GB2624734A - Preparation method for closely coated cobalt oxide and use thereof - Google Patents
Preparation method for closely coated cobalt oxide and use thereof Download PDFInfo
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- GB2624734A GB2624734A GB2310124.9A GB202310124A GB2624734A GB 2624734 A GB2624734 A GB 2624734A GB 202310124 A GB202310124 A GB 202310124A GB 2624734 A GB2624734 A GB 2624734A
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- cobalt oxide
- zirconium
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- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 62
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 46
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 16
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 150000007942 carboxylates Chemical class 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 abstract description 15
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 abstract description 8
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 abstract description 8
- 239000012798 spherical particle Substances 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- OFYFURKXMHQOGG-UHFFFAOYSA-J 2-ethylhexanoate;zirconium(4+) Chemical compound [Zr+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O OFYFURKXMHQOGG-UHFFFAOYSA-J 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PTCGDEVVHUXTMP-UHFFFAOYSA-N flutolanil Chemical compound CC(C)OC1=CC=CC(NC(=O)C=2C(=CC=CC=2)C(F)(F)F)=C1 PTCGDEVVHUXTMP-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- BIBRSALWJZADJC-UHFFFAOYSA-N [O--].[O--].[O--].[Co++].[Zr+4] Chemical compound [O--].[O--].[O--].[Co++].[Zr+4] BIBRSALWJZADJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LTXHKPDRHPMBKA-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2] LTXHKPDRHPMBKA-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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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
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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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Disclosed in the present invention are a preparation method for a closely coated cobalt oxide and the use thereof, the preparation method comprising: synthesizing spherical cobalt hydroxide particles by a coprecipitation method; after drying and dehydrating same, uniformly mixing same with zirconium alkyl carboxylate/aluminum alkyl carboxylate and zirconium hydroxide/aluminum hydroxide and coheating the mixture to enable the zirconium alkyl carboxylate/aluminum alkyl carboxylate and zirconium hydroxide/aluminum hydroxide to react with cobalt hydroxide on the surface layers of the particles, so as to tightly attach same to the surfaces of the cobalt hydroxide spherical particles; and finally, performing calcining to remove organic matters so as to form cobalt oxide spherical particles with closely coating layers on the surfaces. By using chemical bonds to connect the coating layers and a base material, the present invention makes the two more closely attached and not prone to pulverization and falling, thus greatly prolonging the service life of the coating layers, and improving cycle performance of the material.
Description
METHOD FOR PREPARING TIGHTLY COATED COBALT OXIDE AND USE
THEREOF
FIELD
100011 The present disclosure relates to the field of precursors of positive electrode material for lithium ion batteries, and in particular to a method for preparing a tightly coated cobalt oxide and use thereof
BACKGROUND
100021 Lithium cobalt oxide electrode material has high specific capacity and good cycle stability, and it is a positive electrode material which is currently widely used in the field of 3C. With the rapid development of 3C electronic products, manufacturers continue to put forward higher requirements for the processing performance and electrochemical performance of lithium cobalt oxide positive electrode materials. Lithium cobalt oxide, as the earliest commercialized positive electrode material for lithium-ion batteries, is still one of the positive electrode materials with the highest compaction density in practical applications. The lithium cobalt oxide has a typical layered structure, in which cobalt ions and lithium ions are alternately distributed in the voids of the close-packed layers formed by oxygen ions. According to the amount of lithium ions that can be extracted from lithium cobalt oxide, the theoretical mass specific capacity of the lithium cobalt oxide is about 274mAhig.
