CN114105216B - Cobalt hydroxide with micro-crack structure, and preparation method and application thereof - Google Patents
Cobalt hydroxide with micro-crack structure, and preparation method and application thereof Download PDFInfo
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- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title claims abstract description 107
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 125000000129 anionic group Chemical group 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 238000010668 complexation reaction Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 97
- 238000006243 chemical reaction Methods 0.000 claims description 72
- 238000003756 stirring Methods 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 13
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 12
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 12
- 239000011164 primary particle Substances 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- 229910052744 lithium Inorganic materials 0.000 abstract description 17
- 238000001556 precipitation Methods 0.000 abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 239000007788 liquid Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 239000011149 active material Substances 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 238000005245 sintering Methods 0.000 description 17
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- 150000001868 cobalt Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 5
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- -1 electronic industry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Microelectronics & Electronic Packaging (AREA)
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides cobalt hydroxide with a microcrack structure, a preparation method and application thereof, and relates to the technical field of lithium batteries. Cobalt hydroxide slurry is obtained by a complexation control crystallization method, and then cobalt hydroxide is prepared by an electrochemical corrosion principle. The cobalt hydroxide has a grain size of 6-20 mu m and a micro-crack structure. The micro-crack structure is beneficial to release of the anionic impurities contained in the precipitate in the precipitation process, so that the content of the anionic impurities is below 100ppm. The lithium cobaltate anode material obtained by taking the cobalt hydroxide as the raw material has effectively improved impedance performance and multiplying power performance.
Description
Technical Field
The invention relates to the technical field of lithium ion materials, in particular to cobalt hydroxide with a micro-crack structure, a preparation method and application thereof.
Background
Cobalt hydroxide has wide application in industry, is one of important raw materials for preparing lithium ion anode material-lithium cobaltate, and can also be used for preparing electrode materials of super capacitors. Meanwhile, the cobalt hydroxide can be also applied to products such as cobalt acetate and cobalt naphthenate, or applied to the fields of magnetic materials, electronic industry, ceramic technology and the like, and is one of new cobalt materials.
In order to realize large-scale production and reduce material cost, industrial cobalt hydroxide synthesis generally synthesizes cobalt hydroxide in a reaction vessel by taking cobalt sulfate or chloride as a cobalt source. The cobalt hydroxide synthesized by the conventional process is easy to form flocculent precipitate in the synthesis process, so that flocculent, flaky or loose cauliflower-shaped structures are formed, and the cobalt hydroxide has poor fluidity and poor processability. Some researches can obtain cobalt hydroxide with high sphericity, good compactness and fluidity by controlling the crystallization process of cobalt hydroxide synthesis, and the cobalt hydroxide is convenient to process, but the improvement of the internal compactness of the cobalt hydroxide can lead to difficult removal of the anion impurities of the mother solution included in the synthesis process, so that equipment is easily corroded in the subsequent calcination and sintering processes, and the performance of the final lithium ion battery is influenced by the residual lithium cobaltate anode material.
Disclosure of Invention
In order to overcome the defects, the invention provides cobalt hydroxide with a microcrack structure, and a preparation method and application thereof.
A first aspect of the present invention provides a cobalt hydroxide having a microcrack structure, the primary particles of which have a microcrack structure, and the anionic impurity content of which is less than 100ppm.
Further, in one disclosed embodiment, the cobalt hydroxide has a particle size D50 of 6 to 20 μm.
In a second aspect, the present invention provides a method for preparing cobalt hydroxide having a microcrack structure, comprising the steps of:
the synthesis steps are as follows: cobalt solution, precipitator and complexing agent are used as raw materials, and cobalt hydroxide slurry is obtained through a complexation control crystallization method;
and (3) etching: introducing an oxidant into the cobalt hydroxide slurry, regulating the pH value and the reaction temperature, performing electrochemical oxygen absorption reaction, and stopping introducing the oxidant and blocking the electrochemical oxygen absorption reaction after cobalt ions in the cobalt hydroxide slurry are controlled to reach a preset oxidation rate to obtain corrosion slurry;
and (3) forming: and washing, separating and drying the corrosion slurry to obtain the cobalt hydroxide, wherein primary particles of the cobalt hydroxide have a micro-crack structure.
Further, in one disclosed embodiment, in the etching step, the pre-set oxidation rate of the cobalt ions is 25% to 88%, the oxidation rate being the ratio of the content of trivalent cobalt ions to the content of all cobalt ions in the etching slurry.
