CN112591805B - 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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- C01—INORGANIC CHEMISTRY
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Abstract
A method for increasing the width of particle size distribution of a nickel-cobalt-manganese ternary precursor, comprising: the nickel cobalt manganese sulfate solution, the liquid alkali and the ammonia water solution are added into a reaction kettle provided with a base solution in parallel to carry out coprecipitation reaction, the pH value is kept to be 10.0-10.4 by adjusting the dosage of the liquid alkali and the ammonia water in the early 8 hours of the reaction under the conditions of 55-65 ℃ and stirring rotation speed of 150-250r/min, the ammonia concentration is kept to be 9.0-10.5g/L, and the pH value is kept to be 10.5-10.8 by adjusting the dosage of the liquid alkali and the ammonia water in the stage from 8 hours 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 in the initial stage of the reaction, and the particle size distribution width of the corresponding large-particle product in the mixture 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 granularity distribution width of a nickel-cobalt-manganese ternary precursor.
Background
The low-nickel type nickel-cobalt-manganese ternary precursor mixture is an important raw material for preparing the energy storage battery, and has wide application field and various specifications and models. Wherein the particle size distribution of the mixture is an important index affecting the physicochemical properties of the mixture. The particle size distribution width of the mixture is influenced 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 higher PH, higher rotating speed and the like in the early reaction stage, and is not easy to form an aggregate crystal nucleus in the early reaction stage, 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 mixture is narrowed, and the normal production requirements of downstream clients cannot be met stably.
Disclosure of Invention
Aiming at the defects existing in 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 increasing the width of particle size distribution of a nickel-cobalt-manganese ternary precursor, the method comprising:
(1) Ni is added with 2+ 、Co 2+ 、Mn 2+ According to the mol ratio of (33.8+/-1): (33.0+/-1) preparing nickel cobalt manganese sulfate solution with the total metal concentration of 100 g/L-120 g/L;
(2) Preparing reaction base solution in a reaction kettle and introducing N 2 The temperature of the reaction base solution is 55-65 ℃, and the adding amount of the reaction base solution is 55-65% of the volume of the reaction kettle;
(3) Adding the nickel cobalt manganese sulfate solution, the liquid alkali and the ammonia water solution prepared in the step (1) into the bottom solution of the reaction kettle obtained in the step (2) in parallel to carry out coprecipitation reaction, controlling the reaction temperature to be 55-65 ℃, stirring the mixture at a rotating speed of 150-250r/min, adjusting the pH value of a reaction system to be 10.0-10.4 by adjusting the dosage of the liquid alkali and the ammonia water in the early 8 hours of the reaction, maintaining the ammonia concentration to be 9.0-10.5g/L, and adjusting the dosage of the liquid alkali and the ammonia water to stabilize the pH value of the reaction system to be 10.5-10.8 and maintaining the ammonia concentration to be 10-15g/L in the stage from 8 hours 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 (3) 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 value of the reaction base solution is 11-12, and the ammonia concentration is 9.5-11.0g/L; n (N) 2 The flow rate of (2) is 0.5-3.0m 3 /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 invention has the beneficial technical effects that the operation is simple and easy, the particle size distribution width of the product is increased in the initial stage of the reaction by optimizing the production process, the particle size distribution width of the corresponding large-particle product in the mixture can be effectively increased, the (D90-D10)/(D90+D10) x 100= (20-29) is achieved, and the problem that the particle size distribution of the mixture is too narrow is effectively solved; the product produced by the invention can meet various indexes of customer requirements while improving the width of particle size distribution.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
Example 1
Ni is added with 2+ 、Co 2+ 、Mn 2+ The molar ratio is 32.8:34.0:32.2 preparing nickel cobalt manganese sulfate solution with the total metal concentration of 100 g/L; at 12m 3 The reaction kettle of (1) is prepared with pH=11, ammonia concentration=9.5 g/L, temperature is 55 ℃ and volume is 7.5m 3 Introducing nitrogen into the bottom solution of the reaction kettle with the flow of 0.5m 3 And/h, under the condition that the reaction temperature is set to 55 ℃ and the stirring rotation speed of the reaction kettle is 150r/min, simultaneously adding the nickel cobalt manganese sulfate solution, 10% ammonia water solution and 35% liquid alkali into the kettle through corresponding liquid inlet pipes to perform reaction synthesis, fixing the adding amount of the nickel cobalt manganese sulfate solution to 200L/h in the early 8h of the reaction, and simultaneously adjusting the liquid alkali and ammonia water for useThe pH of the reaction system was lowered to 10.0 and the ammonia concentration was maintained at 9.0g/L. In the process from 8 hours to the end of the reaction, fixing the adding amount of the nickel cobalt manganese sulfate solution to 600L/h, and simultaneously adjusting the dosage of liquid alkali and ammonia water to ensure that the PH of a reaction system is stabilized at 10.5, and maintaining the ammonia concentration to be 10g/L; when the material liquid level in the reaction kettle rises to an overflow port, starting material circulation between the reaction kettle and a thickener, stopping feeding reaction after precursor particles D50=10μm, washing and drying finished slurry to obtain the particle size distribution width of: (d90-d10)/(d90+d10) 100= (20-22) large particle nickel cobalt manganese ternary precursor.