[0003] With the rapid development of fields such as smart electronic devices, there is an urgent need for high-energy-density lithium batteries with long cycle life and high safety. Using positive electrodes with high voltage and high specific capacity is an effective way to improve the energy density of batteries. The lithium cobalt oxide positive electrode material has received extensive attention due to its high theoretical specific capacity, but there are still many problems and challenges on its use at high voltages, especially the problems such as the structural phase change at the interface with the electrolyte, the dissolution of transition metals, the precipitation of oxygen, and the continuous oxidative decomposition of the electrolyte, which severely limit the use of the lithium cobalt oxide positive electrode material in high-energy-density lithium batteries 100041 In view of the above problems, in the prior art, the structural properties and electrochemical properties of the particles can be optimized by forming a coating layer on the surface of the material, so as to improve the corrosion resistance of the material, and reduce the side reaction between the material and the electrolyte. By coating a thin and stable coating layer on the surface of the material, wherein the common coating materials are oxides, fluorides, lithium ion conductors and the like, the coating layer can reduce the contact resistance between the particles, and meanwhile separate the material from the electrolyte, so as to reduce the side reaction between the material and the electrolyte, and prevent the corrosion of the positive electrode material by the HP gas generated by the decomposition of the electrolyte.
[0005] The patent document with a publication number CN103359795A discloses a cobaltosic oxide-covered composite multi-element lithium ion battery positive electrode material precursor and a preparation method thereof; in which the "wet coating + sintering" method is used to obtain a very good and compact cobaltosic oxide coating layer on the surface of the sphere. However, the coating layer is easy to be pulverized and shed off during the long-term cycle, so that the lithium cobalt oxide is re-exposed to the electrolyte to be corroded, which affects the cycle performance of the material.
SUMMARY
[0006] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. Therefore, the present invention provides a method for preparing a tightly coated cobalt oxide and use thereof This method can obtain a layer of tightly-coated cobalt oxide, greatly prolonging the life of the coating layer, and further improving the cycle performance of the material [0007] In one aspect, the present invention provides a method for preparing a tightly-coated cobalt oxide, comprising the following steps: [0008] adding a cobalt salt solution, a sodium hydroxide solution and aqueous ammonia in parallel to a base solution to react, until the reaction material reaches the target particle size, performing ageing on the mixture, then subjecting the resulting mixture to solid-liquid separation
_
to obtain a precipitate, and washing and drying the precipitate to obtain a dry material: 100091 52: adding the dry material and hydroxide to an organic solution of metal carboxylate, heating the mixture to evaporate the solvent, and when the evaporation rate of the solvent reaches more than 90%, heating the mixture to 180-200°C to react; wherein the hydroxide is zirconium hydroxide or aluminum hydroxide, and the organic solution of metal carboxylate is an alcohol solution of zirconium alkylcarboxylate or aluminum alkylcarboxylate; [0010] 53: calcining the product after reaction in step 52 in an oxygen atmosphere to obtain the cobalt oxide.
100111 In some embodiments of the present invention, in step Si, the concentration of the cobalt salt solution is 1.0-2.0 mol/L, and the concentration of the sodium hydroxide solution is 4.0-10.0 mol/L.
[0012] In some embodiments of the present invention, in step SI, the concentration of the aqueous ammonia added in parallel is 6.0-12.0 mol/L.
[0013] In some embodiments of the present invention, in step SI, the base solution is a mixed solution of sodium hydroxide and aqueous ammonia, the pH of the base solution is 10-11, and the concentration of ammonia is 5.0-10.0 g/L.
[0014] In some embodiments of the present invention, in step Sl, the temperature of the reaction is controlled to be 55-65°C, the pH of the reaction material is controlled to be 10-11, and the concentration of the ammonia is controlled to be 5-10 g/L.
[0015] In some embodiments of the present invention, in step SI, the target particle size of the reaction material is 2.0 pm-15.0 gm.
[0016] In some embodiments of the present invention, in step SI, the duration of the aging is I-2h.
100171 In some embodiments of the present invention, in step Si, the temperature of the drying is 100-120°C, and the duration of the drying is 4-6 h. [0018] In some embodiments of the present invention, in step 52, the ratio of the weight of the dry material to the volume of the organic solution of the metal carboxylate (solid-liquid ratio) is 1 g: (1-5) mL, and the concentration of the metal carboxylate in the organic solution of the metal -3 -carboxylate is 0.1-0.2mol/L.
