CN117550652B - Aluminum-doped cobaltosic oxide and preparation method and application thereof - Google Patents
Aluminum-doped cobaltosic oxide and preparation method and application thereof Download PDFInfo
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- CN117550652B CN117550652B CN202311598109.5A CN202311598109A CN117550652B CN 117550652 B CN117550652 B CN 117550652B CN 202311598109 A CN202311598109 A CN 202311598109A CN 117550652 B CN117550652 B CN 117550652B
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- 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 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 40
- 239000008139 complexing agent Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 cobalt oxyhydroxide Chemical compound 0.000 claims abstract description 17
- 239000000919 ceramic Substances 0.000 claims abstract description 11
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 13
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000012544 monitoring process Methods 0.000 claims description 9
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 abstract description 18
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- 239000011164 primary particle Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 241000276425 Xiphophorus maculatus Species 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005056 compaction Methods 0.000 description 3
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
- C01P2006/11—Powder tap density
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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
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Abstract
The invention relates to aluminum-doped cobaltosic oxide, a preparation method and application thereof, and belongs to the technical field of lithium ion batteries. The invention discloses a preparation method of aluminum-doped cobaltosic oxide, which comprises the following steps: preparing industrial cobalt chloride and aluminum chloride into a mixed solution according to a certain proportion. Heating distilled water, adding a mixed solution, a complexing agent, a sodium hydroxide solution and hydrogen peroxide, stirring and mixing, introducing air into the mixture for synthesis reaction, adjusting the pH value, and then placing the mixture into a ceramic sagger for thermal decomposition to obtain the aluminum-doped cobaltosic oxide. The complexing agent provides the function of an oxidant in the reaction, promotes the formation of aluminum-doped cobaltosic oxide, and can effectively control the reduction and oxidation states of metal ions in the reaction. Hydrogen peroxide can increase the oxygen content in the system, promote oxidation and thus raise the oxidation potential of the material. The method can prepare the primary particles of the cobalt oxyhydroxide which grow in a platy structure, thereby obtaining the uniform and high-compactness aluminum-doped cobaltosic oxide material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to aluminum-doped cobaltosic oxide, a preparation method and application thereof.
Background
The lithium cobaltate has the advantages of high specific capacity, long cycle life, high compaction density and the like, and is widely applied to the anode material of the lithium ion battery. At present, the industrialized high-voltage lithium cobaltate is firstly prepared by using aluminum-doped cobaltate as a precursor, and the compaction density of a lithium cobaltate material pole piece is improved, so that the energy density of the lithium cobaltate material pole piece is improved, and the improvement of the compaction density of the lithium cobaltate material is generally realized by matching with cobaltate precursor particles with different sizes. The prior art has the technical difficulty of improving the compactness. Generally, the lower the particle size, the shorter the synthesis time, the lower the compactibility, and the lower compactibility of the tricobalt tetraoxide material is unfavorable for improving the energy density of lithium cobaltate. The formation of primary particles is a key for influencing compactness, and the primary particles are the minimum units without structures such as accumulation, flocculation and the like in the particles.
In addition, in the process of preparing aluminum-doped cobaltosic oxide, aluminum can be caused to form flaky precipitation. The reason for this is that trivalent aluminum and divalent cobalt have large differences in radii and valence states, and aluminum is difficult to enter into a crystal lattice, so that aluminum is caused to form plate-like precipitation.
Disclosure of Invention
The invention relates to aluminum-doped cobaltosic oxide, a preparation method and application thereof, and belongs to the technical field of lithium ion batteries. The invention discloses a preparation method of aluminum-doped cobaltosic oxide, which comprises the following steps: preparing industrial cobalt chloride and aluminum chloride into a mixed solution according to a certain proportion. Heating distilled water, adding a mixed solution, a complexing agent, a sodium hydroxide solution and hydrogen peroxide, stirring and mixing, introducing air into the mixture for synthesis reaction, adjusting the pH value, and then placing the mixture into a ceramic sagger for thermal decomposition to obtain the aluminum-doped cobaltosic oxide. The complexing agent provides the function of an oxidant in the reaction, promotes the formation of aluminum-doped cobaltosic oxide, and can effectively control the reduction and oxidation states of metal ions in the reaction. Hydrogen peroxide can increase the oxygen content in the system, promote oxidation and thus raise the oxidation potential of the material. The method can prepare the primary particles of the cobalt oxyhydroxide which grow in a platy structure, thereby obtaining the uniform and high-compactness aluminum-doped cobaltosic oxide material.