Example 2
Ni is added with 2+ ，Co 2+ ，Mn 2+ The molar ratio is 34.8:32.0:34.2 preparing a nickel cobalt manganese sulfate solution with the total metal concentration of 120 g/L; at 12m 3 The reaction kettle of (1) is prepared with pH=12, ammonia concentration=10.9 g/L, temperature is 65 ℃ and volume is 7.0m 3 Introducing nitrogen into the bottom solution of the reaction kettle with the flow rate of 3m 3 And/h, setting the reaction temperature to 65 ℃, simultaneously adding the salt solution, 20% ammonia water solution and 25% liquid alkali into the reaction kettle through corresponding liquid inlet pipes under the condition of the stirring rotating speed of the reaction kettle of 250r/min, synthesizing the reaction, fixing the adding amount of the salt solution for 8h in the early stage of the reaction, and simultaneously adjusting the using amount of the liquid alkali and the ammonia water to enable the PH of the reaction system to be reduced to 10.4 while maintaining the ammonia concentration to be 10.5g/L. After 8 hours, fixing the adding amount of the salt solution to 700L/h, and simultaneously adjusting the dosage of liquid alkali and ammonia water to ensure that the PH of a reaction system is stabilized at 10.8, and maintaining the ammonia concentration to be 15g/L; when the material liquid level in the reaction kettle rises to an overflow port, starting material circulation between the reaction kettle and a thickener, stopping feeding reaction after precursor particles D50=11μm, washing and drying finished slurry to obtain the particle size distribution width of: (d90-d10)/(d90+d10) 100= (25-28) large particle nickel cobalt manganese ternary precursor.
The foregoing description of the preferred embodiments of the invention is merely illustrative of the invention and is not intended to be limiting. It should be noted that, for those skilled in the art, other equivalent modifications can be made in light of the technical teaching provided by the present invention, and the present invention can be implemented as the scope of protection.
Claims (3)
1. A method for increasing the width of particle size distribution of a nickel-cobalt-manganese ternary precursor, the method comprising:
(1) Ni is added with 2+ 、Co 2+ 、Mn 2+ According to the mol ratio of (33.8+/-1): (33.0+/-1) preparing nickel cobalt manganese sulfate solution with the total metal concentration of 100 g/L-120 g/L;
(2) Preparing reaction base solution in a reaction kettle and introducing N 2 The temperature of the reaction base solution is 55-65 ℃, the adding amount of the reaction base solution is 55-65% of the volume of the reaction kettle, and the pH of the reaction base solution is 11-12;
(3) Adding the nickel cobalt manganese sulfate solution, the liquid alkali and the ammonia water solution prepared in the step (1) into the bottom solution of the reaction kettle obtained in the step (2) in parallel to carry out coprecipitation reaction, controlling the reaction temperature to be 55-65 ℃, stirring the mixture at a rotating speed of 150-250r/min, adjusting the pH value of a reaction system to be 10.0-10.4 by adjusting the dosage of the liquid alkali and the ammonia water in the early 8 hours of the reaction, maintaining the ammonia concentration to be 9.0-10.5g/L, and adjusting the dosage of the liquid alkali and the ammonia water to stabilize the pH value of the reaction system to be 10.5-10.8 and maintaining the ammonia concentration to be 10-15g/L in the stage from 8 hours 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; the flow rate of the nickel cobalt manganese sulfate solution is 200-700L/h;
(4) And (3) 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, and the ammonia concentration is 9.5-11.0g/L; n (N) 2 The flow rate of the catalyst is 0.5-3.0 m/h.
3. The method of claim 1, wherein the concentration of the liquid alkali in the step (3) is 25% -35% and the concentration of the aqueous ammonia solution is 10% -20%.
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| 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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