CN211998850U - Nickel-cobalt-manganese ternary precursor preparation device with stable particle size - Google Patents
Nickel-cobalt-manganese ternary precursor preparation device with stable particle size Download PDFInfo
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- CN211998850U CN211998850U CN202020144082.8U CN202020144082U CN211998850U CN 211998850 U CN211998850 U CN 211998850U CN 202020144082 U CN202020144082 U CN 202020144082U CN 211998850 U CN211998850 U CN 211998850U
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Abstract
The utility model discloses a nickel cobalt manganese ternary precursor preparation device with stable granularity, which comprises a reaction kettle; the reaction kettle comprises a kettle body, a kettle cover arranged at the top of the kettle body, a stirring shaft arranged in the kettle body, a motor arranged outside the kettle body and connected with one end of the stirring shaft in a matching way, and a stirring paddle arranged in the kettle body and connected with the other end of the stirring shaft in a matching way; the kettle cover is provided with a main material pipe, an auxiliary material pipe, an alkali liquor pipe, a complexing agent pipe and an air inlet pipe; the liquid outlet of the main material pipe is far away from the liquid outlet of the alkali liquor pipe; the liquid outlet of the auxiliary material pipe is close to the liquid outlet of the alkali liquor pipe; the distance between the liquid outlet of the main material pipe and the liquid outlet of the alkali liquor pipe is larger than the distance between the liquid outlet of the auxiliary material pipe and the liquid outlet of the alkali liquor pipe. The utility model discloses a under the stable prerequisite of pH in the control reation kettle, the nucleation of messenger's reaction in-process tiny particle goes on with growing up simultaneously steadily to reach granularity stability control's purpose.
Description
Technical Field
The utility model relates to a lithium ion battery technical field, concretely relates to stable nickel cobalt manganese ternary precursor preparation facilities of particle size.
Background
Lithium ion batteries are widely used due to their advantages of high voltage, high specific capacity, environmental protection, etc. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material and electrolyte, wherein the positive electrode material plays an important role in the performance of the lithium ion battery. The precursor of the anode material is very important for the performance of the anode material. At present, the precursor is mainly produced by adopting a coprecipitation method in China, the method comprises a continuous method and an intermittent method, and the granularity of the precursor influences key indexes such as tap density, compaction density and cycle performance of the anode material.
In the existing continuous process, the particle size is changed by mostly adopting a pH lifting mode. At a higher pH, the precipitation reaction is mainly nucleation and can generate a large amount of fine powder with small particles, and at a lower pH, the precipitation reaction is mainly growth and can form coarse powder with large particles; in addition, in the process of increasing and decreasing the pH, the reaction system has large fluctuation, the nucleation and growth process is unstable, the granularity is difficult to stably control, and the product performance is negatively influenced.
SUMMERY OF THE UTILITY MODEL
The utility model aims to solve the technical problem that the granularity fluctuation is big, the unstable technical defect of control in overcoming lithium cell positive pole material precursor production provides a nickel cobalt manganese ternary precursor preparation facilities that the granularity is stable. The utility model discloses a under the stable prerequisite of pH in the control reation kettle, the nucleation of messenger's reaction in-process tiny particle goes on with growing up simultaneously steadily to reach granularity stability control's purpose.