The aim of the invention can be achieved by the following technical scheme:
The preparation method of the aluminum-doped cobaltosic oxide comprises the following steps:
A1: preparing industrial cobalt chloride and aluminum chloride into a mixed solution;
A2: heating distilled water, adding mixed solution, sodium hydroxide, complexing agent and hydrogen peroxide, stirring and mixing, introducing air, reacting, monitoring granularity, and adding carbonic acid to regulate pH after the reaction is finished;
A3: and (5) placing the filtered filter residues into a ceramic sagger for calcination, and cooling to obtain the aluminum-doped cobaltosic oxide.
Further, the mass concentration of cobalt ions in the mixed solution in the step A1 is 130-135g/L, and the mass concentration of aluminum ions is 0.72-0.75g/L.
Further, heating in the step A2 means heating to 69-71 ℃, wherein the mass ratio of the distilled water, the mixed solution, the sodium hydroxide, the complexing agent and the hydrogen peroxide is 1-1.5:1-1.2:0.05-0.15:0.5-0.8:0.1-1.
Further, the complexing agent in the step A2 consists of ethylenediamine and nitroformic acid in a mass ratio of 2:1, and the reaction is stopped when the particle size is 33+/-0.1 mu m.
Further, the stirring speed in the step A2 is 500-600r/min, and the pH is 7.0-7.3.
Further, the calcination time and the calcination temperature in the step A3 are respectively 1-1.5h and 600-700 ℃, and the cooling is that the temperature is cooled to 23-30 ℃.
The aluminum-doped cobaltosic oxide is prepared by adopting the preparation method.
An application of aluminum-doped cobaltosic oxide is disclosed, which is applied to the technical field of lithium ion batteries.
The invention has the beneficial effects that:
1. The ethylenediamine in the complexing agent has stronger coordination effect with aluminum ions and cobalt ions, and can effectively control the reduction and oxidation states of metal ions in the reaction, so that the prepared aluminum-doped cobaltosic oxide has better performance. The nitrobenzoic acid provides an oxidizing agent in the reaction while promoting the formation of aluminum-doped tricobalt tetraoxide.
2. Hydrogen peroxide can increase the oxygen content in the system, promote oxidation and thus raise the oxidation potential of the material. The higher the oxidation potential of cobalt ions, the lower the oxidation degree of cobalt, and primary particles grow in the plate-like structure direction. In contrast, the cobalt has high oxidation degree, primary particles are in a long and thin strip shape, and the thin strip shape is easy to agglomerate into hollow secondary spherical particles, so that the compactness is greatly influenced by the deficiency of granularity. The invention can prepare the cobalt oxyhydroxide primary particles which grow in a platy structure, thereby obtaining the aluminum-doped cobaltosic oxide material with high compactness.
3. The pH value is regulated by adding carbonic acid to enable aluminum to form an amorphous product, and the amorphous product can be uniformly distributed in cobalt oxyhydroxide so as to obtain the uniform aluminum-doped cobaltosic oxide material.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description will refer to the specific embodiments, structures, features and effects according to the present invention in conjunction with examples.
Example 1
The preparation method of the aluminum-doped cobaltosic oxide comprises the following steps:
A1: preparing industrial cobalt chloride and aluminum chloride into a mixed solution;
A2: heating distilled water, adding mixed solution, sodium hydroxide, complexing agent and hydrogen peroxide, stirring and mixing, introducing air, reacting, monitoring granularity, and adding carbonic acid to regulate pH after the reaction is finished;
A3: and (5) placing the filtered filter residues into a ceramic sagger for calcination, and cooling to obtain the aluminum-doped cobaltosic oxide.
The mass concentration of cobalt ions in the mixed solution in the step A1 is 130g/L, and the mass concentration of aluminum ions is 0.72g/L.
Heating in the step A2 refers to heating to 69 ℃, wherein the mass ratio of the distilled water to the mixed solution to the sodium hydroxide to the complexing agent to the hydrogen peroxide is 1:1:0.05:0.5:0.1.
The complexing agent in the step A2 consists of ethylenediamine and nitroformic acid in a mass ratio of 2:1, and the reaction is stopped when the granularity is 33 mu m.
