CN108275730B - Synthesis method of 13-15 micron battery-grade spherical cobalt carbonate seed crystal - Google Patents
Synthesis method of 13-15 micron battery-grade spherical cobalt carbonate seed crystal Download PDFInfo
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- CN108275730B CN108275730B CN201810096602.XA CN201810096602A CN108275730B CN 108275730 B CN108275730 B CN 108275730B CN 201810096602 A CN201810096602 A CN 201810096602A CN 108275730 B CN108275730 B CN 108275730B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01G51/00—Compounds of cobalt
- C01G51/06—Carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention discloses a method for synthesizing a 13-15 micron battery-grade spherical cobalt carbonate seed crystal, which comprises the following steps: simultaneously adding an ammonium bicarbonate solution and a cobalt salt solution into an ammonium bicarbonate base solution, controlling the reaction temperature and the stirring speed to be 50-60 ℃ and 100-250rpm respectively, increasing the adding speed of the cobalt salt solution at intervals, controlling the pH value to be 7.15-7.25 within 0.5-1h of reaction, keeping the pH value to be 7.05-7.15 after 2-4h of reaction, and ending the reaction until spherical cobalt carbonate seed crystals grow to a preset size; the method has the advantages that the feeding rate of the cobalt salt solution is controlled at different stages, the slow change of the pH value after the reaction is controlled, the generation reaction of the crystal seeds is promoted to be carried out smoothly, the purpose of effectively controlling the reasonable and controllable growth of the cobalt carbonate crystal seeds is achieved, the production efficiency is high, the reaction temperature is reasonable, the required equipment is simple and easy to obtain, the method is suitable for large-scale industrial production, and the application prospect is wide.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery anode materials, and particularly relates to a method for synthesizing a 13-15 micron battery-grade spherical cobalt carbonate crystal seed.
Background
With the continuous development of society, the scientific and technological speed is increasing, and the informatization society has come, and the electronic products are promoted to be updated continuously, and lithium battery products widely applied to the electronic products are also endlessly developed, and lithium cobaltate is still used as a main flow product in the lithium battery products nowadays. In addition, since lithium cobaltate is mainly obtained by sintering cobaltosic oxide, which is obtained by calcining cobalt carbonate, and lithium carbonate or lithium hydroxide, the quality of lithium cobaltate is determined by the quality of the raw material cobalt carbonate.
In the prior art, the most common production method of spherical cobalt carbonate is to use cobalt chloride and ammonium bicarbonate to react at a high temperature, the reaction process mainly comprises two steps of seed crystal generation and crystal growth, wherein the synthesis of the cobalt carbonate seed crystal and the sphericity and size thereof are crucial to the subsequent crystal growth, the microstructure, the size control and the compactness of the subsequent cobalt carbonate product can be determined to a great extent, and the performance of the subsequent spherical cobalt carbonate product is finally determined.
In recent years, people put forward more strict requirements on cobalt carbonate products, which not only need higher sphericity, but also need higher tap density, and meanwhile, the requirements on the yield and the content of small particles in the products are increasingly strict to meet the requirements on the application of practical electronic products.
Therefore, on the basis of the existing research results, the research and development of the synthetic method of the spherical cobalt carbonate seed crystal with high sphericity and controllable size has important theoretical and practical significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for synthesizing a battery-grade spherical cobalt carbonate crystal seed with the particle size of 13-15 microns.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing 13-15 micron battery-grade spherical cobalt carbonate seed crystals comprises the following steps: simultaneously adding an ammonium bicarbonate solution and a cobalt salt solution into an ammonium bicarbonate base solution, controlling the reaction temperature and the stirring speed to be 50-60 ℃ and 250rpm, increasing the adding speed of the cobalt salt solution at intervals, controlling the pH value to be 7.15-7.25 within 0.5-1h of reaction, keeping the pH value to be 7.05-7.15 after 2-4h of reaction, reacting until the spherical cobalt carbonate seed crystal grows to a preset size, and finishing the reaction.