Further, in one embodiment of the disclosure, in the etching step, the oxidizing agent is selected from one or more of air, pure oxygen, and hydrogen peroxide.
Further, in one disclosed embodiment, in the etching step, the alkalinity of the cobalt hydroxide slurry is adjusted to 0.1 to 5mol/L by adding an alkali solution.
Further, in one embodiment disclosed, in the etching step, continuous stirring is performed during the reaction, and the stirring speed is 100 to 600rpm.
Further, in one disclosed embodiment, the synthesizing step comprises: adding the precipitant solution and the complexing agent solution under stirring until the pH of the mixed solution reaches 10-12, adding the cobalt solution, and continuously adding the precipitant solution to maintain the pH of the reaction process at 10-12.
Further, in one disclosed embodiment, the reaction time of the synthesis step is 60 to 300 hours, the reaction temperature is 35 to 70 ℃, and the stirring speed is 100 to 600rpm.
According to a third aspect of the invention, there is provided a lithium cobalt oxide active material, obtained according to the preparation method described above, wherein the lithium cobalt oxide active material is obtained by mixing the cobalt hydroxide with a lithium source and sintering the mixture.
Further, in one disclosed embodiment, the lithium ion battery made of the lithium cobaltate active material has a direct current internal resistance of less than 10Ω under 5V and 10% soc conditions.
Further, in one disclosed embodiment, the lithium ion battery made of the lithium cobaltate active material has a floating charge flow breakthrough time of more than 230h at 4.5V and 60 ℃ of 0.1A.
A third aspect of the invention provides a lithium ion battery or capacitor comprising a lithium cobaltate active material as described above.
The cobalt hydroxide with the micro-crack structure, the preparation method and the application thereof have the beneficial effects that:
the cobalt hydroxide slurry is obtained by a complexation control crystallization method, so that the sphericity, compactness and fluidity of cobalt hydroxide can be effectively improved, and the processing performance of cobalt hydroxide is greatly improved. And then, the cobalt hydroxide slurry is corroded in an electrochemical corrosion mode, a micro-crack structure can be formed on the cobalt hydroxide primary particles, so that the release of anionic impurities contained in the cobalt hydroxide primary particles in the precipitation process is facilitated, and the content of the anionic impurities is effectively reduced. The content of the anion impurity of the cobalt hydroxide obtained by the embodiment of the invention is lower than 100ppm, and the lithium cobaltate obtained by taking the cobalt hydroxide as a precursor has lower impedance value and stronger multiplying power discharge capacity. And the preparation process of the cobalt hydroxide is simple, various parameters are easy to control, and the cobalt hydroxide is suitable for industrial mass production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the internal characteristics of a cross-section of cobalt hydroxide particles of example 1;
FIG. 2 is an enlarged view of a portion of FIG. 1;
FIG. 3 is an SEM image of the internal characteristics of a cross-section of cobalt hydroxide particles of example 2;
FIG. 4 is an SEM image of the internal characteristics of a cross-section of cobalt hydroxide particles of example 3;
FIG. 5 is an SEM image of the cross-section of the cobalt hydroxide particles of example 4;
FIG. 6 is an SEM image of the cross-section of the cobalt hydroxide particles of comparative example 1;
FIG. 7 is an enlarged view of a portion of FIG. 5;
FIG. 8 is an SEM image of the cross-section of the cobalt hydroxide particles of comparative example 2;
fig. 9 is a high temperature float comparative plot of the LCO products obtained in example 1 and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The cobalt hydroxide with the micro-crack structure, the preparation method and the application thereof in the embodiment of the invention are specifically described below.
The embodiment of the invention provides cobalt hydroxide with a micro-crack structure, wherein primary particles of the cobalt hydroxide have the micro-crack structure, and the content of anionic impurities of the cobalt hydroxide is less than 100ppm. The cobalt hydroxide has a particle diameter D50 of 6 to 20 mu m.