100191 In some embodiments of the present invention, in step S2, the addition amount of the hydroxide is 1-5% of the weight of the dry material.
[0020] In some embodiments of the present invention, in step S2, the temperature of the heating to evaporate the solvent is 70-80°C.
[0021] In some embodiments of the present invention, in step S2, the duration of the reaction is 15-30 min. [0022] In some embodiments of the present invention, in step S2, the number of carbon atoms in the alkyl segment in the zirconium alkylcarboxylate or the aluminum alkylcarboxylate is 6-10.
100231 In some embodiments of the present invention, in step S3, the temperature of the calcining is 500-750°C.
[0024] In some embodiments of the present invention, in step S3, the duration of the calcining is 2-611 [0025] The present invention also provides application of the method in the preparation of lithium cobalt oxide or lithium ion batteries.
100261 According to a preferred embodiment of the present invention, it has at least the following beneficial effects: [0027] 1. In the present invention, spherical cobalt hydroxide particles are first synthesized by a co-precipitation method, then the spherical cobalt hydroxide particles are dried, dehydrated, and uniformly mixed with zirconium alkylcarboxylate/alumin um alkylcarboxylate and zirconium hydroxide/aluminum hydroxide, then the mixture is co-heated to react with the cobalt hydroxide on the particle surface, so as to closely adhere to the surface of the cobalt hydroxide spherical particles, and finally, the particles are calcined to remove the organic matter to form cobalt oxide spherical particles with a tight coating layer on the surface. The reaction equation thereof is as follows: [0028] In the co-precipitation reaction: [0029] Co2++201-1-->Co (OH)2; [0030] Taking zirconium hydroxide and zirconium alkylcarboxylate as an example, in the co-thermal reaction: 100311 (RnC00)4Zr+4Zr(OH)4->[RnC00-Zr(OH)2-0]4-Zr+4H20; [0032] (RnC00)4Zry4Co(OH)2-0.6C00-Co-0)4-ZrE4H20; [0033] Referring to the above reaction, in the present invention, a Co-O-Zr-O-Co or Co-O-Al-O-Co bond can be formed during the co-thermal reaction in step S2, so that the subsequent zirconium/aluminum and cobalt are closely connected through an oxide bond. The addition of zirconium hydroxide/aluminum hydroxide can increase the zirconium/aluminum content of the coating layer and reduce the cobalt content.
[0034] 2. The coating on the surface of the spherical particles is not pure zirconia/alumina, but cobalt zirconium oxide or cobalt aluminum oxide that formed by the connection between the zirconium/aluminum with the cobalt oxide through chemical bonds on the particle surface. Compared with the traditional coating method, in the present invention, the coating layer and the base material are connected through chemical bonds, making the two adhere to each other more closely, so that the coating layer is not easy to be pulverized and shed off, greatly prolonging the life of the coating layer, and improving the cycle performance of the material. Subsequently in the preparation of positive electrode material of lithium cobalt oxide, due to the zirconia/alumina on the surface of cobalt oxide, the problem of cobalt dissolution in lithium cobalt oxide due to long-term cycle can be prevented, further improving the cycle performance of the material.
BRIEF DESCRIPTION OF DRAWINGS
[0035] The present invention will be further described below in conjunction with the drawings and examples, wherein: [0036] FIG. 1 is the SEM image of the cobalt oxide prepared in Example 1 of the present 25 invention.
