CN114843497B - A modified high-nickel ternary positive electrode material and preparation method thereof - Google Patents
A modified high-nickel ternary positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN114843497B CN114843497B CN202210312506.0A CN202210312506A CN114843497B CN 114843497 B CN114843497 B CN 114843497B CN 202210312506 A CN202210312506 A CN 202210312506A CN 114843497 B CN114843497 B CN 114843497B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- positive electrode
- nickel ternary
- nickel
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 110
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 114
- 239000010941 cobalt Substances 0.000 claims abstract description 114
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 114
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 13
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000011247 coating layer Substances 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims description 58
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 41
- 239000002243 precursor Substances 0.000 claims description 40
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 27
- 239000011572 manganese Substances 0.000 claims description 26
- 229910001416 lithium ion Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 229910013716 LiNi Inorganic materials 0.000 claims description 12
- 229940126062 Compound A Drugs 0.000 claims description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- -1 cobalt oxyhydroxide Chemical compound 0.000 claims description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims 4
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000002301 combined effect Effects 0.000 abstract 1
- 238000005507 spraying Methods 0.000 description 37
- 238000000498 ball milling Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 27
- 238000003756 stirring Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- 239000010405 anode material Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种改性高镍三元正极材料及其制备方法。所述改性高镍三元正极材料为钴元素掺杂和钴元素包覆的高镍三元正极材料。其中，钴元素掺杂的质量分数为0.2～2％，钴元素包覆层的厚度为20～200nm。掺杂在高镍三元正极材料表面的钴元素可以提升高镍三元正极材料的循环性能，在微波处理包覆钴元素时氢氧化钴与材料表面的残余锂发生反应，可以降低材料表面的残余锂含量。在掺杂和包覆的共同作用下，高镍三元正极材料的性能得到明显的提升。且本发明中的制备方法简单、成本低、环境友好，适用于大规模工业生产。The present invention discloses a modified high-nickel ternary positive electrode material and a preparation method thereof. The modified high-nickel ternary positive electrode material is a high-nickel ternary positive electrode material doped with cobalt and coated with cobalt. The mass fraction of the cobalt element doping is 0.2-2%, and the thickness of the cobalt element coating layer is 20-200 nm. The cobalt element doped on the surface of the high-nickel ternary positive electrode material can improve the cycle performance of the high-nickel ternary positive electrode material. When the cobalt element is coated by microwave treatment, cobalt hydroxide reacts with the residual lithium on the surface of the material, which can reduce the residual lithium content on the surface of the material. Under the combined effect of doping and coating, the performance of the high-nickel ternary positive electrode material is significantly improved. The preparation method of the present invention is simple, low-cost, environmentally friendly, and suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a modified high-nickel ternary positive electrode material and a preparation method thereof.
Background
The requirement of the power battery on high energy density promotes the development of high-nickel positive electrode materials, lithium-rich manganese-based positive electrode materials, lithium-sulfur batteries and the like, and the high-nickel ternary positive electrode material LiNi xCoyMn1-x-yO2 (NCM) has the advantages of high specific capacity, good multiplying power performance, relatively low cost and the like, is in an absolute leading position in various positive electrode materials, and is considered as one of the positive electrode materials of the power battery with the most application prospect.
However, the high-nickel ternary cathode material has the defects of poor circularity, thermal stability, safety and the like. The layered structure of the high-nickel ternary positive electrode material is changed into a rock salt structure in the processes of high-temperature synthesis, air storage and repeated charge and discharge, and the transition has an inhibiting effect on the transmission of lithium ions from the surface of the high-nickel ternary positive electrode material to the inside of the high-nickel ternary positive electrode material. In addition, during storage in air, the high nickel ternary cathode material reacts with moisture and carbon dioxide in air, thereby forming residual lithium compounds containing LiOH, liHCO 3, and Li 2CO3 on the surface thereof. These residual lithium compounds can have an adverse effect on the lithium ion battery, can cause the lithium ion battery to generate gas during the cycle process, and can also cause the slurry of the high nickel ternary positive electrode material to gel during the manufacturing process of the lithium ion battery.
Based on the problems existing in the high-nickel ternary cathode material, the development of a technology for effectively improving or overcoming the defects of the high-nickel ternary cathode material is of great significance, and is favorable for promoting the further development and utilization of the high-nickel ternary cathode material.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a modified high-nickel ternary positive electrode material and a preparation method thereof, wherein the material modification is realized by doping cobalt element and coating cobalt element, the doping of cobalt element is beneficial to improving the cycle performance of the high-nickel ternary positive electrode material, and the cobalt layer coated by using a microwave heating method can reduce the residual lithium content in the high-nickel ternary positive electrode material, so that the gas production problem in the battery cycle process is effectively solved. The preparation method is simple, low in cost and environment-friendly, and is suitable for large-scale industrial production.