The embodiment of the invention also provides a preparation method of the cobalt hydroxide with the micro-crack structure, which comprises the following steps:
s1, synthesizing: cobalt solution, precipitator and complexing agent are used as raw materials, and cobalt hydroxide slurry is obtained through a complexation control crystallization method;
s2, etching: introducing an oxidant into the cobalt hydroxide slurry, regulating the pH value and the reaction temperature, performing electrochemical oxygen absorption reaction, and stopping introducing the oxidant and blocking the electrochemical oxygen absorption reaction after cobalt ions in the cobalt hydroxide slurry are controlled to reach a preset oxidation rate to obtain corrosion slurry;
s3, forming: and washing, separating and drying the corrosion slurry to obtain the cobalt hydroxide, wherein primary particles of the cobalt hydroxide have a micro-crack structure.
Specifically, step S1 includes:
adding the precipitant solution and the complexing agent solution under stirring until the pH of the mixed solution reaches 10-12, adding the cobalt solution, and continuously adding the precipitant solution to maintain the pH of the reaction process at 10-12.
In one embodiment disclosed, the cobalt solution is a cobalt salt and no brine configuration, preferably with a concentration of cobalt salt of 10 to 150g/L. Further, the cobalt salt is selected from one or two of cobalt chloride and cobalt sulfate. It will be appreciated that the anionic impurities of cobalt hydroxide are mainly introduced by the anions of cobalt salts, when cobalt chloride is selected as the cobalt salt, chloride impurities are introduced, and when cobalt sulphate is selected as the cobalt salt, sulphate impurities are introduced.
In one embodiment of the disclosure, the precipitant is a soluble alkali metal hydroxide, such as one or more of sodium hydroxide, lithium hydroxide, potassium hydroxide, and the like. Preferably, the molar concentration of the precipitant solution is 0.1 to 11mol/L.
In one embodiment of the disclosure, the complexing agent is selected from one or more of liquid ammonia, concentrated aqueous ammonia, and hydrazine. Preferably, the complexing agent solution has a molar solubility of 5 to 8mol/L.
Further, in one disclosed embodiment, the reaction time for the synthesis step is 60 to 300 hours, the reaction temperature is 35 to 70 ℃, and the stirring speed is 100 to 600rpm.
Specifically, the synthesis reaction is carried out in a reaction kettle, a stirring device of the reaction kettle is started, a certain amount of non-salt water is added into the reaction kettle, then a precipitant solution and a complexing agent solution are pumped in through a peristaltic pump and other devices, after the pH value reaches 10-12, a cobalt solution is pumped in, then the precipitant solution is continuously added, and the pH value of the solution in the reaction kettle is regulated to be maintained within a range of 10-12 by regulating the adding speed of the precipitant solution. In the precipitation process, a precise filter is continuously used for extracting mother liquor generated by the reaction so as to ensure the progress of the precipitation reaction. It is further preferred that the precipitant solution is added at a rate of 0.4 to 0.6L/h and the cobalt solution is added at a feed rate of 0.8 to 1.2L/h. After adding the cobalt solution, continuously adding the precipitant solution at a feeding speed of 0.1-0.5L/h for pH value adjustment.
Specifically, the step S2 includes: adding an oxidant into a reaction container, regulating the alkalinity of the slurry by adding liquid alkali, maintaining a certain stirring speed in the reaction container, stopping introducing the oxidant and blocking the electrochemical oxygen absorption reaction after the oxidation degree of the slurry reaches, and obtaining the corrosion slurry.
In this step, the main equation of the electrochemical oxygen uptake reaction is as follows:
anode: co (Co) 2+ –e→Co 3+ ;
And (3) cathode: o (O) 2 +2H 2 O→4OH - ;
General reaction formula: 4Co (OH) 2 +O 2 +2H 2 O→4Co(OH) 3
In one embodiment disclosed, in this step, the pre-set oxidation rate of the cobalt ions is 25% to 88% and the oxidation rate is the ratio of the trivalent cobalt ion content to all cobalt ion content in the corrosion slurry. It is understood that the oxidation rate may be determined by redox titration. More preferably, the reaction time is controlled to be about 200 to 400 minutes, and the oxidation rate is 25 to 88%.
In one embodiment disclosed, in this step, the oxidizing agent is selected from one or more of air, pure oxygen, and hydrogen peroxide. Further preferably, when the oxidant is air or pure oxygen, the addition rate is 150-250L/h; when the oxidant is hydrogen peroxide, the adding speed is 0.3-0.8L/h.
In one embodiment disclosed, the electrochemical oxygen uptake reaction is blocked by the introduction of an inert gas after the reaction has reached the end of the reaction. The inert gas is, for example, nitrogen, helium or the like.