The utility model provides an above-mentioned technical problem adopted technical scheme as follows:
a preparation method of a nickel-cobalt-manganese ternary precursor with stable particle size comprises the following steps:
(1) introducing deionized water into the reaction kettle;
(2) introducing alkali liquor into the deionized water; the alkali liquor is gradually diffused in the aqueous solution in the reaction kettle, the concentration is gradually diluted, the alkali liquor before being completely diluted forms a high pH environment, the alkali liquor after being completely diluted forms a low pH environment, and the pH of the high pH environment is greater than that of the low pH environment;
(3) continuously introducing a main material flow and a complexing agent into the low-pH environment, controlling the stirring speed of the reaction kettle, and carrying out coprecipitation reaction to generate nickel-cobalt-manganese ternary precursor particles;
(4) measuring the particle size of the nickel-cobalt-manganese ternary precursor particles at intervals, introducing an auxiliary material flow to the high-pH environment when the particle size of the nickel-cobalt-manganese ternary precursor particles reaches the qualified range of the preset D50 particle size, maintaining the pH of the low-pH environment to be basically unchanged, measuring the particle size of the nickel-cobalt-manganese ternary precursor at intervals, and if the particle size of the nickel-cobalt-manganese ternary precursor is continuously reduced, reducing the flow rate of the auxiliary material flow, otherwise, increasing the flow rate of the auxiliary material flow; when the granularity of the nickel-cobalt-manganese ternary precursor is basically unchanged, maintaining the flow rate of the auxiliary material flow, and finally preparing the nickel-cobalt-manganese ternary precursor with stable granularity;
in the technical scheme, the main material flow and the auxiliary material flow comprise soluble nickel salt solution, soluble cobalt salt solution and soluble manganese salt solution; the flow rate of the main stream is greater than the flow rate of the auxiliary stream.
In the above technical solution, the preset particle size D50 is a preset theoretical value of the particle size D50 of the final product nickel-cobalt-manganese ternary precursor.
Preferably, in the step (1), the volume of the reaction kettle is 5m3。
Preferably, in the step (1), the deionized water is added to the reaction kettle 20cm below an overflow port.
Preferably, in the step (1), inert gas is introduced into the reaction kettle.
More preferably, in the step (1), the inert gas is nitrogen.
Preferably, in the step (1), the flow rate of the inert gas is 5-10 m3/h。
Preferably, in the step (1), alkali liquor is introduced into the reaction kettle until the pH value of the system is 10.90-11.60.
More preferably, the lye is a NaOH solution.
Preferably, in the step (1), the complexing agent is introduced into the reaction kettle until the concentration of the complexing agent in the system is 0.3-0.6 mol/L.
Preferably, the complexing agent is ammonia.
Preferably, in the step (1), the temperature of the reaction kettle is increased to 45-65 ℃.
More preferably, in the step (1), the temperature of the reaction kettle is increased to 59.5-60.5 ℃.
Preferably, in the step (2), the alkali liquor is a NaOH solution.
Preferably, in the step (2), the concentration of the alkali liquor is 5-8 mol/L.
More preferably, in the step (2), the concentration of the alkali liquor is 8 mol/L.
Preferably, in the step (2), the flow rate of the alkali liquor is 50-180L/h.
More preferably, in the step (2), the flow rate of the alkali liquor is 50-65L/h.
Preferably, in the step (2), the pH of the high-pH environment is more than 11.40, and the pH of the low-pH environment is 10.40-11.40.
Preferably, in the step (3), the concentration of the main stream is 1.5 mol/L.
Preferably, in the step (3), the flow rate of the main stream is 150 to 300L/h.
More preferably, in step (3), the flow rate of the main stream is 150L/h.
Preferably, in the step (3), the complexing agent is introduced into the reaction kettle until the concentration of the complexing agent in the system is 0.3-0.6 mol/L.
Preferably, in the step (3), the complexing agent is ammonia water.
Preferably, in the step (3), the flow rate of the complexing agent is 5-25L/h.
Preferably, in the step (3), the stirring speed is 150-200 rpm.
Preferably, in the step (4), the certain time interval is 2 h.
Preferably, in the step (4), the preset particle size of D50 is 3 μm to 15 μm.
More preferably, in the step (4), the preset particle size of D50 is 3 μm, 10 μm, or 15 μm.
Preferably, in the step (4), the qualified range of the preset D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 0.9 and 1.1 times of the preset D50 particle size.
More preferably, in the step (4), the preset qualified range of the D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 3+0.3 μm, 10 ± 0.5 μm and 15 ± 0.5 μm respectively.
Preferably, in the step (4), the flow rate of the auxiliary stream is 3% to 10% of the flow rate of the main stream.
Preferably, in the step (4), the flow rate of the auxiliary stream is 5-20L/h.