In a first aspect of the invention, a high-nickel ternary cathode material is provided, wherein the ternary cathode material is a cobalt-doped and cobalt-coated high-nickel ternary cathode material.
According to the first aspect of the present invention, in some embodiments of the present invention, the mass fraction of the cobalt element doping in the high nickel ternary cathode material is 0.2-2%.
In some preferred embodiments of the present invention, in the high nickel ternary cathode material, the thickness of the cobalt element coating layer is 20nm to 200nm.
In some preferred embodiments of the present invention, in the high nickel ternary cathode material, the thickness of the cobalt element coating layer is 50nm to 100nm.
According to a second aspect of the invention, there is provided a preparation method of the high nickel ternary cathode material according to the first aspect of the invention, the preparation method comprising the following steps:
(1) Coating a cobalt-containing compound A on the surface of a nickel cobalt manganese hydroxide precursor Ni xCoyMn1-x-y(OH)2 to prepare a nickel cobalt manganese hydroxide precursor with the surface coated with cobalt element;
(2) Mixing and calcining the nickel cobalt manganese hydroxide precursor with the cobalt element coated on the surface in the step (1) and a lithium-containing compound to prepare a high-nickel ternary positive electrode material with the cobalt element doped on the surface;
(3) And (3) mixing the high-nickel ternary cathode material with the surface doped with the cobalt element in the step (2) with a cobalt-containing compound B, and performing microwave treatment to obtain the high-nickel ternary cathode material with the surface doped with the coated cobalt element LiNi xMnyCo1-x-yO2·nLiCoO2.
According to a second aspect of the invention, in some embodiments of the invention, 1.00> x.gtoreq.0.6, y >0,1-x-y >0 in the chemical formula Ni xCoyMn1-x-y(OH)2 of the nickel cobalt manganese hydroxide precursor described in step (1).
In some preferred embodiments of the present invention, the nickel cobalt manganese hydroxide precursor Ni xCoyMn1-x-y(OH)2 in step (1) is Ni 0.95Co0.03Mn0.02(OH)2.
In some preferred embodiments of the invention, the Ni 0.95Co0.03Mn0.02(OH)2 is available from guangdong bang circulating technologies, inc.
In some preferred embodiments of the present invention, in the chemical formula LiNi xMnyCo1-x-yO2·nLiCoO2 of the high-nickel ternary positive electrode material with the surface doped with the cladding cobalt element described in the step (3), 1.00> x is equal to or greater than 0.6, y >0,1-x-y >0, and n >0.
Among them, liCoO 2 exists in LiNi xMnyCo1-x-yO2 in a doped and coated form.
In some preferred embodiments of the invention, the specific steps in the step (1) are that a solution formed by dissolving the cobalt-containing compound A in water is placed in spraying equipment for standby, a nickel cobalt manganese hydroxide precursor Ni xCoyMn1-x-y(OH)2 is placed in mixing equipment with a heating function for stirring, and in the stirring process, the cobalt-containing compound A is coated on the surface of Ni xCoyMn1-x-y(OH)2 by using a spraying method, so that the nickel cobalt manganese hydroxide precursor coated with cobalt is prepared.
In some preferred embodiments of the invention, the stirring speed of the nickel cobalt manganese hydroxide precursor Ni xCoyMn1-x-y(OH)2 is 200-800rpm.
In some preferred embodiments of the invention, ni xCoyMn1-x-y(OH)2 continues to be stirred after spraying is complete.
In some more preferred embodiments of the invention, the stirring is continued for a period of 30-300 minutes after the spraying is completed.
In some more preferred embodiments of the present invention, the spraying time of the spraying method is 5 to 120min.
In some more preferred embodiments of the present invention, the spraying time of the spraying method is 20 to 100 minutes.
In some more preferred embodiments of the present invention, the spraying time of the spraying method is 30 to 60 minutes.
In some more preferred embodiments of the present invention, the spraying flow rate of the spraying method is 3-6 mL/min.
In some more preferred embodiments of the present invention, the mass ratio of the cobalt-containing compound A to water is 1 (1-100).
In some preferred embodiments of the present invention, the cobalt-containing compound a in step (1) comprises at least one of cobalt chloride hexahydrate, cobalt nitrate hexahydrate, cobalt acetate tetrahydrate, cobalt sulfate heptahydrate.
In some preferred embodiments of the present invention, the molar ratio of Ni xCoyMn1-x-y(OH)2 to cobalt element in the cobalt-containing compound a in the step (1) is 1 (0.002-0.02).
In some preferred embodiments of the present invention, the lithium-containing compound in step (2) comprises at least one of lithium hydroxide, lithium carbonate, lithium fluoride, lithium chloride, lithium nitrate.
In some preferred embodiments of the present invention, the molar ratio of Ni xCoyMn1-x-y(OH)2 to lithium element in the lithium-containing compound in step (2) is 1 (1 to 1.2).