The stirring speed in the step A2 is 500r/min, and the pH is 7.0.
The calcination time and the calcination temperature in the step A3 are respectively 1h and 600 ℃, and the cooling refers to cooling to 23 ℃.
The aluminum-doped cobaltosic oxide is prepared by adopting the preparation method.
An application of aluminum-doped cobaltosic oxide is disclosed, which is applied to the technical field of lithium ion batteries.
Example 2
The preparation method of the aluminum-doped cobaltosic oxide comprises the following steps:
A1: preparing industrial cobalt chloride and aluminum chloride into a mixed solution;
A2: heating distilled water, adding mixed solution, sodium hydroxide, complexing agent and hydrogen peroxide, stirring and mixing, introducing air, reacting, monitoring granularity, and adding carbonic acid to regulate pH after the reaction is finished;
A3: and (5) placing the filtered filter residues into a ceramic sagger for calcination, and cooling to obtain the aluminum-doped cobaltosic oxide.
The mass concentration of cobalt ions in the mixed solution in the step A1 is 132g/L, and the mass concentration of aluminum ions is 0.73g/L.
Heating in the step A2 refers to heating to 70 ℃, wherein the mass ratio of the distilled water to the mixed solution to the sodium hydroxide to the complexing agent to the hydrogen peroxide is 1.2:1:0.05:0.5:0.1.
The complexing agent in the step A2 consists of ethylenediamine and nitroformic acid in a mass ratio of 2:1, and the reaction is stopped when the granularity is 33 mu m.
The stirring speed in the step A2 is 550r/min, and the pH is 7.1.
The calcination time and the calcination temperature in the step A3 are respectively 1.2h and 650 ℃, and the cooling refers to cooling to 26 ℃.
The aluminum-doped cobaltosic oxide is prepared by adopting the preparation method.
An application of aluminum-doped cobaltosic oxide is disclosed, which is applied to the technical field of lithium ion batteries.
Example 3
The preparation method of the aluminum-doped cobaltosic oxide comprises the following steps:
A1: preparing industrial cobalt chloride and aluminum chloride into a mixed solution;
A2: heating distilled water, adding mixed solution, sodium hydroxide, complexing agent and hydrogen peroxide, stirring and mixing, introducing air, reacting, monitoring granularity, and adding carbonic acid to regulate pH after the reaction is finished;
A3: and (5) placing the filtered filter residues into a ceramic sagger for calcination, and cooling to obtain the aluminum-doped cobaltosic oxide.
The mass concentration of cobalt ions in the mixed solution in the step A1 is 135g/L, and the mass concentration of aluminum ions is 0.75g/L.
Heating in the step A2 refers to heating to 71 ℃, wherein the mass ratio of the distilled water, the mixed solution, the sodium hydroxide, the complexing agent and the hydrogen peroxide is 1.5:1.2:0.15:0.8:1.
The complexing agent in the step A2 consists of ethylenediamine and nitroformic acid in a mass ratio of 2:1, and the reaction is stopped when the granularity is 33 mu m.
The stirring speed in the step A2 is 600r/min, and the pH is 7.3.
The calcination time and the calcination temperature in the step A3 are respectively 1.5h and 700 ℃, and the cooling refers to cooling to 30 ℃.
The aluminum-doped cobaltosic oxide is prepared by adopting the preparation method.
An application of aluminum-doped cobaltosic oxide is disclosed, which is applied to the technical field of lithium ion batteries.
Comparative example 1
On the basis of the embodiment 2, the preparation method of the aluminum-doped cobaltosic oxide comprises the following steps of:
A1: preparing industrial cobalt chloride and aluminum chloride into a mixed solution;
A2: heating distilled water, adding mixed solution, sodium hydroxide, complexing agent and hydrogen peroxide, stirring and mixing, introducing air, reacting, monitoring granularity, and adding carbonic acid to regulate pH after the reaction is finished;
A3: and (5) placing the filtered filter residues into a ceramic sagger for calcination, and cooling to obtain the aluminum-doped cobaltosic oxide.
The mass concentration of cobalt ions in the mixed solution in the step A1 is 132g/L, and the mass concentration of aluminum ions is 0.73g/L.
Heating in the step A2 refers to heating to 70 ℃, wherein the mass ratio of the distilled water to the mixed solution to the sodium hydroxide to the complexing agent to the hydrogen peroxide is 1.2:1:0.05:0.5:0.1.