In the technical scheme, the pH value of the ammonium bicarbonate base solution is 8.0-9.0.
Preferably, in the technical scheme, the descending speed of the pH value within 0.5-1h of reaction is 0.03-0.05min-1。
In the technical scheme, the concentration of the cobalt salt solution is 140 g/L in terms of the amount of metal cobalt, and the addition rate of the cobalt salt solution is 1000L/h in terms of 300-.
In the technical scheme, the concentration of the ammonium bicarbonate solution is 200-240g/L, and the adding rate of the ammonium bicarbonate solution is 500-1200L/h.
In the above technical scheme, the cobalt salt is any one of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate.
In the technical scheme, the concentration of the ammonium bicarbonate base solution is 3-6g/L, and the addition amount of the ammonium bicarbonate base solution is 4.0-4.5m3。
Preferably, in the above technical solution, the initial adding rate of the cobalt salt solution is 300-350L/h, and the adding rate of the cobalt salt solution is increased by 30-50L/h at intervals of 16-20 h.
Further preferably, in the above technical solution, the stirring speed is controlled to be 175-200rpm and 150-175rpm respectively after the first 24h and the second 24 h.
The invention also aims to provide the spherical cobalt carbonate seed crystal synthesized by the method, wherein the sphericity of the spherical cobalt carbonate seed crystal is 0.93-0.97, the D10 is 11.8-12.6 μm, the D50 is 13-15 μm, and the D90 is 14.8-15.7 μm.
The invention has the advantages and effects that:
(1) according to the method, the feeding rate of the cobalt salt solution is controlled at different crystal seed generation stages, the addition amount of the ammonium bicarbonate solution is adjusted in a matching manner, particularly the preparation of the ammonium bicarbonate base solution and the slow control of the pH value after reaction are carried out, so that the crystal seed generation reaction is promoted to be carried out smoothly, the purpose of effectively controlling the reasonable and controllable growth of the cobalt carbonate crystal seed is achieved, the phenomena of violent local reaction, too fast crystal seed growth and overlarge morphology difference are effectively avoided, and finally the spherical cobalt carbonate crystal seed with high sphericity and uniform particle size is prepared;
(2) the method for preparing the cobalt carbonate seed crystal has high production efficiency, reasonable reaction temperature and simple and easily-obtained required equipment, and is suitable for large-scale industrial production; the method can be used for preparing the spherical cobalt carbonate with the particle size D50 ranging from 13 to 15 mu m, and the product has high sphericity and wide application prospect, and has important theoretical and practical significance.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
The raw materials used in the invention are industrial-grade ammonium bicarbonate and industrial-grade cobalt chloride.
Example 1
Preparing an ammonium bicarbonate solution with the concentration of 235g/L and a cobalt chloride solution with the concentration of 140 g/L calculated by the amount of metal cobalt for later use; firstly adding deionized water 4m into a reaction kettle3Then continuously adding 6min ammonium bicarbonate solution into the reaction kettle at a rate of 850L/h by a metering pump, uniformly stirring to obtain ammonium bicarbonate base solution with a pH value of 8.55, heating to control the temperature in the reaction kettle to be constant at 54 ℃, starting stirring, controlling the stirring speed to be 200rpm, simultaneously starting a cobalt chloride metering pump and an ammonium bicarbonate metering pump, controlling the initial addition rate of the cobalt chloride solution to be 340L/h, increasing the addition rate of the cobalt chloride solution by 45L/h at intervals of 20h, simultaneously controlling the pH value of a reaction system to be reduced to 7.25 after reacting for 45min, controlling the pH value to be 7.15 after reacting for 3h, adjusting the stirring speed to be 160rpm after reacting for 24h, monitoring and detecting the particle size of cobalt carbonate seed crystals until the cobalt carbonate seed crystals grow to a preset size, and finishing the reaction to obtain the spherical cobalt carbonate seed crystal.
