CN112645393A - Preparation method of cobaltosic oxide - Google Patents
Preparation method of cobaltosic oxide Download PDFInfo
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- CN112645393A CN112645393A CN202011542520.7A CN202011542520A CN112645393A CN 112645393 A CN112645393 A CN 112645393A CN 202011542520 A CN202011542520 A CN 202011542520A CN 112645393 A CN112645393 A CN 112645393A
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- C01—INORGANIC CHEMISTRY
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- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- C01P2006/12—Surface area
Abstract
The invention discloses a preparation method of cobaltosic oxide, which comprises the following steps: adding a complexing agent into a cobalt salt solution to obtain a mixed solution, adding the mixed solution, a precipitator solution and air into a reaction kettle in a parallel flow manner to carry out a synthetic reaction, and controlling the pH value and the reaction temperature of a reaction system; stopping reaction when the granularity of the synthesized cobaltosic oxide reaches a set value, and carrying out centrifugal washing and drying; and after low-temperature calcination is carried out on the obtained dried material, centrifugal washing and drying are carried out again, and then high-temperature calcination is carried out. Through a two-step calcination method, impurity ions adsorbed on the surfaces and the interior of particles are washed away by utilizing the larger specific surface area of cobaltosic oxide calcined at low temperature; the cobaltosic oxide material with more complete crystal form and low impurity can be sintered by decomposing substances containing water or gas in the drying material at low temperature and then calcining at high temperature.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a preparation method of cobaltosic oxide.
Background
Lithium cobaltate materials have always dominated the 3C market due to higher energy density and excellent cycling stability. In recent years, with the high-speed development of products such as smart phones, tablet computers and unmanned aerial vehicles, the requirements on batteries are higher and higher, and higher requirements on the charging voltage and the cycle life of lithium cobaltate are also provided.
Under a higher charging voltage and after a longer period of charging and discharging, the more fully the lithium cobaltate material is soaked by the electrolyte, the more easily the surface of the material is corroded, and therefore, the single crystallization of lithium cobaltate is a developing direction. Once single-crystallized, the smaller the area of the material that is corroded by contact with the electrolyte, the longer the time for the material to stabilize in structure. However, when the precursor of lithium cobaltate, i.e. cobaltosic oxide, is synthesized by a wet method, the sodium ion content in the cobaltosic oxide is higher due to the existence of a precipitator, i.e. sodium hydroxide or sodium carbonate, so that the subsequent sintering process of the lithium cobaltate is seriously influenced, and the single crystallization degree of the lithium cobaltate is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of low-impurity cobaltosic oxide.
The invention is realized by the following technical scheme.
A preparation method of cobaltosic oxide is characterized by comprising the following steps:
(1) adding a complexing agent into a cobalt salt solution to obtain a mixed solution, adding the mixed solution, a precipitator solution and air into a reaction kettle in a parallel flow manner to carry out a synthetic reaction, and controlling the pH value and the reaction temperature of a reaction system;
(2) stopping the reaction when the granularity of the cobaltosic oxide synthesized in the step (1) reaches a set value, and carrying out centrifugal washing and drying;
(3) and (3) calcining the dried material obtained in the step (2) at a low temperature, then carrying out centrifugal washing and drying again, and then carrying out high-temperature calcination.
Further, the cobalt salt solution in the step (1) is a mixed solution of one or more of cobalt chloride, cobalt sulfate and cobalt nitrate solution, and the concentration of the cobalt salt solution is 1-2 mol/L; the complexing agent is one of EDTA, citric acid and ammonia water, and the concentration of the complexing agent is 0.1-2 mol/L.
Further, the precipitant solution in step (1) is a mixed solution of one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the concentration of the precipitant solution is 5-10mol/L,
further, the pH value of the reaction system in the step (1) is 9-11, and the reaction temperature is 50-80 ℃.
Further, the flow rates of the mixed solution, the precipitant solution and the air in the step (1) are respectively 200-400L/h, 80-200L/h and 10-25m3/h。
Further, the particle size of the cobaltosic oxide in the step (2) is 3-5 um.
Further, the low-temperature calcination temperature range of the step (3) is 450-650 ℃, and the calcination time is 5-8 h.
Further, the high-temperature calcination temperature range of the step (3) is 700-900 ℃, and the calcination time is 3-6 h.
