CN112591805A - Method for improving particle size distribution width of nickel-cobalt-manganese ternary precursor - Google Patents
Method for improving particle size distribution width of nickel-cobalt-manganese ternary precursor Download PDFInfo
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Abstract
A method for improving the particle size distribution width of a nickel-cobalt-manganese ternary precursor comprises the following steps: adding a nickel-cobalt-manganese sulfate solution, liquid caustic soda and an ammonia water solution into a reaction kettle provided with a base solution in a concurrent flow manner to carry out a coprecipitation reaction, adjusting the dosages of the liquid caustic soda and the ammonia water to enable the pH value to be 10.0-10.4 and the ammonia concentration to be 9.0-10.5g/L within 8h before the reaction under the conditions of 55-65 ℃ and the stirring speed of 150-250r/min, and adjusting the dosages of the liquid caustic soda and the ammonia water to enable the pH value to be stabilized at 10.5-10.8 and the ammonia concentration to be 10-15g/L at the stage from 8h to the end of the reaction; and (3) growing crystal particles generated by the coprecipitation reaction to a particle size D50: stopping the reaction after 10.0-11.0 μm; and washing and drying the obtained semi-finished product slurry to obtain the nickel-cobalt-manganese ternary precursor. By optimizing the production process, the particle size distribution width of the product is increased at the initial stage of the reaction, and the particle size distribution width of the corresponding large-particle product in the mixed product can be effectively increased.
Description
Technical Field
The invention relates to the field of preparation of new energy battery material precursors, in particular to a method for improving the particle size distribution width of a nickel-cobalt-manganese ternary precursor.
Background
The low-nickel-cobalt-manganese ternary precursor mixture is an important raw material for preparing the energy storage battery, and has wide application field and various specification models. The particle size distribution of the mixture is an important index influencing the physical and chemical properties of the mixture. The particle size distribution width of the mixed product is affected by the corresponding single product, and the particle size and the distribution width of the single product need to be strictly controlled in the production process. In actual production, the existing preparation method has the problems of high PH and high rotating speed in the early stage of reaction, and the aggregate crystal nucleus is not easily formed in the early stage of reaction, so that the particle size distribution of the large-particle product is too narrow: (D90-D10)/(D90+ D10) × 100 ═ 13-20. The particle size distribution of the mixed product is narrow directly, and the normal production requirement of downstream customers cannot be stably met.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for improving the particle size distribution width of a nickel-cobalt-manganese ternary precursor.
The invention is realized by the following technical scheme.
A method for improving the particle size distribution width of a nickel-cobalt-manganese ternary precursor is characterized by comprising the following steps:
(1) mixing Ni2+、Co2+、Mn2+According to the molar ratio of (33.8 +/-1): (33.0 +/-1) preparing a nickel-cobalt-manganese sulfate solution with the total metal concentration of 100 g/L-120 g/L (33.2 +/-1);
(2) preparing reaction base liquid in a reaction kettle and introducing N2The temperature of the reaction bottom liquid is 55-65 ℃, and the adding amount of the reaction bottom liquid is 55-65% of the volume of the reaction kettle;
(3) adding the nickel-cobalt-manganese sulfate solution prepared in the step (1), liquid caustic soda and an ammonia water solution into the reaction kettle bottom solution obtained in the step (2) in a concurrent flow manner for carrying out a coprecipitation reaction, controlling the reaction temperature to be 55-65 ℃ and the stirring speed to be 250r/min, adjusting the use amounts of the liquid caustic soda and the ammonia water within 8h before the reaction to ensure that the pH of the reaction system is 10.0-10.4 and the ammonia concentration is maintained at 9.0-10.5g/L, and adjusting the use amounts of the liquid caustic soda and the ammonia water to ensure that the pH of the reaction system is stabilized at 10.5-10.8 and the ammonia concentration is maintained at 10-15g/L at the stage from 8h to the end of the reaction; and (3) growing crystal particles generated by the coprecipitation reaction to a particle size D50: stopping the reaction after 10.0-11.0 μm;
(4) and (4) washing and drying the semi-finished product slurry obtained in the step (3) to obtain the nickel-cobalt-manganese ternary precursor.