In some preferred embodiments of the present invention, the calcination temperature in step (2) is 700 to 1000 ℃.
In some preferred embodiments of the present invention, the calcination time in step (2) is 10 to 20 hours.
In some preferred embodiments of the present invention, the cobalt-containing compound B in step (3) includes at least one of cobalt oxide, tricobalt tetraoxide, cobalt oxyhydroxide, cobalt hydroxide, cobaltosic oxide, cobalt carbonate, cobalt acetate, cobalt oxalate.
In some preferred embodiments of the present invention, the molar ratio of the high nickel ternary positive electrode material doped with cobalt element on the surface in the step (3) to cobalt element of the cobalt-containing compound B is 1 (0.002-0.02).
In some preferred embodiments of the invention, the power of the microwave treatment described in step (3) is in the range 1000W to 1800W.
In some preferred embodiments of the present invention, the temperature of the microwave treatment in step (3) is 200 to 400 ℃.
In some preferred embodiments of the present invention, the time of the microwave treatment in the step (3) is 10 to 120min.
In a third aspect of the present invention, there is provided a positive electrode sheet, wherein the active material in the positive electrode sheet is the high nickel ternary positive electrode material in the first aspect of the present invention.
According to a third aspect of the present invention, in some embodiments of the present invention, the positive electrode sheet further includes a conductive agent and a binder.
In some preferred embodiments of the present invention, the mass ratio of the active material, the conductive agent, and the binder in the positive electrode sheet is 90:5:5.
In some preferred embodiments of the invention, the positive plate is prepared by dispersing active substances, conductive agents and binders in N-methylpyrrolidone, stirring for 4 hours, coating the mixture on the surface of aluminum foil, and vacuum drying at 120 ℃ to obtain the positive plate.
In a fourth aspect of the present invention, there is provided a lithium ion battery assembled using the positive electrode sheet according to the third aspect of the present invention.
According to the fourth aspect of the invention, in some embodiments of the invention, the method for assembling the lithium ion battery comprises the steps of taking the positive plate according to the third aspect of the invention as a positive electrode of the lithium ion battery, taking metal lithium as a counter electrode of the lithium ion battery, and assembling the button cell in a glove box filled with high-purity argon.
In some preferred embodiments of the invention, the button cell is a lithium ion battery of CR2032 type.
The beneficial effects of the invention are as follows:
1. According to the invention, the precursor of the high-nickel ternary cathode material is coated by adopting a spray coating method, the formed coating layer is more uniform, the coated precursor is sintered with the lithium-containing compound to prepare the high-nickel ternary cathode material with the cobalt doped on the surface, and the high-nickel ternary cathode material with the cobalt doped on the surface is coated by adopting a microwave heating method. The preparation method is simple, low in cost and environment-friendly, and is suitable for large-scale industrial production.
2. The cobalt element in the cobalt element doped and cobalt element coated high-nickel ternary positive electrode material prepared by the method is distributed at different depths, so that a protective layer is formed on the surface of the positive electrode material, the lithium nickel mixed discharge phenomenon in the positive electrode material in the battery cycle process can be inhibited, and the high-nickel ternary positive electrode material has excellent cycle performance.
3. According to the invention, the cobalt element doped on the surface layer of the high-nickel ternary positive electrode material is beneficial to improving the cycle performance of the positive electrode material, and the cobalt element coated on the surface layer of the positive electrode material can react with the residual lithium on the surface of the positive electrode material when being coated by microwave heating, so that the content of the residual lithium on the surface of the positive electrode material is reduced, and the gas production problem in the battery cycle process can be effectively solved. Under the combined action of surface doping and surface cladding of cobalt element, the electrochemical performance of the high-nickel ternary anode material is obviously improved.
Drawings
FIG. 1 is an SEM image of a high nickel ternary cathode material prepared in example 1 of the invention;
FIG. 2 is an XRD pattern of the product of microwave heating of a mixture of cobalt hydroxide, lithium hydroxide and lithium carbonate;
fig. 3 is a graph showing the change of the capacity retention rate of the lithium ion battery assembled by the high nickel ternary cathode material in examples 1 to 3 and comparative examples 1 to 3 with the number of cycles.
Detailed Description
The invention will be further described with reference to specific embodiments, and advantages and features of the invention will become apparent from the description. These examples are merely exemplary and do not limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the technical solution of the present invention may be made without departing from the spirit and scope of the present invention, but these changes and substitutions fall within the scope of the present invention.