The preparation method of the low-impurity cobaltosic oxide has the beneficial technical effects that through a two-step calcination method, impurity ions adsorbed on the surfaces and the interior of particles are washed away by utilizing the larger specific surface area of the cobaltosic oxide calcined at low temperature; the cobaltosic oxide material with more complete crystal form and low impurity can be sintered by decomposing substances containing water or gas in the drying material at low temperature and then calcining at high temperature.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
(1) Adding ammonia water into a cobalt chloride solution to obtain a mixed solution, wherein the concentration of the cobalt chloride solution is 2mol/L, the concentration of the ammonia water is 0.5mol/L, and preparing a sodium hydroxide solution of 8 mol/L; (2) the mixed solution, sodium hydroxide solution and air are respectively mixed at the flow rates of 200L/h, 150L/h and 15m3The reaction solution is added into a reaction kettle in a concurrent flow manner for synthetic reaction, the reaction kettle is started to control the pH of the reaction system to be 11, and the temperature is 55 ℃; (3) stopping reaction when the granularity of the cobaltosic oxide reaches 3.5um, and carrying out centrifugal washing (pure water) and drying; (4) calcining the dried material at the low temperature of 600 ℃ for 5 hours;the specific surface area of the cobaltosic oxide material at this time was 10.5m2(ii)/g; (5) carrying out centrifugal washing again to remove impurity ions; (6) after washing, drying and calcining for 6h at 800 ℃.
Table one shows the physical properties of the aluminum-doped cobaltosic oxide.
Example 2
(1) Adding EDTA (ethylene diamine tetraacetic acid) into a cobalt sulfate solution to obtain a mixed solution, wherein the concentration of the cobalt sulfate solution is 1mol/L, EDTA, the concentration is 2mol/L, and a sodium carbonate solution with the concentration of 5mol/L is prepared; (2) mixing the mixed solution, sodium carbonate solution and air at flow rates of 400L/h, 80L/h and 25m3The reaction solution is added into a reaction kettle in a concurrent flow manner for synthetic reaction, the reaction kettle is started to control the pH of the reaction system to be 9, and the temperature is 80 ℃; (3) stopping reaction when the granularity of the synthesized cobaltosic oxide reaches 5um, and carrying out centrifugal washing and drying; (4) calcining the dried material at the low temperature of 450 ℃ for 7 hours; the specific surface area of the cobaltosic oxide material at this time was 6.5m2(ii)/g; (5) carrying out centrifugal washing again to remove impurity ions; (6) after washing, drying and calcining at 700 ℃ for 4 h.
The second table is the physical property of the aluminum-doped cobaltosic oxide
Example 3
(1) Adding citric acid into a mixed cobalt salt solution of a cobalt sulfate solution and a cobalt nitrate solution to prepare a mixed solution, wherein the concentration of the mixed cobalt salt solution is 1.5mol/L, the concentration of citric acid is 0.1mol/L, and a mixed precipitant solution of a sodium carbonate solution and a sodium bicarbonate solution is prepared; (2) respectively mixing the mixed solution, the mixed precipitant solution and air at flow rates of 300L/h, 200L/h and 10m3The reaction solution is added into a reaction kettle in a concurrent flow manner for synthetic reaction, the reaction kettle is started to control the pH of the reaction system to be 10, and the temperature is 65 ℃; (3) when synthesizing cobaltosic oxideStopping reaction after the granularity reaches 4um, and carrying out centrifugal washing and drying; (4) calcining the dried material at the low temperature of 650 ℃ for 8 hours; at this time, the specific surface area of the cobaltosic oxide material was 12m2(ii)/g; (5) carrying out centrifugal washing again to remove impurity ions; (6) after washing, drying and calcining at 900 ℃ for 3 h.
Physical properties of aluminum-doped cobaltosic oxide
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (8)
1. A preparation method of cobaltosic oxide is characterized by comprising the following steps:
(1) adding a complexing agent into a cobalt salt solution to obtain a mixed solution, adding the mixed solution, a precipitator solution and air into a reaction kettle in a parallel flow manner to carry out a synthetic reaction, and controlling the pH value and the reaction temperature of a reaction system;
(2) stopping the reaction when the granularity of the cobaltosic oxide synthesized in the step (1) reaches a set value, and carrying out centrifugal washing and drying;
(3) and (3) calcining the dried material obtained in the step (2) at a low temperature, then carrying out centrifugal washing and drying again, and then carrying out high-temperature calcination.