DETAILED DESCRIPTION -5 -
[0037] The concept of the present invention and the technical effects produced by the present invention will be clearly and completely described below with reference to the examples, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described examples are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the examples of the present invention, other examples obtained by those skilled in the art without creative efforts are all within the protection scope of the present invention
Example 1
[0038] In this example, a tightly-coated cobalt oxide was prepared. The specific process is: [0039] Step 1 a cobalt sulfate solution with a concentration of 2.0mol/L was prepared; [0040] Step 2: a sodium hydroxide solution with a concentration of 10.0mol/L was prepared as a precipitating agent; [0041] Step 3: an aqueous ammonia w with concentration of 12.0mol/L was prepared as a complexing agent; [0042] Step 4: pure water was added to a reaction kettle to overflow the bottom stirring paddle, then a certain amount of sodium hydroxide solution prepared in step 2 and aqueous ammonia prepared in step 3 were added to the kettle to form a base solution for starting reaction, wherein the pH value of the base solution was 10.5, and the concentration of ammonia was 5, OWL; [0043] Step 5: the cobalt salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, and the aqueous ammonia prepared in step 3 were added in parallel to the reaction kettle to react. In the reaction kettle, the stirring speed was controlled to be 500r/min, the pH was controlled to be 10.5, the temperature was controlled to be 55°C, and the concentration of ammonia was controlled to be 5g/L; [0044] Step 6: when the D50 of the material in the reaction kettle was detected to reach 15.0 pm, the feeding was stopped, and the material was aged for 2h; 100451 Step 7: the material in the kettle was subjected to solid-liquid separation, and then the obtained precipitate was washed with pure water, and dried at 120°C for 4 hours to obtain a dried material; [0046] Step 8: according to the solid-liquid ratio of lg:5mL, the dried material was added to an ethanol solution of aluminum octoate (CAS No. 6028-57-5) with a concentration of 0.2mol/L, then aluminum hydroxide with an amount of 5% of the weight of the dried material was added to the mixture. The obtained mixture was mixed uniformly, and heated (temperature was 70-80°C) under constant stirring to evaporate the organic solvent, and the organic solvent was recovered. When the organic solvent recovery rate reached more than 90%, the heating on the mixture was strengthened, and when the temperature reached 200°C, the temperature was maintained for 15min; 100471 Step 9: the product obtained in step 8 was calcined at 500°C in an oxygen atmosphere for 6 hours to obtain a tightly-coated cobalt oxide.
Example 2
100481 In this example, a tightly-coated cobalt oxide was prepared. The specific process is: 100491 Step 1 a cobalt nitrate solution with a concentration of 1.5mol/L was prepared; [0050] Step 2: a sodium hydroxide solution with a concentration of 7.0mol/L was prepared as a precipitating agent, [0051] Step 3: an aqueous ammonia with a concentration of 10.0mol/L was prepared as a complexing agent; [0052] Step 4: pure water was added to a reaction kettle to overflow the bottom stirring paddle, then a certain amount of sodium hydroxide solution prepared in step 2 and aqueous ammonia prepared in step 3 were added to the kettle to form a base solution for starting reaction, wherein the pH value of the base solution was 10.8, and the concentration of ammonia was 7g/L; [0053] Step 5: the cobalt salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, and the aqueous ammonia prepared in step 3 were added in parallel to the reaction kettle to react. In the reaction kettle, the stirring speed was controlled to be 350r/min, the pH was controlled to be 10.8, the temperature was controlled to be 60°C, and the concentration of ammonia was controlled to be 7g/L; 100541 Step 6: when the D50 of the material in the reaction kettle was detected to reach 10.0 pm, the feeding was stopped, and the material was aged for 1.5h; [0055] Step 7: the material in the kettle was subjected to solid-liquid separation, and then the obtained precipitate was washed with pure water, and dried at 110°C for 5 hours to obtain a dried material; [0056] Step 8: according to the solid-liquid ratio of Ig:3mL, the dried material was added to an ethanol solution of zirconium octoate (CAS: 18312-04-4) with a concentration of 0.15mol/L, then zirconium hydroxide with an amount of 3% of the weight of the dried material was added to the mixture. The obtained mixture was mixed uniformly, and heated (temperature was 70-80°C) under constant stirring to evaporate the organic solvent, and the organic solvent was recovered. When the organic solvent recovery rate reached more than 90%, the heating on the mixture was strengthened, and when the temperature reached 190°C, the temperature was maintained for 20min, [0057] Step 9: the product obtained in step 8 was calcined at 650°C in an oxygen atmosphere for 4 hours to obtain a tightly-coated cobalt oxide.