Example 1 preparation of modified high Nickel ternary cathode Material
(1) Preparing a nickel cobalt manganese hydroxide precursor with a cobalt element coated on the surface:
45.82g of cobalt chloride hexahydrate was dissolved in 120mL of deionized water to prepare an aqueous cobalt chloride solution, and the aqueous cobalt chloride solution was placed in a spraying apparatus. 1111.7g of Ni 0.95Co0.03Mn0.02(OH)2, a nickel cobalt manganese hydroxide precursor, is placed in a high-efficiency mixer with a heating function for stirring, the heating temperature is 150 ℃, and the stirring speed is 600rpm. Spraying by using spraying equipment filled with cobalt chloride aqueous solution in the process of stirring the precursor at a high speed, controlling the spraying time to be 30min, controlling the spraying flow to be 4mL/min, and continuously stirring the solution for 120min by using a high-efficiency mixer with a heating function after the spraying is finished until Ni 0.95Co0.03Mn0.02(OH)2 is sufficiently dried to prepare the nickel-cobalt-manganese hydroxide precursor with the surface coated with cobalt element;
(2) Preparing a high-nickel ternary positive electrode material with a cobalt element doped on the surface:
Placing 1kg of the nickel cobalt manganese hydroxide precursor with the surface coated with the cobalt element prepared in the step (1) and 462g of lithium hydroxide into a ball mill for ball milling and mixing, wherein the ball milling speed is 500rpm, the ball milling time is 4 hours, and then calcining at 800 ℃ for 15 hours to prepare the high-nickel ternary anode material with the surface doped with the cobalt element;
(3) Preparing the high-nickel ternary anode material with the surface doped with the coating cobalt element:
975.6g of the high-nickel ternary cathode material with the surface doped with the cobalt element obtained in the step (2) and 13.95g of cobalt hydroxide are placed in a ball mill for ball milling and mixing, the ball milling speed is 500rpm, the ball milling time is 4 hours, then the high-nickel ternary cathode material is subjected to microwave treatment in a high-power microwave oven, the power of the microwave treatment is 1600W, the temperature of the microwave treatment is 300 ℃, and the microwave treatment time is 60 minutes. The high-nickel ternary anode material with the surface doped with the coating cobalt element is prepared, and the chemical formula of the high-nickel ternary anode material with the surface doped with the coating cobalt element is LiNi 0.936Co0.044Mn0.02O2·0.015LiCoO2.
Example 2 preparation of modified high Nickel ternary cathode Material
(1) Preparing a nickel cobalt manganese hydroxide precursor with a cobalt element coated on the surface:
34.92g of cobalt nitrate was dissolved in 120mL of deionized water to prepare an aqueous cobalt nitrate solution, which was placed in a spraying apparatus. 1111.7g of Ni 0.95Co0.03Mn0.02(OH)2, a nickel cobalt manganese hydroxide precursor, is placed in a high-efficiency mixer with a heating function for stirring, the heating temperature is 150 ℃, and the stirring speed is 600rpm. Spraying by using spraying equipment filled with cobalt nitrate aqueous solution in the process of stirring the precursor at a high speed, controlling the spraying time to be 30min, controlling the spraying flow to be 4mL/min, and continuously stirring the solution for 120min by using a high-efficiency mixer with a heating function after the spraying is finished until the precursor is sufficiently dried, so as to prepare the nickel cobalt manganese hydroxide precursor with the surface coated with cobalt element;
(2) Preparing a high-nickel ternary positive electrode material with a cobalt element doped on the surface:
Placing 1kg of the nickel cobalt manganese hydroxide precursor with the surface coated with the cobalt element prepared in the step (1) and 462g of lithium hydroxide into a ball mill for ball milling and mixing, wherein the ball milling speed is 500rpm, the ball milling time is 4 hours, and then calcining at 800 ℃ for 15 hours to prepare the high-nickel ternary anode material with the surface doped with the cobalt element;
(3) Preparing the high-nickel ternary anode material with the surface doped with the coating cobalt element:
975.6g of the high-nickel ternary cathode material with the surface doped with the cobalt element obtained in the step (2) and 9.30g of cobalt hydroxide are placed in a ball mill for ball milling and mixing, the ball milling speed is 500rpm, the ball milling time is 4 hours, then the mixture is heated in a high-power microwave oven by microwaves, the power of the microwave heating is 1600W, the temperature of the microwave heating is 300 ℃, and the time of the microwave heating is 60 minutes. The high-nickel ternary anode material with the surface doped with the coating cobalt element is prepared, and the chemical formula of the high-nickel ternary anode material with the surface doped with the coating cobalt element is LiNi 0.94Co0.04Mn0.02O2·0.01LiCoO2.