And (3) stopping the reaction when the complexing agent in the step A2 is ethylenediamine and the granularity is 33 mu m.
The stirring speed in the step A2 is 550r/min, and the pH is 7.1.
The calcination time and the calcination temperature in the step A3 are respectively 1.2h and 650 ℃, and the cooling refers to cooling to 26 ℃.
The aluminum-doped cobaltosic oxide is prepared by adopting the preparation method.
An application of aluminum-doped cobaltosic oxide is disclosed, which is applied to the technical field of lithium ion batteries.
Comparative example 2
On the basis of the embodiment 2, the preparation method of the aluminum-doped cobaltosic oxide comprises the following steps of:
A1: preparing industrial cobalt chloride and aluminum chloride into a mixed solution;
A2: heating distilled water, adding mixed solution, sodium hydroxide, complexing agent and hydrogen peroxide, stirring and mixing, introducing air, reacting, monitoring granularity, and adding carbonic acid to regulate pH after the reaction is finished;
A3: and (5) placing the filtered filter residues into a ceramic sagger for calcination, and cooling to obtain the aluminum-doped cobaltosic oxide.
The mass concentration of cobalt ions in the mixed solution in the step A1 is 132g/L, and the mass concentration of aluminum ions is 0.73g/L.
Heating in the step A2 refers to heating to 70 ℃, wherein the mass ratio of the distilled water to the mixed solution to the sodium hydroxide to the complexing agent to the hydrogen peroxide is 1.2:1:0.05:0.5:0.1.
And (3) stopping the reaction when the complexing agent in the step A2 is nitro formic acid and the granularity is 33 mu m.
The stirring speed in the step A2 is 550r/min, and the pH is 7.1.
The calcination time and the calcination temperature in the step A3 are respectively 1.2h and 650 ℃, and the cooling refers to cooling to 26 ℃.
The aluminum-doped cobaltosic oxide is prepared by adopting the preparation method.
An application of aluminum-doped cobaltosic oxide is disclosed, which is applied to the technical field of lithium ion batteries.
Comparative example 3
On the basis of the embodiment 2, the preparation method of the aluminum-doped cobaltosic oxide comprises the following steps of:
A1: preparing industrial cobalt chloride and aluminum chloride into a mixed solution;
A2: heating distilled water, adding mixed solution, sodium hydroxide and complexing agent, stirring and mixing, introducing air and flow into the mixture for reaction, monitoring granularity, and adding carbonic acid to regulate pH after the reaction is finished;
A3: and (5) placing the filtered filter residues into a ceramic sagger for calcination, and cooling to obtain the aluminum-doped cobaltosic oxide.
The mass concentration of cobalt ions in the mixed solution in the step A1 is 132g/L, and the mass concentration of aluminum ions is 0.73g/L.
Heating in the step A2 means heating to 70 ℃, wherein the mass ratio of the distilled water to the mixed solution to the sodium hydroxide to the complexing agent is 1.2:1:0.05:0.5.
The complexing agent in the step A2 consists of ethylenediamine and nitroformic acid in a mass ratio of 2:1, and the reaction is stopped when the granularity is 33 mu m.
The stirring speed in the step A2 is 550r/min, and the pH is 7.1.
The calcination time and the calcination temperature in the step A3 are respectively 1.2h and 650 ℃, and the cooling refers to cooling to 26 ℃.
The aluminum-doped cobaltosic oxide is prepared by adopting the preparation method.
An application of aluminum-doped cobaltosic oxide is disclosed, which is applied to the technical field of lithium ion batteries.
Comparative example 4
On the basis of the embodiment 2, the preparation method of the aluminum-doped cobaltosic oxide comprises the following steps of:
A1: preparing industrial cobalt chloride and aluminum chloride into a mixed solution;
A2: heating distilled water, adding the mixed solution, sodium hydroxide, complexing agent and hydrogen peroxide, stirring and mixing, introducing air and flowing into the mixture for reaction, and monitoring the granularity;
A3: and (5) placing the filtered filter residues into a ceramic sagger for calcination, and cooling to obtain the aluminum-doped cobaltosic oxide.
The mass concentration of cobalt ions in the mixed solution in the step A1 is 132g/L, and the mass concentration of aluminum ions is 0.73g/L.