In one embodiment disclosed, in this step, the alkalinity of the cobalt hydroxide slurry is adjusted to between 0.1 and 5mol/L by adding an alkaline solution. The alkali solution is, for example, sodium hydroxide solution or the like.
In one embodiment disclosed, in this step, stirring is continued during the reaction at a rate of 100 to 600ppm.
The invention further provides a lithium cobalt oxide active material, cobalt hydroxide is obtained according to the preparation method, and the lithium cobalt oxide active material is obtained by mixing cobalt hydroxide with a lithium source and sintering.
In one embodiment of the disclosure, the lithium source may be LiOH H 2 O、Li 2 CO 3 、LiNO 3 、 CH 3 COOLi·2H 2 One or more of O. The molar ratio of cobalt hydroxide to lithium source is 1:1.01-1.1, more preferably 1:1.01-1.07. Further preferably, the sintering temperature is 860 to 1070 ℃ and the sintering time is 8 to 12 hours.
In one disclosed embodiment, the lithium ion battery made of the lithium cobaltate active material has a DC internal resistance of less than 10Ω under 5V and 10% SOC conditions.
Further, in one disclosed embodiment, the lithium ion battery prepared from the lithium cobaltate active material has a time of 0.1A breakthrough of a floating charge-discharge current of more than 230h under the conditions of 4.5V and 60 ℃.
The embodiment of the invention also provides a lithium ion battery or a capacitor, which comprises the lithium cobaltate active material. The lithium ion battery or capacitor obtained by the lithium cobalt oxide active material has excellent impedance performance and rate performance.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The lithium ion active material provided in this embodiment is obtained according to the following steps:
(1) Preparing liquid: coSO with concentration of 120g/L 4 The solution is solution a; preparing 10mol/L sodium hydroxide solution, namely solution b; preparing an ammonia water solution with the concentration of 6.7mol/L, namely a solution c;
(2) And (3) synthesis reaction: the reaction vessel was started to stir at 600rpm. 10L of brine-free solution was added, 500mL of solution c was added, and then solution b was added at a rate of 0.5L/h until the pH of the liquid in the reaction vessel reached 12.00. After heating in a water bath to a temperature of 65℃solution a was added at a feed rate of 1L/h and solution c was added at a feed rate of 0.1L/h, and the pH of the liquid in the vessel was maintained at 12.00.+ -. 0.05 by adjusting the pH of the liquid in the vessel with solution b. The precipitation process is continuously carried out by using a precision filter to extract the reaction to generate mother liquor, and the precipitation is carried out for 200 hours.
(3) Corrosion reaction: clean air was introduced into the reaction vessel at a rate of 200L/h, and the alkalinity of the slurry was adjusted to 2.3mol/L by adding sodium hydroxide, and the reaction vessel was maintained at a stirring rate of 450rpm. After 300min of reaction, the oxidation degree of the slurry is 54%. Nitrogen is introduced to block the oxidation reaction. And then washing, dehydrating and drying the materials in the reaction container to obtain the cobalt hydroxide. The D50 of the cobalt hydroxide is 5-7 mu m. And the primary particles of cobalt hydroxide have a microcrack structure.
(4) And (3) sintering reaction: and (3) uniformly mixing cobalt hydroxide and lithium carbonate obtained in the step (3) according to a molar ratio of 1:1.02, and sintering at 1000 ℃ for 8 hours to obtain an LCO finished product.
Example 2
The lithium ion active material provided in this embodiment is obtained according to the following steps:
(1) Preparing liquid: coSO with concentration of 110g/L 4 The solution is solution a; preparing 10mol/L sodium hydroxide solution, namely solution b; preparing an ammonia water solution with the concentration of 6.7mol/L, namely a solution c;
(2) And (3) synthesis reaction: the reaction vessel was started to stir at 450rpm. 20L of saline-free water was added, 1000mL of solution c was added, and then solution b was added at a rate of 0.5L/h until the pH of the liquid in the reaction vessel reached 12.00. After heating in a water bath to a temperature of 50℃solution a was added at a feed rate of 1L/h. Solution c was added at a feed rate of 0.2L/h and the pH of the liquid in the vessel was maintained at 12.00.+ -. 0.05 by solution b adjustment. The precipitation process is continuously carried out by using a precision filter to extract the reaction to generate mother liquor, and the precipitation is carried out for 150 hours.