Example 3 preparation of modified high Nickel ternary cathode Material
(1) Preparing a nickel cobalt manganese hydroxide precursor with a cobalt element coated on the surface:
84.65g of cobalt acetate tetrahydrate was dissolved in 120mL of deionized water to prepare an aqueous cobalt acetate solution, and the aqueous cobalt acetate solution was placed in a spraying apparatus. 1kg of Ni 0.95Co0.03Mn0.02(OH)2, a precursor of nickel cobalt manganese hydroxide, is placed in a high-efficiency mixer with a heating function for stirring, the heating temperature is 150 ℃, and the stirring speed is 600rpm. Spraying by using spraying equipment filled with cobalt acetate aqueous solution in the process of stirring the precursor at a high speed, controlling the spraying time to be 30min, controlling the spraying flow to be 4mL/min, and continuously stirring the solution for 120min by using a high-efficiency mixer with a heating function after the spraying is finished until the precursor is sufficiently dried, so as to prepare the nickel cobalt manganese hydroxide precursor with the surface coated with cobalt element;
(2) Preparing a high-nickel ternary positive electrode material with a cobalt-containing element doped on the surface:
Ball-milling and mixing 1kg of the nickel cobalt manganese hydroxide precursor with the surface coated with the cobalt element prepared in the step (1) with 462g of lithium hydroxide, wherein the ball milling speed is 500rpm, the ball milling time is 4 hours, and then calcining at 800 ℃ for 15 hours to prepare the high-nickel ternary positive electrode material with the surface doped with the cobalt element;
(3) Preparing the high-nickel ternary anode material with the surface doped with the coating cobalt element:
Mixing 1kg of the high-nickel ternary cathode material with the surface doped with the cobalt element prepared in the step (2) with 4.65g of cobalt hydroxide through ball milling, wherein the ball milling speed is 500rpm, the ball milling time is 4 hours, and then heating the mixture in a high-power microwave oven with the microwave heating power of 1600W, the microwave heating temperature of 300 ℃ and the microwave heating time of 60 minutes. The high-nickel ternary anode material with the surface doped with the coating cobalt element is prepared, and the chemical formula of the high-nickel ternary anode material with the surface doped with the coating cobalt element is LiNi 0.945Co0.035Mn0.02O2·0.005LiCoO2.
Comparative example 1
Compared with the example 1, the difference is that the high-nickel ternary positive electrode material prepared in the comparative example 1 is not coated with cobalt element or doped with cobalt element, and the specific steps are as follows:
And (3) ball-milling and mixing 1kg of Ni 0.95Co0.03Mn0.02(OH)2 which is a nickel cobalt manganese hydroxide precursor with 462g of lithium hydroxide, wherein the ball milling speed is 500rpm, the ball milling time is 4 hours, and then calcining at 800 ℃ for 15 hours to prepare the high-nickel ternary cathode material LiNi 0.95Co0.03Mn0.02O2.
Comparative example 2
Comparative example 2 is different from example 1 in that the high nickel ternary cathode material prepared in comparative example 2 is only coated with cobalt element, and is not doped with cobalt element, and the specific steps are as follows:
(1) And (3) ball-milling and mixing 1kg of Ni 0.95Co0.03Mn0.02(OH)2 which is a nickel cobalt manganese hydroxide precursor with 462g of lithium hydroxide, wherein the ball milling speed is 500rpm, the ball milling time is 4 hours, and then calcining at 800 ℃ for 15 hours to prepare the high-nickel ternary anode material.
(2) 975.6G of the high-nickel ternary cathode material obtained in the step (1) and 13.95g of cobalt hydroxide are mixed through ball milling, the ball milling speed is 500rpm, the ball milling time is 4 hours, then the mixture is heated in a high-power microwave oven with the microwave heating power of 1600W, the microwave heating temperature is 300 ℃, and the microwave heating time is 60 minutes. And (3) preparing the high-nickel ternary cathode material LiNi 0.95Co0.03Mn0.02O2 with the surface coated with the cobalt element.
Comparative example 3
Comparative example 3 is different from example 1 in that the high nickel ternary cathode material prepared in comparative example 3 is only a cobalt-doped high nickel ternary cathode material, and is not cobalt-coated, and the steps of the bulk are:
(1) 45.82g of cobalt chloride hexahydrate was dissolved in 120mL of deionized water to prepare an aqueous cobalt chloride solution, and the aqueous cobalt chloride solution was placed in a spraying apparatus. 1111.7g of Ni 0.95Co0.03Mn0.02(OH)2, a nickel cobalt manganese hydroxide precursor, is placed in a high-efficiency mixer with a heating function for stirring, the heating temperature is 150 ℃, and the stirring speed is 600rpm. Spraying by using spraying equipment filled with cobalt chloride aqueous solution in the process of stirring the precursor at a high speed, controlling the spraying time to be 30min, controlling the spraying flow to be 4mL/min, and continuously stirring the solution for 120min by using a high-efficiency mixer with a heating function after the spraying is finished until the precursor is sufficiently dried to obtain a nickel-cobalt-manganese hydroxide precursor with the surface coated with cobalt element;
(2) And (3) ball-milling and mixing 1kg of the nickel cobalt manganese hydroxide precursor with the surface coated with the cobalt element prepared in the step (1) with 462g of lithium hydroxide, wherein the ball milling speed is 500rpm, the ball milling time is 4 hours, and then calcining at 800 ℃ for 15 hours to prepare the high-nickel ternary positive electrode material with the surface doped with the cobalt element, and the chemical formula of the high-nickel ternary positive electrode material with the surface doped with the cobalt element is LiNi 0.936Co0.044Mn0.02O2·0.015LiCoO2.