2. The preparation method according to claim 1, wherein the cobalt salt solution in step (1) is a mixture of one or more of cobalt chloride, cobalt sulfate and cobalt nitrate solution, and the concentration of the cobalt salt solution is 1-2 mol/L; the complexing agent is one of EDTA, citric acid and ammonia water, and the concentration of the complexing agent is 0.1-2 mol/L.
3. The preparation method according to claim 1, wherein the precipitant solution in step (1) is a mixture of one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the concentration of the precipitant solution is 5-10 mol/L.
4. The preparation method according to claim 1, wherein the pH value of the reaction system in the step (1) is 9-11, and the reaction temperature is 50-80 ℃.
5. The method as claimed in claim 1, wherein the flow rates of the mixed solution, the precipitant solution and the air in step (1) are respectively 400L/h, 80-200L/h and 10-25m3/h。
6. The method according to claim 1, wherein the particle size of the cobaltosic oxide of step (2) is 3-5 um.
7. The preparation method of claim 1, wherein the low-temperature calcination temperature in step (3) is 450-650 ℃ and the calcination time is 5-8 h.
8. The preparation method of claim 1, wherein the high-temperature calcination temperature in the step (3) is 700-900 ℃ and the calcination time is 3-6 h.
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Citations (9)
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|---|---|---|---|---|
| CN103224257A (en) * | 2012-11-28 | 2013-07-31 | 江苏大学 | Method for preparing Co3O4 from waste and old lithium ion batteries |
| CN105668650A (en) * | 2016-03-23 | 2016-06-15 | 荆门市格林美新材料有限公司 | Method for preparing low-sodium cobaltosic oxide |
| CN105776356A (en) * | 2016-03-22 | 2016-07-20 | 阳江市联邦金属化工有限公司 | Preparation method of spherical compact tricobalt tetroxide |
| CN105800699A (en) * | 2016-04-20 | 2016-07-27 | 湖南海纳新材料有限公司 | Method for preparing high-sphericity-degree and large-particle cobaltosic oxide |
| CN106082358A (en) * | 2016-06-22 | 2016-11-09 | 荆门市格林美新材料有限公司 | The preparation method of Cobalto-cobaltic oxide |
| CN106882843A (en) * | 2017-01-19 | 2017-06-23 | 衢州华友钴新材料有限公司 | A kind of preparation method of fine and close crystal formation cobaltosic oxide |
| CN207046881U (en) * | 2017-05-15 | 2018-02-27 | 江苏凯力克钴业股份有限公司 | A kind of preparation facilities of low sodium cobaltosic oxide |
| CN108862405A (en) * | 2017-05-15 | 2018-11-23 | 江苏凯力克钴业股份有限公司 | A kind of preparation method and device of low sodium cobaltosic oxide |
| CN109942030A (en) * | 2019-05-05 | 2019-06-28 | 衢州华友钴新材料有限公司 | A kind of preparation method of high-densit small particle spherical cobaltic-cobaltous oxide |
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2020
- 2020-12-21 CN CN202011542520.7A patent/CN112645393A/en active Pending
Patent Citations (9)
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|---|---|---|---|---|
| CN103224257A (en) * | 2012-11-28 | 2013-07-31 | 江苏大学 | Method for preparing Co3O4 from waste and old lithium ion batteries |
| CN105776356A (en) * | 2016-03-22 | 2016-07-20 | 阳江市联邦金属化工有限公司 | Preparation method of spherical compact tricobalt tetroxide |
| CN105668650A (en) * | 2016-03-23 | 2016-06-15 | 荆门市格林美新材料有限公司 | Method for preparing low-sodium cobaltosic oxide |
| CN105800699A (en) * | 2016-04-20 | 2016-07-27 | 湖南海纳新材料有限公司 | Method for preparing high-sphericity-degree and large-particle cobaltosic oxide |
| CN106082358A (en) * | 2016-06-22 | 2016-11-09 | 荆门市格林美新材料有限公司 | The preparation method of Cobalto-cobaltic oxide |
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