Preferably, in the step (4), when the auxiliary material flow is introduced into the high-pH environment, the flow rate of the main material flow is reduced to be the flow rate of the auxiliary material flow, and the pH of the low-pH environment is maintained to be basically unchanged; since the total stream (main stream + auxiliary stream) and the base stream are unchanged, a low pH environment is achieved with substantially unchanged pH.
Preferably, in the step (4), the pH at which the pH of the low-pH environment is substantially unchanged is ± 0.07 of the pH at the acceptable range.
Preferably, in the step (4), the liquid outlet of the auxiliary material flow in the aqueous solution of the reaction kettle is 2-5 cm away from the liquid outlet of the alkali liquor in the aqueous solution of the reaction kettle.
Preferably, in the step (4), the included angle between the liquid outlet direction of the auxiliary material flow in the aqueous solution of the reaction kettle and the liquid outlet direction of the alkali liquor in the aqueous solution of the reaction kettle is 90 °.
Preferably, in the step (4), the particle size is not changed basically, and the particle size of the D50 of the nickel-cobalt-manganese ternary precursor fluctuates between 0.95 and 1.05 times of the preset particle size of D50.
Preferably, in the step (4), the particle size of the D50 of the nickel-cobalt-manganese ternary precursor with stable particle size fluctuates between 0.95 and 1.05 times of the preset particle size of D50.
More preferably, in the step (4), the particle size of the D50 of the nickel-cobalt-manganese ternary precursor with stable particle size fluctuates between 3.05 ± 0.10 μm, 10.00 ± 0.35 μm and 15 ± 0.4 μm respectively.
Preferably, the composition of the main stream and the subsidiary stream is nickel sulfate, cobalt sulfate and manganese sulfate.
More preferably, the ratio of the nickel sulfate, the cobalt sulfate and the manganese sulfate is 8: 1 or 0.9: 0.05 by mole ratio.
In the technical scheme, when the preset particle size of D50 is 3 μm, in the step (2), the pH value of the high-pH environment is greater than 11.40, and the pH value of the low-pH environment is 11.05-11.40; in the step (4), the qualified range of the preset D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 3 +/-0.3 mu m; in the step (4), the flow rate of the auxiliary material flow is 3-10% of that of the main material flow; in the step (4), the pH value of the low-pH environment is 11.08 +/-0.05 when the pH value is basically unchanged; in the step (4), the particle size is basically unchanged, and the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 3.05 +/-0.10 microns.
In the technical scheme, when the preset particle size of D50 is 10 μm, in the step (2), the pH value of the high-pH environment is greater than 11.40, and the pH value of the low-pH environment is 10.65-11.05; in the step (4), the qualified range of the preset D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 10 +/-0.5 mu m; in the step (4), the flow rate of the auxiliary material flow is 3-10% of that of the main material flow; in the step (4), the pH value of the low-pH environment when the pH value is basically unchanged is 10.74 +/-0.07; in the step (4), the particle size is basically unchanged, and the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 10.00 +/-0.35 mu m.
In the technical scheme, when the preset particle size of D50 is 15 μm, in the step (2), the pH value of the high-pH environment is greater than 11.40, and the pH value of the low-pH environment is 10.48-11.02; in the step (4), the qualified range of the preset D50 particle size is that the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 15 +/-0.5 mu m; in the step (4), the flow rate of the auxiliary material flow is 3-10% of that of the main material flow; in the step (4), the pH value of the low-pH environment is 10.55 +/-0.05 when the pH value is basically unchanged; in the step (4), the granularity is basically unchanged, and the D50 particle size of the nickel-cobalt-manganese ternary precursor fluctuates between 15 +/-0.4 mu m.
The nickel-cobalt-manganese ternary precursor with stable particle size is prepared by the preparation method.