Characterization and performance test of modified high-nickel ternary cathode material
(1) Morphology characterization:
Fig. 1 is an SEM image of the modified high-nickel ternary cathode material prepared in example 1, and it can be seen from the image that the particle surface of the modified high-nickel ternary cathode material has micro powder distribution (such as the circled part in fig. 1), which is a substance formed after cobalt hydroxide reacts with residual lithium on the surface of the modified high-nickel ternary cathode material under the condition of microwave heating.
(2) Testing of residual lithium content in high nickel ternary cathode material:
Dispersing the high-nickel ternary cathode material in deionized water, stirring for 30 minutes, filtering by a vacuum filtration device, collecting filtrate, weighing, placing the filtrate in a potentiometric titrator, performing potentiometric titration by using hydrochloric acid labeling solution with the concentration of 0.1mol/L until the pH value is less than or equal to 4, and recording the consumption volume of hydrochloric acid at a mutation point in a titration curve. And then processing the data according to a conventional method in the field, and calculating to obtain the residual lithium content in the high-nickel ternary cathode material.
The test results of the residual lithium contents in the high nickel ternary cathode materials prepared in examples 1 to 3 and comparative examples 1 to 3 are shown in table 1, and it can be seen from the data in table 1 that the residual lithium contents in examples 1 to 3 are lower than those in comparative examples 1 to 3, because cobalt hydroxide reacts with the residual lithium (composed of lithium hydroxide and lithium carbonate) on the surface of the material when the microwave coats cobalt element, and lithium cobaltate is generated, thereby reducing the residual lithium content on the surface of the material. Fig. 2 is an XRD pattern of a product of microwave heating of a mixture of cobalt hydroxide, lithium hydroxide and lithium carbonate, wherein the molar ratio of cobalt hydroxide, lithium hydroxide and lithium carbonate is 2:1:1, and it can be seen from fig. 2 that peaks in the XRD pattern are characteristic peaks of LiCoO 2, which further illustrates that in the microwave heating process of the modified high-nickel ternary cathode material prepared in the embodiment of the invention, cobalt hydroxide reacts with residual lithium consisting of lithium hydroxide and lithium carbonate, thereby generating LiCoO 2.
Table 1 statistics of residual lithium content in the high nickel ternary cathode materials prepared in examples 1 to 3 and comparative examples 1 to 3
| Sample of | Residual lithium content (%) |
| Example 1 | 0.1782 |
| Example 2 | 0.1945 |
| Example 3 | 0.2069 |
| Comparative example 1 | 0.2744 |
| Comparative example 2 | 0.2146 |
| Comparative example 3 | 0.2698 |
(3) Electrochemical performance test
And (3) assembling the lithium ion battery, namely mixing a conductive agent and a binder according to a certain proportion, adding the mixture into 1-methyl 2-pyrrolidone, fully stirring in a vacuum stirrer, adding the positive electrode material in the embodiment or the comparative example (wherein the mass ratio of the positive electrode material to the binder to the conductive agent is 90:5:5), fully stirring uniformly to obtain the slurry of the electrode material, coating the slurry on an aluminum foil, and drying and grinding to obtain the positive electrode sheet, wherein the surface density of the positive electrode sheet in the embodiment is 3.7g/cm 2. The obtained positive plate is used as a positive electrode, metal lithium is used as a counter electrode, and the CR2032 type lithium ion button cell is assembled for testing electrochemical performance. Wherein the electrolyte is E20, purchased from Shenzhen New SappaTechno Co., ltd.
The electrochemical performance test of the lithium ion battery comprises the steps that the test equipment is a blue battery test system, the voltage window is 2.8V-4.3V, the current density is 1C, and the test temperature is normal temperature.
Fig. 3 shows the change of the capacity retention rate with the number of cycles of the lithium ion batteries assembled by using the positive electrode materials of examples 1 to 3 and comparative examples 1 to 3, and it can be seen from the data in fig. 3 that the capacity retention rate of the lithium ion batteries assembled by using the positive electrode materials of examples 1 to 3 is slower with the decreasing rate of the number of cycles and has a higher capacity retention rate than that of comparative examples 1 to 3. The method shows that the cycle performance of the high-nickel ternary positive electrode material is further improved by simultaneously carrying out cobalt element doping and cobalt element cladding on the high-nickel ternary positive electrode material, and the electrochemical performance of the lithium ion battery assembled by the positive electrode material is superior to that of a lithium ion battery assembled by a pure cobalt element doping or cobalt element cladding positive electrode material. In addition, the capacity retention rate of the lithium ion batteries assembled with the cathode materials of comparative examples 2 and 3 is slower than that of the lithium ion battery assembled with the cathode material of comparative example 1, which indicates that the single coating or doping of the high-nickel ternary cathode material with cobalt element can improve the cycle performance of the high-nickel ternary cathode material.