Further, the reaction base solution in the step (2) is prepared by pure water, ammonia water and liquid alkali, the pH of the reaction base solution is 11-12, and the ammonia concentration is 9.5-11.0 g/L; n is a radical of2The flow rate of (A) is 0.5-3.0m3/h。
Further, the flow rate of the nickel-cobalt-manganese sulfate solution in the step (3) is 200-700L/h.
Further, the concentration of the liquid alkali in the step (3) is 25% -35%, and the concentration of the ammonia water solution is 10% -20%.
The method has the beneficial technical effects that the operation is simple and feasible, the particle size distribution width of the product is increased at the initial stage of the reaction by optimizing the production process, the particle size distribution width of the corresponding large-particle product in the mixed product can be effectively increased, and the purposes of (D90-D10)/(D90+ D10) × 100 ═ 20-29 are achieved, so that the problem of too narrow particle size distribution of the mixed product is effectively solved; the product produced by the invention can meet various indexes of customer requirements while improving the particle size distribution width.
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
Mixing Ni2+、Co2+、Mn2+The molar ratio of the raw materials is 32.8: 34.0:32.2 preparing a nickel-cobalt-manganese sulfate solution with the total metal concentration of 100 g/L; at 12m3The pH value of the reaction kettle is 11, the ammonia concentration is 9.5g/L, the temperature is 55 ℃, and the volume is 7.5m3Introducing nitrogen gas with the flow rate of 0.5m into the bottom liquid of the reaction kettle3And h, setting the reaction temperature to be 55 ℃ and the stirring speed of the reaction kettle to be 150r/min, simultaneously adding the nickel-cobalt-manganese sulfate solution, 10% ammonia water solution and 35% caustic soda solution into the kettle through corresponding liquid inlet pipes for reaction synthesis, wherein in 8h before the reaction, the adding amount of the nickel-cobalt-manganese sulfate solution is fixed to be 200L/h, simultaneously adjusting the using amounts of the caustic soda solution and the ammonia water to reduce the pH of the reaction system to 10.0, and maintaining the ammonia concentration to be 9.0 g/L. In the process from 8 hours to the end of the reaction, while the adding amount of the nickel-cobalt-manganese sulfate solution is fixed to 600L/h, the use amounts of liquid caustic soda and ammonia water are adjusted to stabilize the pH of the reaction system at 10.5, and the concentration of ammonia is maintained at 10 g/L; and (3) starting material circulation between the reaction kettle and the thickener after the material liquid level in the reaction kettle rises to the overflow port, stopping feeding reaction after precursor particles D50 are 10 mu m, washing and drying the finished product slurry to obtain the slurry with the particle size distribution width: (D90-D10)/(D90+ D10) × 100 ═ 20-22) large particle size nickel cobalt manganese ternary precursor.
Example 2
Mixing Ni2+，Co2+，Mn2+The molar ratio of the raw materials is 34.8: 32.0:34.2 preparing a nickel-cobalt-manganese sulfate solution with the total metal concentration of 120 g/L; at 12m3The pH value of the reaction kettle is 12, the ammonia concentration is 10.9g/L, the temperature is 65 ℃, and the volume is 7.0m3Introducing nitrogen gas with the flow rate of 3m into the bottom liquid of the reaction kettle3And h, setting the reaction temperature to be 65 ℃ and the stirring speed of the reaction kettle to be 250r/min, simultaneously adding the salt solution, 20% ammonia water solution and 25% caustic soda solution into the kettle through corresponding liquid inlet pipes for reaction synthesis, wherein the dosage of the salt solution is fixed for 8h in the early stage of the reaction, the dosage of the caustic soda solution and the ammonia water is adjusted to reduce the pH of the reaction system to 10.4 while the dosage of the salt solution is fixed for 250L/h, and the ammonia concentration is maintained to be 10.5 g/L. After 8h, fixing the adding amount of the salt solution to 700L/h, adjusting the use amounts of liquid caustic soda and ammonia water to stabilize the pH of the reaction system at 10.8, and maintaining the ammonia concentration at 15 g/L; and (3) starting material circulation between the reaction kettle and the thickener after the material liquid level in the reaction kettle rises to the overflow port, stopping feeding reaction after precursor particles D50 are 11 microns, washing and drying the finished product slurry to obtain the slurry with the particle size distribution width: (D90-D10)/(D90+ D10) × 100 ═ 25-28) large particle size nickel cobalt manganese ternary precursor.