Example 3
100581 In th s example, a tightly-coated cobalt ox de was prepared. The specific process is: [0059] Step 1 a cobalt chloride solution with a concentration of 1.0moUL was prepared; [0060] Step 2: a sodium hydroxide solution with a concentration of 4.0mol/L was prepared as a precipitating agent; [0061] Step 3: an aqueous anunon a with a concentra on of 6.0mol/L was prepared as a complexing agent; [0062] Step 4: pure water was added to a reaction kettle to overflow the bottom stirring paddle, then a certain amount of sodium hydroxide solution prepared in step 2 and aqueous ammonia prepared in step 3 were added to the kettle to form a base solution for starting reaction, wherein the pH value of the base solution was 11, and the concentration of ammonia was 10.0g/L; [0063] Step 5: the cobalt salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, and the aqueous ammonia prepared in step 3 were added in parallel to the reaction kettle to react. In the reaction kettle, the stirring speed was controlled to be 200r/min, the pH was controlled to be 11, the temperature was controlled to be 65°C, and the concentration of -g -ammonia was controlled to be IOWL; 100641 Step 6: when the D50 of the material in the reaction kettle was detected to reach 5.0 the feeding was stopped, and the material was aged for lh, [0065] Step 7: the material in the kettle was subjected to solid-liquid separation, and then the obtained precipitate was washed with pure water, and dried at 100°C for 6 hours to obtain a dried material; [0066] Step 8: according to the solid-liquid ratio of I g:lmL, the dried material was added to an ethanol solution of zirconium 2-ethylhexanoate (CAS: 2233-42-3) with a concentration of 0.1mon, then zirconium hydroxide with an amount of 1% of the weight of the dried material was added to the mixture. The obtained mixture was mixed uniformly, and heated (temperature was 70-80°C) under constant stirring to evaporate the organic solvent, and the organic solvent was recovered. When the organic solvent recovery rate reached more than 90%, the heating on the mixture was strengthened, and when the temperature reached 180°C, the temperature was maintained for 30min; 100671 Step 9: the product obtained in step 8 was calcined at 750°C in an air atmosphere for 2 hours to obtain a tightly-coated cobalt oxide.
Comparative Example 1 [0068] In this example, a cobalt oxide was prepared, which differs from Example 1 in that aluminum octoate was not added The specific process is: [0069] Step 1. a cobalt sulfate solution with a concentration of 2.0mol/L was prepared; [0070] Step 2: a sodium hydroxide solution with a concentration of 10.0mol/L was prepared as a precipitating agent; [0071] Step 3: an aqueous ammonia with a concentration of 12.0mon was prepared as a complexing agent; [0072] Step 4: pure water was added to a reaction kettle to overflow the bottom stirring paddle, then a certain amount of sodium hydroxide solution prepared in step 2 and aqueous ammonia prepared in step 3 were added to the kettle to form a base solution for starting reaction, wherein the pH value of the base solution was 10.5, and the concentration of ammonia was 5.0g/L; [0073] Step 5: the cobalt salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, and the aqueous ammonia prepared in step 3 were added in parallel to the reaction kettle to react. In the reaction kettle, the stirring speed was controlled to be 500r/min, the pH was controlled to be 10.5, the temperature was controlled to be 55°C, and the concentration of ammonia was controlled to be 5g/L; [0074] Step 6: when the D50 of the material in the reaction kettle was detected to reach 15.0 Ism, the feeding was stopped, and the material was aged for 2h; [0075] Step 7: the material in the kettle was subjected to solid-liquid separation, and then the obtained precipitate was washed with pure water, and dried at 120°C for 4 hours to obtain a dried material; 100761 Step 8: according to the solid-liquid ratio of lg:5mL, the dried material was added to an ethanol solution, then aluminum hydroxide with an amount of 12.8% of the weight of the dried material was added to the mixture. The obtained mixture was mixed uniformly, and heated (temperature was 70-80°C) under constant stirring to evaporate the organic solvent, and the organic solvent was recovered. When the organic solvent recovery rate reached more than 90%, the heating on the mixture was strengthened, and when the temperature reached 200°C, the temperature was maintained for 15min; 100771 Step 9: the product obtained in step 8 was calcined at 500°C in an oxygen atmosphere for 6 hours to obtain a coated cobalt oxide.
Comparative Example 2 [0078] In this example, a cobalt oxide was prepared, which differs from Example 2 in that zirconium octoate was not added. The specific process is: [0079] Step I a cobalt nitrate solution with a concentration of 1 5mol/L was prepared; [0080] Step 2: a sodium hydroxide solution with a concentration of 7.0mol/L was prepared as a precipitating agent; 100811 Step 3: an aqueous ammonia with a concentration of 10.0mon was prepared as a complexing agent; [0082] Step 4: pure water was added to a reaction kettle to overflow the bottom stirring paddle, then a certain amount of sodium hydroxide solution prepared in step 2 and aqueous ammonia prepared in step 3 were added to the kettle to form a base solution for starting reaction, wherein the pH value of the base solution was 10.8, and the concentration of ammonia was 7g/L; [0083] Step 5: the cobalt salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, and the aqueous ammonia prepared in step 3 were added in parallel to the reaction kettle to react. In the reaction kettle, the stirring speed was controlled to be 350r/min, the pH was controlled to be 10.8, the temperature was controlled to be 60°C, and the concentration of ammonia was controlled to be 7g/L; [0084] Step 6: when the D50 of the material in the reaction kettle was detected to reach 10.0 gm, the feeding was stopped, and the material was aged for 1.5h; 100851 Step 7: the material in the kettle was subjected to solid-liquid separation, and then the obtained precipitate was washed with pure water, and dried at 110°C for 5 hours to obtain a dried material; [0086] Step 8: according to the solid-liquid ratio of lg:3mL, the dried material was added to an ethanol solution, then zirconium hydroxide with an amount of 14.5% of the weight of the dried material was added to the mixture. The obtained mixture was mixed uniformly, and heated (temperature was 70-80°C) under constant stirring to evaporate the organic solvent, and the organic solvent was recovered. When the organic solvent recovery rate reached more than 90%, the heating on the mixture was strengthened, and when the temperature reached 190°C, the temperature was maintained for 20min; [0087] Step 9: the product obtained in step 8 was calcined at 650°C in an oxygen atmosphere for 4 hours to obtain a coated cobalt oxide.
Comparative Example 3 [0088] In this example, a cobalt oxide was prepared, which differs from Example 3 in that zirconium 2-ethylhexanoate was not added. The specific process is: [0089] Step 1: a cobalt chloride solution with a concentration of 1.0mol/L was prepared; 100901 Step 2: a sodium hydroxide solution with a concentration of 4.0mol/L was prepared as a precipitating agent; [0091] Step 3: an aqueous ammonia with a concentration of 6.0mol/L was prepared as a complexing agent; 100921 Step 4: pure water was added to a reaction kettle to overflow the bottom stirring paddle, then a certain amount of sodium hydroxide solution prepared in step 2 and aqueous ammonia prepared in step 3 were added to the kettle to form a base solution for starting reaction, wherein the pH value of the base solution was 11, and the concentration of ammonia was 10.0g/L; [0093] Step 5: the cobalt salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, and the aqueous ammonia prepared in step 3 were added in parallel to the reaction kettle to react. In the reaction kettle, the stirring speed was controlled to be 200r/min, the pH was controlled to be 11, the temperature was controlled to be 65°C, and the concentration of ammonia was controlled to be IOWL; 100941 Step 6: when the D50 of the material in the reaction kettle was detected to reach 5.0 pm, the feeding was stopped, and the material was aged for lh; [0095] Step 7: the material in the kettle was subjected to solid-liquid separation, and then the obtained precipitate was washed with pure water, and dried at 100°C for 6 hours to obtain a dried material; [0096] Step 8: according to the solid-liquid ratio of I g:lmL, the dried material was added to an ethanol solution, then zirconium hydroxide with an amount of 3.5% of the weight of the dried material was added to the mixture. The obtained mixture was mixed uniformly, and heated (temperature was 70-80°C) under constant stirring to evaporate the organic solvent, and the organic solvent was recovered. When the organic solvent recovery rate reached more than 90%, the heating on the mixture was strengthened, and when the temperature reached 180°C, the temperature was maintained for 30min; [0097] Step 9: the product obtained in step 8 was calcined at 750°C in an air atmosphere for 2 hours to obtain a tightly-coated cobalt oxide.
Test example
[0098] The cobalt oxides obtained in Examples 1-3 and Comparative Examples 1-3 were respectively mixed with lithium carbonate, wherein the molar ratio of Li:Co was controlled to be 1.06, and the mixture was subjected to high-temperature solid-phase sintering in a push-plate kiln at a sintering temperature of 1000°C for 12h to obtain a lithium cobalt oxide positive electrode material respectively: [0099] The lithium cobalt oxide materials obtained by the examples and the comparative examples served as active material, acetylene black served as a conductive agent, and PVDF served as a binding agent. The active material, the conductive agent and the binding agent were weighed in the ratio of 92:4:4 and mixed, a certain amount of the organic solvent NMP was added to the mixture, then the obtained mixture was stirred and coated on an aluminum foil to form a positive electrode sheet, the negative electrode was made of a metal lithium sheet, and a CR2430 button battery was made in an argon-filled glove box. The battery was subjected to the electrical performance test in a CT2001A blue battery test system. Test conditions: 3.0-4.48V test temperature 25±1°C. The test results are shown in Table 1.
[00100] Table 1
Discharge capacity at 0.1C/4.48V Capacity retention rate for 600 cycles at 0.1C/4.48V mAh/g Example 1 211.2 84.1% Example 2 213.7 83.7% Example 3 210.6 84.2% Comparative Example 1 206.8 75.9% Comparative Example 2 203.9 75.6% Comparative Example 3 205.1 76.7% [00101] It can be seen from Table 1 that the cycle retention rate of the comparative examples was significantly lower than that of the examples, this is because the cobalt oxides obtained in the comparative examples only had a common coating, and their coating layer (zirconia/alumina) -13 -cannot form a tight connection with the cobalt hydroxide base material, so that in the process of long-term cycling, the phenomenon of pulverization and shedding occurs, for which the lithium cobalt oxide is re-exposed to the electrolyte to be corroded, thereby affecting the cycle performance of the material.
[00102] The examples of the present invention have been described in detail above in conjunction with the drawings, but the present invention is not limited to the above-mentioned examples, and various changes can also be made within the scope of knowledge possessed by those of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, the examples of the present invention and features in the examples may be combined with each other without conflict.
Claims (10)
- CLAIMSI. A method for preparing a tightly-coated cobalt oxide, comprising the following steps: Si: adding a cobalt salt solution, a sodium hydroxide solution and aqueous ammonia in parallel to a base solution to react, until the reaction material reaches the target particle size, performing ageing on the mixture, then subjecting the resulting mixture to solid-liquid separation to obtain a precipitate, and washing and drying the precipitate to obtain a dry material; S2: adding the dry material and hydroxide to an organic solution of metal carboxylate, heating the mixture to evaporate the solvent, and when the evaporation rate of the solvent reaches more than 90%, heating the mixture to 180-200°C to react; wherein the hydroxide is zirconium hydroxide or aluminum hydroxide, and the organic solution of metal carboxylate is an alcohol solution of zirconium alkyl carboxylate or aluminum alkyl carboxylate; 53: calcining the product after reaction in step S2 in an oxygen atmosphere to obtain the cobalt oxide.
- 2. The method according to claim 1, wherein in step Si, the concentration of the cobalt salt solution is 1.0-2.0 mol/L, and the concentration of the sodium hydroxide solution is 4.0-10.0 mol/L.
- 3. The method according to claim 1, wherein in step S 1, the base solution is a mixed solution of sodium hydroxide and aqueous ammonia, the pH of the base solution is 10-11, and the concentration of ammonia is 5.0-10.0 g/L.
- 4. The method according to claim 1, wherein in step Si, the temperature of the reaction is controlled to be 55-65°C, the pH of the reaction material is controlled to be 10-11, and the concentration of the ammonia is controlled to be 5-10 g/L.
- 5. The method according to claim 1, wherein in step S2, the ratio of the weight of the dry material to the volume of the organic solution of the metal carboxylate is 1 g: (1-5) mL, and the concentration of the metal carboxylate in the organic solution of the metal carboxylate is 0.1-0.2mol/L.
- 6. The method according to claim 1, wherein in step S2, the addition amount of the hydroxide is 1-5% of the weight of the dry material.
- 7. The method according to claim 1, wherein in step S2, the number of carbon atoms in the alkyl segment in the zirconium alkyl carboxylate or the aluminum alkyl carboxylate is 6-10.
- 8. The method according to claim 1, wherein in step S2, the duration of the reaction is 15-30 min.
- 9. The method according to claim I, wherein in step 53, the temperature of the calcining is 500-750°C.
- 10. Use of the method according to any one of claims 1-9 in the preparation of lithium cobalt oxide or lithium ion batteries. -6-
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| CN111115705A (en) * | 2018-10-31 | 2020-05-08 | 格林美（江苏）钴业股份有限公司 | Preparation method of cobalt oxide coated with zirconium |
| CN112366302A (en) * | 2020-11-13 | 2021-02-12 | 格林美（江苏）钴业股份有限公司 | Preparation method of coated cobaltosic oxide precursor |
| CN112687857A (en) * | 2020-12-24 | 2021-04-20 | 广州明美新能源股份有限公司 | Lithium cobaltate positive electrode material and preparation method thereof |
| CN114188525A (en) * | 2020-09-14 | 2022-03-15 | 株式会社东芝 | Electrode, secondary battery, battery pack, and vehicle |
| CN115064673A (en) * | 2022-06-28 | 2022-09-16 | 广东邦普循环科技有限公司 | Preparation method and application of tightly-coated cobalt oxide |
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| JP2019192513A (en) * | 2018-04-26 | 2019-10-31 | 住友金属鉱山株式会社 | Positive electrode active material for non-aqueous electrolyte secondary battery and method of manufacturing the same |
| CN111115705A (en) * | 2018-10-31 | 2020-05-08 | 格林美（江苏）钴业股份有限公司 | Preparation method of cobalt oxide coated with zirconium |
| CN114188525A (en) * | 2020-09-14 | 2022-03-15 | 株式会社东芝 | Electrode, secondary battery, battery pack, and vehicle |
| CN112366302A (en) * | 2020-11-13 | 2021-02-12 | 格林美（江苏）钴业股份有限公司 | Preparation method of coated cobaltosic oxide precursor |
| CN112687857A (en) * | 2020-12-24 | 2021-04-20 | 广州明美新能源股份有限公司 | Lithium cobaltate positive electrode material and preparation method thereof |
| CN115064673A (en) * | 2022-06-28 | 2022-09-16 | 广东邦普循环科技有限公司 | Preparation method and application of tightly-coated cobalt oxide |
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