Table 2 shows electrochemical properties of lithium ion batteries assembled with the high nickel ternary cathode materials prepared in examples 1 to 3 and comparative examples 1 to 3, and table 2 includes a specific first-week discharge capacity, a first-week efficiency, and a capacity retention rate of 100 cycles. As can be seen from table 2, the lithium ion battery prepared from the high-nickel ternary cathode material in examples 1-3 has higher first-cycle discharge specific capacity and first-cycle efficiency than the lithium ion battery assembled from the high-nickel ternary cathode material in comparative examples 1-3, and the 100-cycle capacity retention rate of the lithium ion battery assembled from the high-nickel ternary cathode material in examples 1-3 is significantly higher than that of the lithium ion battery assembled from the high-nickel ternary cathode material in comparative examples 1-3, which indicates that the cobalt element doping and cobalt element coating of the high-nickel ternary cathode material by the method in the examples of the invention can significantly improve the cycle performance and cycle life of the high-nickel ternary cathode material.
Table 2 electrochemical Properties of the high Nickel ternary cathode materials prepared in examples 1 to 3 and comparative examples 1 to 3
| Sample of | Specific discharge capacity at first week (mAh/g) | First week efficiency (%) | Capacity retention of 100 cycles (%) |
| Example 1 | 229.8 | 92.7 | 83.74 |
| Example 2 | 228.9 | 92.0 | 81.53 |
| Example 3 | 227.3 | 92.1 | 80.31 |
| Comparative example 1 | 226.8 | 90.9 | 69.38 |
| Comparative example 2 | 226.7 | 91.7 | 78.55 |
| Comparative example 3 | 226.9 | 91.0 | 74.55 |
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210312506.0A CN114843497B (en) | 2022-03-28 | 2022-03-28 | A modified high-nickel ternary positive electrode material and preparation method thereof |
| PCT/CN2022/131917 WO2023184996A1 (en) | 2022-03-28 | 2022-11-15 | Modified high-nickel ternary positive electrode material and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210312506.0A CN114843497B (en) | 2022-03-28 | 2022-03-28 | A modified high-nickel ternary positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114843497A CN114843497A (en) | 2022-08-02 |
| CN114843497B true CN114843497B (en) | 2025-01-10 |
Family
ID=82563491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210312506.0A Active CN114843497B (en) | 2022-03-28 | 2022-03-28 | A modified high-nickel ternary positive electrode material and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114843497B (en) |
| WO (1) | WO2023184996A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114843497B (en) * | 2022-03-28 | 2025-01-10 | 广东邦普循环科技有限公司 | A modified high-nickel ternary positive electrode material and preparation method thereof |
| CN117164017A (en) * | 2023-09-06 | 2023-12-05 | 荆门市格林美新材料有限公司 | Modified lithium-rich manganese-based precursor and preparation method and application thereof |
| CN117525386B (en) * | 2024-01-08 | 2024-05-14 | 宁波容百新能源科技股份有限公司 | High-nickel positive electrode material, and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185962A (en) * | 2015-08-31 | 2015-12-23 | 宁波金和锂电材料有限公司 | High-nickel cathode material and preparation method thereof and lithium-ion battery |
| CN106898751A (en) * | 2017-03-31 | 2017-06-27 | 中南大学 | A kind of nickelic ternary material with rich cobalt top layer and its preparation method and application |
| CN110247031A (en) * | 2019-05-24 | 2019-09-17 | 乳源东阳光磁性材料有限公司 | Nickelic tertiary cathode material of a kind of cobalt acid lithium cladding and preparation method thereof |
| CN111200120A (en) * | 2018-11-20 | 2020-05-26 | 深圳市贝特瑞纳米科技有限公司 | Ternary cathode material, preparation method thereof and lithium ion battery |
| CN112750999A (en) * | 2020-12-28 | 2021-05-04 | 北京当升材料科技股份有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN113353995A (en) * | 2021-07-07 | 2021-09-07 | 远景动力技术(江苏)有限公司 | Cathode material with low cobalt content and preparation method and application thereof |
| CN114243014A (en) * | 2021-10-29 | 2022-03-25 | 广东邦普循环科技有限公司 | A kind of single crystal ternary cathode material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180009911A (en) * | 2016-07-20 | 2018-01-30 | 주식회사 엘지화학 | Positive Electrode Active Material Comprising High-voltage Lithium Cobalt Oxide for Lithium Secondary Battery and Method of Manufacturing the Same |
| KR102654264B1 (en) * | 2018-08-13 | 2024-04-02 | 에스케이온 주식회사 | Cathode active material for lithium secondary battery, method of preparing the same and lithium secondary battery including the same |