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 (4)
1. A method for improving the particle size distribution width of a nickel-cobalt-manganese ternary precursor is characterized by comprising the following steps:
(1) mixing Ni2+、Co2+、Mn2+According to the molar ratio of (33.8 +/-1): (33.0 +/-1) preparing a nickel-cobalt-manganese sulfate solution with the total metal concentration of 100 g/L-120 g/L (33.2 +/-1);
(2) preparing reaction base liquid in a reaction kettle and introducing N2The temperature of the reaction bottom liquid is 55-65 ℃, and the adding amount of the reaction bottom liquid is 55-65% of the volume of the reaction kettle;
(3) adding the nickel-cobalt-manganese sulfate solution prepared in the step (1), liquid caustic soda and an ammonia water solution into the reaction kettle bottom solution obtained in the step (2) in a concurrent flow manner for carrying out a coprecipitation reaction, controlling the reaction temperature to be 55-65 ℃ and the stirring speed to be 250r/min, adjusting the use amounts of the liquid caustic soda and the ammonia water within 8h before the reaction to ensure that the pH of the reaction system is 10.0-10.4 and the ammonia concentration is maintained at 9.0-10.5g/L, and adjusting the use amounts of the liquid caustic soda and the ammonia water to ensure that the pH of the reaction system is stabilized at 10.5-10.8 and the ammonia concentration is maintained at 10-15g/L at the stage from 8h to the end of the reaction; and (3) growing crystal particles generated by the coprecipitation reaction to a particle size D50: stopping the reaction after 10.0-11.0 μm;
(4) and (4) washing and drying the semi-finished product slurry obtained in the step (3) to obtain the nickel-cobalt-manganese ternary precursor.
2. The method according to claim 1, wherein the reaction base solution in the step (2) is prepared by pure water, ammonia water and liquid alkali, the pH of the reaction base solution is 11-12, and the ammonia concentration is 9.5-11.0 g/L; n is a radical of2The flow rate of (A) is 0.5-3.0m3/h。
3. The method as claimed in claim 1, wherein the flow rate of the nickel cobalt manganese sulfate solution in step (3) is 200-700L/h.
4. The method as claimed in claim 1, wherein the concentration of the alkali solution in the step (3) is 25% -35%, and the concentration of the ammonia water solution is 10% -20%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114180651A (en) * | 2021-12-22 | 2022-03-15 | 天齐创锂科技(深圳)有限公司 | Method for making peak of wide particle size distribution ternary precursor material |
| CN114477315A (en) * | 2022-02-25 | 2022-05-13 | 荆门市格林美新材料有限公司 | Synthesis method of nickel-cobalt-manganese ternary positive electrode material precursor |
| CN114573043A (en) * | 2021-12-31 | 2022-06-03 | 北京当升材料科技股份有限公司 | Positive electrode material and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114180651A (en) * | 2021-12-22 | 2022-03-15 | 天齐创锂科技(深圳)有限公司 | Method for making peak of wide particle size distribution ternary precursor material |
| CN114180651B (en) * | 2021-12-22 | 2023-10-27 | 天齐创锂科技(深圳)有限公司 | Method for peaking ternary precursor material with wide particle size distribution |
| CN114573043A (en) * | 2021-12-31 | 2022-06-03 | 北京当升材料科技股份有限公司 | Positive electrode material and preparation method and application thereof |
| CN114573043B (en) * | 2021-12-31 | 2023-12-22 | 北京当升材料科技股份有限公司 | Positive electrode material, preparation method and application thereof |
| CN114477315A (en) * | 2022-02-25 | 2022-05-13 | 荆门市格林美新材料有限公司 | Synthesis method of nickel-cobalt-manganese ternary positive electrode material precursor |
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