(3) Corrosion reaction: pure oxygen was introduced into the reaction vessel at a rate of 200L/h, and the alkalinity of the slurry was adjusted to 0.8mol/L by adding sodium hydroxide, and the reaction vessel was maintained at a stirring rate of 450rpm. After 300min of reaction, the oxidation degree of the slurry is 65%. Nitrogen is introduced to block the oxidation reaction. And then washing, dehydrating and drying the materials in the reaction container to obtain the cobalt hydroxide. The D50 of the cobalt hydroxide is 6-14 mu m. And the primary particles of cobalt hydroxide have a microcrack structure.
(4) And (3) sintering reaction: and (3) uniformly mixing cobalt hydroxide and lithium carbonate obtained in the step (3) according to a molar ratio of 1:1.05, and sintering at 1030 ℃ for 10 hours to obtain an LCO finished product.
Example 3
The lithium ion active material provided in this embodiment is obtained according to the following steps:
(1) Preparing liquid: coSO with concentration of 110g/L 4 The solution is solution a; preparing 10mol/L sodium hydroxide solution, namely solution b; preparing an ammonia water solution with the concentration of 6.7mol/L, namely a solution c;
(2) And (3) synthesis reaction: the reaction vessel was started to stir at 400rpm. 20L of saline-free water was added, and 1500mL of solution c was added, followed by 0.5L/h of solution b to reach a pH of 11.00 in the reaction vessel. After heating in a water bath to a temperature of 50℃solution a was added at a feed rate of 1L/h. Solution c was added at a feed rate of 0.2L/h and the pH of the liquid in the vessel was maintained at 12.00.+ -. 0.05 by solution b adjustment. The precipitation process is continuously carried out by using a precision filter to extract the reaction to generate mother liquor, and the precipitation is carried out for 150 hours.
(3) Corrosion reaction: hydrogen peroxide was introduced into the reaction vessel at a rate of 0.6L/h, and the alkalinity of the slurry was adjusted to 1.0mol/L by adding sodium hydroxide, and the reaction vessel was maintained at a stirring rate of 450rpm. After 300min of reaction, the oxidation degree of the slurry is 35%. Nitrogen is introduced to block the oxidation reaction. And then washing, dehydrating and drying the materials in the reaction container to obtain the cobalt hydroxide. The D50 of the cobalt hydroxide is 17-22 mu m. And the primary particles of cobalt hydroxide have a microcrack structure.
(4) And (3) sintering reaction: and (3) uniformly mixing cobalt hydroxide and lithium carbonate obtained in the step (3) according to a molar ratio of 1:1.07, and sintering at 1060 ℃ for 12 hours to obtain an LCO finished product.
Example 4
The lithium ion active material provided in this embodiment is obtained according to the following steps:
(1) Preparing liquid: coCl with concentration of 120g/L 2 The solution is solution a; preparing 10mol/L sodium hydroxide solution, namely solution b; configured to be 6.7mol/LAn ammonia water solution, namely a solution c;
(2) And (3) synthesis reaction: the reaction vessel was started to stir at 600rpm. 10L of brine-free solution was added, 500mL of solution c was added, and then solution b was added at a rate of 0.5L/h until the pH of the liquid in the reaction vessel reached 12.00. After heating in a water bath to a temperature of 65℃solution a was added at a feed rate of 1L/h and solution c was added at a feed rate of 0.1L/h, and the pH of the liquid in the vessel was maintained at 12.00.+ -. 0.05 by adjusting the pH of the liquid in the vessel with solution b. The precipitation process is continuously carried out by using a precision filter to extract the reaction to generate mother liquor, and the precipitation is carried out for 200 hours.
(3) Corrosion reaction: clean air was introduced into the reaction vessel at a rate of 200L/h, and the alkalinity of the slurry was adjusted to 2.3mol/L by adding sodium hydroxide, and the reaction vessel was maintained at a stirring rate of 450rpm. After 300min of reaction, the oxidation degree of the slurry is 54%. Nitrogen is introduced to block the oxidation reaction. And then washing, dehydrating and drying the materials in the reaction container to obtain the cobalt hydroxide. The D50 of the cobalt hydroxide is 5-7 mu m. And the primary particles of cobalt hydroxide have a microcrack structure.