| CN109860534B (en) * | 2018-12-18 | 2022-04-15 | 廊坊绿色工业技术服务中心 | A kind of ternary cathode material decorated with carbon quantum dots and preparation method thereof |
| CN114843497B (en) * | 2022-03-28 | 2025-01-10 | 广东邦普循环科技有限公司 | A modified high-nickel ternary positive electrode material and preparation method thereof |
-
2022
- 2022-03-28 CN CN202210312506.0A patent/CN114843497B/en active Active
- 2022-11-15 WO PCT/CN2022/131917 patent/WO2023184996A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105185962A (en) * | 2015-08-31 | 2015-12-23 | 宁波金和锂电材料有限公司 | High-nickel cathode material and preparation method thereof and lithium-ion battery |
| CN106898751A (en) * | 2017-03-31 | 2017-06-27 | 中南大学 | A kind of nickelic ternary material with rich cobalt top layer and its preparation method and application |
| CN111200120A (en) * | 2018-11-20 | 2020-05-26 | 深圳市贝特瑞纳米科技有限公司 | Ternary cathode material, preparation method thereof and lithium ion battery |
| CN110247031A (en) * | 2019-05-24 | 2019-09-17 | 乳源东阳光磁性材料有限公司 | Nickelic tertiary cathode material of a kind of cobalt acid lithium cladding and preparation method thereof |
| CN112750999A (en) * | 2020-12-28 | 2021-05-04 | 北京当升材料科技股份有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN113353995A (en) * | 2021-07-07 | 2021-09-07 | 远景动力技术(江苏)有限公司 | Cathode material with low cobalt content and preparation method and application thereof |
| CN114243014A (en) * | 2021-10-29 | 2022-03-25 | 广东邦普循环科技有限公司 | A kind of single crystal ternary cathode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023184996A1 (en) | 2023-10-05 |
| CN114843497A (en) | 2022-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107452948B (en) | Prussian blue composite lithium ion battery ternary cathode material and preparation method thereof | |
| CN114843497B (en) | A modified high-nickel ternary positive electrode material and preparation method thereof | |
| CN112018341A (en) | High-capacity high-nickel cathode material and preparation method thereof | |
| CN111762768B (en) | Spinel type lithium manganate-phosphate composite cathode material and preparation method thereof | |
| CN110649252A (en) | Ternary material LiNi of lithium battery0.8Co0.1Mn0.1O2Surface coated with Li2ZrO3Method (2) | |
| CN102214819B (en) | Method for manufacturing cobalt nickel lithium manganate oxide as gradient anode active material of lithium ion battery | |
| CN105826550B (en) | A kind of preparation method of iron containing compoundses coating manganate cathode material for lithium | |
| CN106602009A (en) | Lithium-rich positive electrode modified material of lithium ion battery and preparation method of lithium-rich positive electrode modified material | |
| CN106486657B (en) | A kind of surface in-situ coated lithium-rich material and preparation method thereof | |
| CN106602024B (en) | Surface in-situ modification type lithium-rich material and preparation method thereof | |
| CN100416895C (en) | A kind of positive electrode active material of lithium ion battery and preparation method thereof | |
| CN110233249A (en) | Lithium iron phosphate nano powder coats nickelic tertiary cathode material and its preparation method and application | |
| CN109728277A (en) | Method, product and battery for surface treatment of high nickel ternary cathode material | |
| KR20240011822A (en) | Surface coated cathode material and manufacturing method thereof, lithium ion battery | |
| CN113571679A (en) | Spinel oxide coated lithium-rich manganese-based positive electrode material | |
| CN113871603A (en) | High-nickel ternary cathode material and preparation method thereof | |
| CN111003733A (en) | Method for preparing high-nickel ternary lithium battery anode material through microwave intelligent frequency conversion second-order sintering | |
| CN114094060B (en) | Preparation method of high-voltage positive electrode material with core-shell structure | |
| CN114551835A (en) | A kind of ultra-high nickel quaternary cathode material, preparation method and application thereof | |
| CN110190277B (en) | Lithium ion battery anode material LiMnO2@ C and preparation method thereof | |
| CN110581277A (en) | A kind of surface coating method of positive electrode material of lithium ion battery | |
| CN112786825A (en) | Positive electrode material and preparation method and application thereof | |
| CN106784701A (en) | A kind of lithium ion battery composite cathode material and preparation method thereof | |
| CN115064670B (en) | A method for preparing doped and coated sodium nickel manganate cathode material | |
| CN114212834B (en) | Metal-doped modified ternary positive electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |