 1.90-2.10%, thereby effectively improving the capacity, multiplying power and cycle performance of the battery.
Claims (10)
1. A high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is characterized in that the general formula of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is LiNi x Co y Mn 1-x-y M b O 2 Wherein x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2,0.001 and b is more than or equal to 0.02, and M is one or more of Zr, al, ce, sr, mg, ti, si, la, ba, ta, W, co, nb, cr, mo, ca, Y, in, sn, F, P.
2. The high-nickel single-crystal nickel-cobalt-manganese ternary positive electrode material according to claim 1, wherein the lithium-nickel mixed discharge rate of the high-nickel single-crystal nickel-cobalt-manganese ternary positive electrode material is 1.90-2.10%; and/or
The lattice stress of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is 0.02-0.07; and/or
The specific surface area of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is 0.4-0.8m 2 /g; and/or
The compaction density of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is more than or equal to 3.35g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The granularity D50 of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is 3-6 mu m; and/or
The granularity distribution (D90-D10)/D50 of the high-nickel monocrystal nickel-cobalt-manganese ternary positive electrode material is 0.8-1.2; and/or
The single crystal grain size of the high nickel single crystal nickel cobalt manganese ternary positive electrode material is 1.5-3 mu m.
3. The high nickel single crystal nickel cobalt manganese ternary positive electrode material according to claim 1 or 2, wherein a coating agent is introduced on the surface; the coating agent is a compound containing one or more of Ti, mg, W, al, ce, co, F, P and B elements.
4. A method for preparing the high nickel single crystal nickel cobalt manganese ternary cathode material according to any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) Uniformly mixing a nickel-cobalt-manganese ternary positive electrode material precursor, a lithium source and a compound containing an element M;
(2) Sintering the mixture obtained in the step (1) for one time in an oxygen-containing atmosphere; the primary sintering is multiple variable-temperature sintering, and sequentially comprises a rapid heating section I, a slow heating sintering section II, a rapid heating section III, a rapid cooling section IV, a slow cooling sintering section V and a cooling section VI;
wherein the final temperature of the slow heating sintering section II is 50-150 ℃ higher than that of the fast heating section I, the final temperature of the fast heating section III is 50-100 ℃ higher than that of the slow heating sintering section II, the final temperature of the fast cooling section IV is the same as that of the slow heating sintering section II, and the final temperature of the slow cooling sintering section V is 100-200 ℃ lower than that of the slow heating sintering section II;
(3) Crushing the material subjected to the primary sintering in the step (2), sieving, and performing secondary sintering to obtain the high-nickel monocrystal nickel-cobalt-manganese ternary anode material.
5. The method of claim 4, wherein the nickel-cobalt-manganese ternary positive electrode material precursor in step (1) has a structural formula of Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than or equal to 0.8 and less than 1, and y is more than or equal to 0 and less than 0.2;
preferably, the nickel-cobalt-manganese ternary positive electrode material precursor is Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 、Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 、Ni 0.92 Co 0.04 Mn 0.04 (OH) 2 、Ni 0.92 Co 0.06 Mn 0.02 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The lithium source in the step (1) is selected from one or more of lithium salts and oxygen-containing compounds of lithium, preferably one or more of lithium carbonate, lithium nitrate, lithium hydroxide, lithium oxide, lithium acetate and lithium oxalate; and/or
The compound containing the element M in the step (1) is selected from one or more of oxides, hydroxides, sulfates and carbonates of the element M, preferably one or more of the oxides and hydroxides of the element M; and/or
The nickel-cobalt-manganese ternary positive electrode material precursor and a lithium source and a compound containing an element M in the step (1) are mixed according to the total amount of Ni, co and Mn, the lithium element and the element M, wherein the mixing molar ratio is 1:0.9-1.1:0.001-0.02, preferably 1:1.0-1.05:0.001-0.003; and/or
In the mixing process in the step (1), firstly, mixing materials for 5-10min at a rotating speed of 200-500rpm, and then mixing materials for 20-40min at a rotating speed of 1000-1200 rpm.
6. The preparation method according to claim 4 or 5, wherein in the step (2), the final temperature of the rapid heating section I is 700-830 ℃, the final temperature of the slow heating sintering section II is 750-880 ℃, the final temperature of the rapid heating section III is 850-980 ℃, the final temperature of the rapid cooling section IV is the same as the final temperature of the slow heating sintering section II, the final temperature of the slow cooling sintering section V is 800-600 ℃, and the final temperature of the cooling section VI is 25-150 ℃;
preferably, the temperature rising rate of the rapid temperature rising section I is 3-5 ℃/min, the temperature rising rate of the slow temperature rising sintering section II is 0.3-0.5 ℃/min, the temperature rising rate of the rapid temperature rising section III is 5-8 ℃/min, the temperature reducing rate of the rapid temperature reducing section IV is 5-8 ℃/min, the temperature reducing rate of the slow temperature reducing sintering section V is 0.1-0.5 ℃/min, and the temperature reducing rate of the cooling section VI is 3-5 ℃/min; and/or
The oxygen-containing atmosphere in the step (2) is one or more of air atmosphere, oxygen atmosphere or ozone atmosphere;
preferably, the slow cooling sintering section V adopts ozone atmosphere for sintering;
preferably, the primary sintering adopts different oxygen-containing atmospheres at different stages, wherein the slow cooling sintering section V adopts ozone atmosphere sintering, and the other sections adopt air atmosphere sintering.
7. The method of any one of claims 4 to 6, wherein the sieving operation of step (3) has a mesh size of 200 to 500 mesh, preferably 200 to 400 mesh; and/or
The secondary sintering is carried out in the step (3), the temperature is 300-700 ℃ and the time is 8-12h;
preferably, the secondary sintering is performed in an oxygen-containing atmosphere, wherein the oxygen-containing atmosphere is one or more of an air atmosphere, an oxygen atmosphere or an ozone atmosphere.
8. The method according to any one of claims 4 to 7, wherein step (3) is carried out by coating treatment after crushing the material, sieving, comprising adding a coating agent precursor after sieving, mixing uniformly, and carrying out the secondary sintering;
preferably, the coating agent precursor is selected from compounds containing one or more of Ti, mg, W, al, ce, co, F, P and B elements.
9. A positive electrode of a lithium ion battery, comprising the high nickel single crystal nickel cobalt manganese ternary positive electrode material according to any one of claims 1 to 3 or prepared by the method according to any one of claims 4 to 8.
10. A lithium ion battery comprising the positive electrode of claim 9.
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