Heating in the step A2 refers to heating to 70 ℃, wherein the mass ratio of the distilled water to the mixed solution to the sodium hydroxide to the complexing agent to the hydrogen peroxide is 1.2:1:0.05:0.5:0.1.
The complexing agent in the step A2 consists of ethylenediamine and nitroformic acid in a mass ratio of 2:1, and the reaction is stopped when the granularity is 33 mu m.
The stirring rotating speed in the step A2 is 550r/min.
The calcination time and the calcination temperature in the step A3 are respectively 1.2h and 650 ℃, and the cooling refers to cooling to 26 ℃.
The aluminum-doped cobaltosic oxide is prepared by adopting the preparation method.
An application of aluminum-doped cobaltosic oxide is disclosed, which is applied to the technical field of lithium ion batteries.
1. Performance testing
Tap density: the aluminum-doped tricobalt tetraoxide prepared in examples 1 to 3 and comparative examples 1 to 3 was used as a sample, and tap densities (g.cm -3) were measured on the samples using a tap density measuring instrument, respectively.
Uniformity: the aluminum-doped tricobalt tetraoxide prepared in examples 1 to 3 and comparative examples 1 to 4 was used as a sample, and the surface of the sample was observed by using an electron microscope scanner to see whether or not a plate-like substance was precipitated. The test results are shown in Table 1.
Table 1 test results
As can be seen from Table 1, the tap densities of examples 1-3 were greater than those of comparative examples 1-3, and only the surface of comparative example 4 was presented with aluminum flakes in the uniformity test. The ethylenediamine in the complexing agent has stronger coordination effect with aluminum ions and cobalt ions, and can effectively control the reduction and oxidation states of metal ions in the reaction, so that the prepared aluminum-doped cobaltosic oxide has better performance. The nitrobenzoic acid provides an oxidizing agent in the reaction while promoting the formation of aluminum-doped tricobalt tetraoxide. Hydrogen peroxide can increase the oxygen content in the system, promote oxidation and thus raise the oxidation potential of the material. The higher the oxidation potential of cobalt ions, the lower the oxidation degree of cobalt, and primary particles grow in the plate-like structure direction. In contrast, the cobalt has high oxidation degree, primary particles are in a long and thin strip shape, and the thin strip shape is easy to agglomerate into hollow secondary spherical particles, so that the compactness is greatly influenced by the deficiency of granularity. The aluminum is formed into an amorphous product by adjusting the pH with the addition of carbonic acid, and can be uniformly distributed in the cobalt oxyhydroxide. The invention can prepare the cobalt oxyhydroxide primary particles which grow in a platy structure, thereby obtaining the uniform and high-compactness aluminum-doped cobaltosic oxide material.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (4)
1. The preparation method of the aluminum-doped cobaltosic oxide is characterized by comprising the following steps of:
A1: preparing industrial cobalt chloride and aluminum chloride into a mixed solution;
A2: heating distilled water, adding mixed solution, sodium hydroxide, complexing agent and hydrogen peroxide, stirring and mixing, introducing air, reacting, monitoring granularity, and adding carbonic acid to regulate pH after the reaction is finished;
a3: placing the filtered filter residues into a ceramic sagger for calcination, and cooling to obtain aluminum-doped cobaltosic oxide;
Heating in the step A2 means heating to 69-71 ℃, wherein the mass ratio of distilled water to the mixed solution to sodium hydroxide to complexing agent to hydrogen peroxide is 1-1.5:1-1.2:0.05-0.15:0.5-0.8:0.1-1;
the complexing agent in the step A2 consists of ethylenediamine and nitroformic acid in a mass ratio of 2:1, and the reaction is stopped when the granularity is 33+/-0.1 mu m.
2. The method for preparing aluminum-doped cobaltosic oxide according to claim 1, wherein the mass concentration of cobalt ions in the mixed solution in the step A1 is 130-135g/L and the mass concentration of aluminum ions is 0.72-0.75g/L.
3. The method for preparing aluminum-doped cobaltosic oxide according to claim 1, wherein the stirring speed in the step A2 is 500-600r/min, and the pH is 7.0-7.3.
4. The method of claim 1, wherein the calcination time and the calcination temperature in the step A3 are 1-1.5h and 600-700 ℃, respectively, and the cooling is cooling to 23-30 ℃.
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