(4) And (3) sintering reaction: and (3) uniformly mixing cobalt hydroxide and lithium carbonate obtained in the step (3) according to a molar ratio of 1:1.02, and sintering at 1000 ℃ for 8 hours to obtain an LCO finished product.
Comparative example 1
The lithium ion active material provided in this comparative example was obtained according to the following steps:
(1) Preparing liquid: coSO with concentration of 120g/L 4 The solution is solution a; preparing 10mol/L sodium hydroxide solution, namely solution b; preparing an ammonia water solution with the concentration of 6.7mol/L, namely a solution c;
(2) And (3) synthesis reaction: the reaction vessel was started to stir at 600rpm. 10L of brine-free solution was added, 500mL of solution c was added, and then solution b was added at a rate of 0.5L/h until the pH of the liquid in the reaction vessel reached 12.00. After heating in a water bath to a temperature of 65℃solution a was added at a feed rate of 1L/h. Solution c was added at a feed rate of 0.1L/h and the pH of the liquid in the vessel was maintained at 12.00.+ -. 0.05 by solution b adjustment. The precipitation process is continuously carried out by using a precision filter to extract the reaction to generate mother liquor, and the precipitation is carried out for 200 hours.
(3) Cleaning and drying: and (3) washing, dehydrating and drying the materials in the reaction container to obtain the cobalt hydroxide. The D50 of the cobalt hydroxide is 6-10 mu m.
(4) And (3) sintering reaction: and (3) uniformly mixing cobalt hydroxide and lithium carbonate obtained in the step (3) according to a molar ratio of 1:1.02, and sintering at 1000 ℃ for 8 hours to obtain an LCO finished product.
Comparative example 2
The lithium ion active material provided in this comparative example was obtained according to the following steps:
(1) Preparing liquid: preparing a CoCl2 solution with the concentration of 120g/L, namely a solution a; preparing 10mol/L sodium hydroxide solution, namely solution b; preparing an ammonia water solution with the concentration of 6.7mol/L, namely a solution c;
(2) And (3) synthesis reaction: the reaction vessel was started to stir at 600rpm. 10L of brine-free solution was added, 500mL of solution c was added, and then solution b was added at a rate of 0.5L/h until the pH of the liquid in the reaction vessel reached 12.00. After heating in a water bath to a temperature of 65℃solution a was added at a feed rate of 1L/h. Solution c was added at a feed rate of 0.1L/h and the pH of the liquid in the vessel was maintained at 12.00.+ -. 0.05 by solution b adjustment. The precipitation process is continuously carried out by using a precision filter to extract the reaction to generate mother liquor, and the precipitation is carried out for 200 hours.
(3) Cleaning and drying: and (3) washing, dehydrating and drying the materials in the reaction container to obtain the cobalt hydroxide. The D50 of the cobalt hydroxide is 6-10 mu m.
(4) And (3) sintering reaction: and (3) uniformly mixing cobalt hydroxide and lithium carbonate obtained in the step (3) according to a molar ratio of 1:1.02, and sintering at 1000 ℃ for 8 hours to obtain an LCO finished product.
Test example 1 physical Property test
The particle sizes of the obtained cobalt hydroxide particles of examples 1 to 3 and comparative example 1 were measured according to a malvern 2000 test apparatus, and the contents of sulfur and chlorine impurities of the cobalt hydroxide particles were measured using an ICP plasma atomic emission spectrometer, and the results are shown in table 1.
TABLE 1
Project | D10(μm) | D50(μm) | D90(μm) | SO4 2- (ppm) | Cl - (ppm) |
Example 1 | 4.76 | 6.7 | 12.65 | 54 | - |
Example 2 | 6.62 | 9.35 | 13.22 | 68 | - |
Example 3 | 13.09 | 18.01 | 23.5 | 82 | - |
Example 4 | 4.97 | 6.84 | 9.27 | - | 56 |
Comparative example 1 | 4.54 | 6.73 | 13.01 | 3375 | - |
Comparative example 2 | 4.32 | 6.67 | 12.77 | - | 752 |
As can be seen from Table 1, the content of anionic impurities obtained from the cobalt hydroxide of examples 1 to 4, which had D50 values of 6.7 to 18.01 μm, was far lower than that obtained from the comparative example, and it was found that the cobalt hydroxide obtained by this embodiment was effective in reducing the content of anionic impurities.