Example 2
Preparing ammonium bicarbonate solution with the concentration of 215g/L and cobalt chloride solution with the concentration of 128 g/L calculated by the amount of metal cobalt for later use; firstly adding deionized water 4m into a reaction kettle3Then continuously adding an ammonium bicarbonate solution for 9min into the reaction kettle at a rate of 750L/h by using a metering pump, uniformly stirring to obtain an ammonium bicarbonate base solution with a pH value of 8.4, heating to control the temperature in the reaction kettle to be constant at 50 ℃, starting stirring, controlling the stirring speed to be 180rpm, simultaneously starting a cobalt chloride metering pump and an ammonium bicarbonate metering pump, controlling the initial addition rate of the cobalt chloride solution to be 315L/h, increasing the addition rate of the cobalt chloride solution by 30L/h at intervals of 16h, simultaneously controlling the pH value of a reaction system to be reduced to 7.2 after reacting for 60min and to be constant to 7.1 after reacting for 3h by adjusting the addition amount of the ammonium bicarbonate solution, and monitoring and detecting cobalt carbonate crystals after reacting for 24h by adjusting the stirring speed to be 150rpmAnd (4) the grain size of the seed is controlled until the cobalt carbonate seed crystal grows to a preset size, and the reaction is finished to obtain the spherical cobalt carbonate seed crystal.
Comparative example 1
Preparing ammonium bicarbonate solution with the concentration of 215g/L and cobalt chloride solution with the concentration of 128 g/L calculated by the amount of metal cobalt for later use; firstly adding deionized water 4m into a reaction kettle3Then continuously adding an ammonium bicarbonate solution for 9min into the reaction kettle at a rate of 750L/h by using a metering pump, uniformly stirring to obtain an ammonium bicarbonate base solution with a pH value of 8.4, heating to control the temperature in the reaction kettle to be constant at 55 ℃, starting stirring, controlling the stirring speed to be 180rpm, simultaneously starting a cobalt chloride metering pump and an ammonium bicarbonate metering pump, controlling the adding flow of the cobalt chloride solution to be 325L/h, simultaneously controlling the pH value of a reaction system to be constant at 7.15 by adjusting the adding amount of the ammonium bicarbonate solution, adjusting the stirring speed to be 150rpm after reacting for 24h, monitoring and detecting the particle size of the cobalt carbonate seed crystal, and ending the reaction to obtain the spherical cobalt carbonate seed crystal when the cobalt carbonate seed crystal grows to a preset size.
Comparative example 2
Preparing ammonium bicarbonate solution with the concentration of 215g/L and cobalt chloride solution with the concentration of 128 g/L calculated by the amount of metal cobalt for later use; firstly adding deionized water 4m into a reaction kettle3Then continuously adding ammonium bicarbonate solution for 9min into the reaction kettle at the speed of 750L/h by a metering pump, uniformly stirring to obtain ammonium bicarbonate base solution with the pH value of 8.4, heating to control the temperature in the reaction kettle to be constant at 50 ℃, starting stirring, controlling the stirring speed to be 180rpm, simultaneously starting a cobalt chloride metering pump and an ammonium bicarbonate metering pump, controlling the initial adding flow of the cobalt chloride solution to be 315L/h, increasing the adding flow of the cobalt chloride solution by 30L/h at an interval of 16h, meanwhile, the pH value of the reaction system is controlled to be constant at 7.15 by adjusting the adding amount of the ammonium bicarbonate solution, and after 24 hours of reaction, adjusting the stirring speed to 150rpm, monitoring and detecting the particle size of the cobalt carbonate seed crystal until the cobalt carbonate seed crystal grows to a preset size, and finishing the reaction to obtain the spherical cobalt carbonate seed crystal.
Table 1 below shows the results of comparing physicochemical data of spherical cobalt carbonate seeds obtained in examples 1 and 2 of the present invention with those obtained in comparative examples 1 and 2.
TABLE 1 comparison of physicochemical data for cobalt carbonate seeds prepared in examples of the invention and comparative examples
As can be seen from the results in table 1, the feeding rate of the cobalt salt solution is controlled at different seed crystal generation stages, and the addition amount of the ammonium bicarbonate solution is adjusted in a matching manner, particularly, the preparation of the ammonium bicarbonate base solution and the slow control of the pH value after the reaction are performed, so that the seed crystal generation reaction is smoothly performed, the purpose of effectively controlling the reasonable and controllable growth of the cobalt carbonate seed crystal is achieved, the phenomena of violent local reaction, too fast seed crystal growth and too large morphology difference are effectively avoided, and the spherical cobalt carbonate seed crystal with the sphericity of 0.93-0.97 and uniform particle size is finally prepared; in addition, the method has high production efficiency, reasonable reaction temperature, simple and easily-obtained required equipment, is suitable for large-scale industrial production, and has important theoretical and practical significance.
Finally, the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A method for synthesizing 13-15 micron battery-grade spherical cobalt carbonate seed crystals is characterized by comprising the following steps: simultaneously adding an ammonium bicarbonate solution and a cobalt salt solution into an ammonium bicarbonate base solution with the pH value of 8.0-9.0, controlling the reaction temperature and the stirring speed to be 50-60 ℃ and 100-250rpm respectively, increasing the adding speed of the cobalt salt solution at intervals, controlling the pH value to be 7.20-7.25 within 0.5-1h of reaction, keeping the pH value constant to be 7.05-7.15 after 2-4h of reaction, reacting until the spherical cobalt carbonate seed crystal grows to the preset size, and finishing the reaction;
the falling speed of the pH value within 0.5-1h of reaction is 0.03-0.05min-1The concentration of the cobalt salt solution is 1 in terms of the amount of metallic cobalt20-140 g/L, the addition rate of the cobalt salt solution is 300-1000L/h, the sphericity of the spherical cobalt carbonate seed crystal is 0.93-0.97, the D10 is 11.8-12.6 μm, the D50 is 13-15 μm, and the D90 is 14.8-15.7 μm.
2. The method as claimed in claim 1, wherein the concentration of the ammonium bicarbonate solution is 200-240g/L, and the adding rate of the ammonium bicarbonate solution is 500-1200L/h.
3. The synthesis method according to claim 1, wherein the cobalt salt is any one of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate.
4. The synthesis method according to claim 1, wherein the concentration of the ammonium bicarbonate base solution is 3-6g/L, and the addition amount of the ammonium bicarbonate base solution is 4.0-4.5m3。
5. The synthesis method as claimed in claim 4, wherein the initial addition rate of the cobalt salt solution is 300-350L/h, and the addition rate of the cobalt salt solution is increased by 30-50L/h at intervals of 16-20 h.
6. The synthesis method as claimed in claim 5, wherein the stirring speed is controlled to be 175-200rpm and 150-175rpm respectively after the first 24h and the second 24 h.
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| CN113292106B (en) * | 2020-02-24 | 2023-07-25 | 荆门市格林美新材料有限公司 | Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide |
| CN113526568A (en) * | 2020-04-17 | 2021-10-22 | 荆门市格林美新材料有限公司 | Preparation method of large-particle cobalt carbonate for microporous catalyst |
| CN113307308B (en) * | 2021-06-25 | 2023-05-23 | 巴斯夫杉杉电池材料有限公司 | Doped large-particle cobalt carbonate and preparation method thereof |
| CN113816435B (en) * | 2021-08-27 | 2022-11-15 | 广东邦普循环科技有限公司 | Crystal transition precursor and preparation method thereof |
| CN114956197A (en) * | 2022-06-20 | 2022-08-30 | 江西佳纳能源科技有限公司 | Spherical cobalt carbonate, preparation method thereof and lithium ion battery cathode material |
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