FIG. 1 is an SEM image of the internal characteristics of a cross-section of cobalt hydroxide particles of example 1; FIG. 2 is an enlarged view of a portion of FIG. 1; FIG. 3 is an SEM image of the internal characteristics of a cross-section of cobalt hydroxide particles of example 2; FIG. 4 is an SEM image of the internal characteristics of a cross-section of cobalt hydroxide particles of example 3; FIG. 5 is an SEM image of the cross-section of the cobalt hydroxide particles of example 4; FIG. 6 is an SEM image of the cross-section of the cobalt hydroxide particles of comparative example 1; fig. 7 is a partial enlarged view of fig. 6. Fig. 8 is an SEM image of internal features of a cross section of cobalt hydroxide particles of comparative example 2.
As shown in fig. 1 to 5, the primary crystal grains of all examples had developed remarkable cracks, and as shown in fig. 6 to 8, the primary crystal grains of the cobalt hydroxide obtained in the comparative examples were in good condition, and the preserved primary crystal grains were unfavorable for the release of the primary particles entrapped therein during the precipitation process, resulting in higher content of anionic impurities in the products obtained in comparative examples 1, 2.
Test example 2 electrochemical Performance test
LCO obtained in example 1 and comparative example 1 was used as a positive electrode material to prepare an electrode sheet and assembled into a button cell. The specific process is as follows: firstly, fully grinding and mixing LCO, acetylene black and PVDF according to the mass ratio of 8:1:1, then adding NMP to dissolve the mixture, and continuously stirring for 6 hours; and then coated on a clean aluminum foil using a doctor blade. Vacuum drying at 120deg.C for 12 hr, and punching to obtain electrode plate with diameter of 14 mm. This was assembled in a Braun glove box into button half-cells model CR 2032. The CR2032 button half cell was subjected to 1 second 1C discharge at 70%, 40%, 20% and 10% SOC under 0.1C discharge conditions, and the corresponding DCR was calculated from the test results. The results are shown in Table 2:
TABLE 2
And (3) keeping the lithium ion battery at a constant voltage of 4.4V at 60 ℃, and monitoring the current of the complementary power supply to obtain a high-temperature floating charge comparison chart shown in figure 9.
As can be seen from fig. 9, the lithium cobaltate prepared in the example showed the current supply mutation and broken through 0.1A 25h later than the comparative example in the float test process, because the higher anionic impurities contained in the cobalt hydroxide synthesized in the conventional process of the comparative example accelerated the deterioration of the material under the high temperature condition, resulting in early deterioration of the performance; the cobalt hydroxide obtained by the method has low content of anions, so that the material keeps better high-temperature stability.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (2)
1. The preparation method of the cobalt hydroxide with the micro-crack structure is characterized by comprising the following steps:
the synthesis steps are as follows: adding a precipitant solution and a complexing agent solution under stirring until the pH value of the mixed solution reaches 10-12, adding a cobalt solution, and continuously adding the precipitant solution to maintain the pH value of the reaction process at 10-12; obtaining cobalt hydroxide slurry by a complexation control crystallization method; wherein the reaction time is 60-300 h, the reaction temperature is 35-70 ℃, and the stirring speed is 100-600 rpm;
and (3) etching: introducing an oxidant into the cobalt hydroxide slurry, regulating the pH value and the reaction temperature, performing electrochemical oxygen absorption reaction, and stopping introducing the oxidant and blocking the electrochemical oxygen absorption reaction after cobalt ions in the cobalt hydroxide slurry are controlled to reach a preset oxidation rate to obtain corrosion slurry; wherein the oxidant is selected from one or more of air, pure oxygen and hydrogen peroxide; the preset oxidation rate of the cobalt ions is 25% -88%, and the oxidation rate is the ratio of the content of the trivalent cobalt ions to the content of all cobalt ions in the corrosion slurry; regulating the alkalinity of the cobalt hydroxide slurry to be 0.1-5 mol/L by adding alkali liquor;
and (3) forming: washing, separating and drying the corrosion slurry to obtain the cobalt hydroxide, wherein primary particles of the cobalt hydroxide have a micro-crack structure, the content of anionic impurities of the cobalt hydroxide is less than 100ppm, and the particle size D50 of the cobalt hydroxide is 6-20 mu m.
2. The method for producing a microcrack structured cobalt hydroxide according to claim 1 wherein in the etching step, continuous stirring is performed during the reaction at a stirring speed of 100 to 600rpm.
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