A nickel-cobalt-manganese ternary precursor preparation device with stable particle size comprises a reaction kettle; the reaction kettle comprises a kettle body, a kettle cover arranged at the top of the kettle body, a stirring shaft arranged in the kettle body, a motor arranged outside the kettle body and connected with one end of the stirring shaft in a matching manner, and a stirring paddle arranged in the kettle body and connected with the other end of the stirring shaft in a matching manner; the kettle cover is provided with a main material pipe, an auxiliary material pipe, an alkali liquor pipe, a complexing agent pipe and an air inlet pipe; the liquid outlet of the main material pipe is far away from the liquid outlet of the alkali liquor pipe; the liquid outlet of the auxiliary material pipe is close to the liquid outlet of the alkali liquor pipe; the distance between the liquid outlet of the main material pipe and the liquid outlet of the alkali liquor pipe is larger than the distance between the liquid outlet of the auxiliary material pipe and the liquid outlet of the alkali liquor pipe.
Further, the liquid outlet of the main material pipe and the liquid outlet of the alkali liquor pipe face the stirring shaft respectively.
Further, a 180-degree angle is formed between a horizontal connecting line of the main material pipe and the stirring shaft and a horizontal connecting line of the alkali liquor pipe and the stirring shaft.
Further, a horizontal connecting line of the main material pipe and the stirring shaft and a horizontal connecting line of the complexing agent pipe and the stirring shaft form a 90-degree angle.
Further, the horizontal connecting line of the air inlet pipe and the stirring shaft and the horizontal connecting line of the complexing agent pipe and the stirring shaft form an angle of 180 degrees.
Further, the horizontal distance between the main material pipe and the stirring shaft, the horizontal distance between the alkali liquor pipe and the stirring shaft, the horizontal distance between the complexing agent pipe and the stirring shaft, and the horizontal distance between the air inlet pipe and the stirring shaft are equal.
Further, the distance between the liquid outlet of the auxiliary material pipe and the liquid outlet of the alkali liquor pipe is 2-5 cm.
Further, the extension line of the liquid outlet of the auxiliary material pipe and the extension line of the liquid outlet of the alkaline liquid pipe form an included angle of 90 degrees.
Further, a main material pipe is formed at the liquid inlet end of the main material pipe and the liquid inlet end of the auxiliary material pipe; the auxiliary material pipe is provided with a flowmeter and a valve.
Further, the stirring paddle is of a single-layer propelling type.
Further, the stirring paddle is provided with three blades.
Further, the lateral wall of reation kettle sets up the overflow mouth, the overflow mouth with the vertical distance of kettle cover is 15 ~ 20 cm.
The basic principle of the utility model is as follows:
there are two reactions in the coprecipitation reaction: nucleation and growth of small particles. These two reactions are controlled by pH: nucleation predominates at high pH and growth predominates at low pH. In order to allow nucleation and growth to proceed simultaneously, it is necessary to provide both high and low pH environments in one reaction vessel.
There is concentration dilution process after alkali lye gets into reation kettle, consequently, the utility model discloses the utilization is the alkali lye before the complete dilution not provides high pH, and the alkali lye after the complete dilution provides low pH for reation kettle, has had two kinds of environment of high pH and low pH like this. Then, nickel-cobalt-manganese sulfate solution with certain flow is respectively introduced into the two environments, so that the nucleation and the growth are simultaneously carried out.
During nucleation, extremely large amount of small particles are formed, so that a small flow of sulfate solution (called auxiliary material) is needed, and the proportion of the sulfate solution is 3-10% of the total material flow; the nickel-cobalt-manganese sulfate material flow (main material flow + auxiliary material flow) in the total material pipe and the alkali flow are controlled to be unchanged, so that the pH is unchanged; the size of the auxiliary stream is then adjusted according to the particle size, as follows: after opening the auxiliary stream:
a. if the particle size of the material is continuously reduced, the auxiliary material flow is higher, the generated small particles are excessive, and at the moment, the opening of an auxiliary material valve needs to be reduced, so that the number of the small particles is reduced;
b. if the particle size of the material is continuously increased, the auxiliary material flow is low, the generated small particles are few, and at the moment, the opening of an auxiliary material valve needs to be increased, so that the number of the small particles is increased;
in the adjustment process, the change of the granularity is slow, large fluctuation can not be caused, and the nickel-cobalt-manganese ternary precursor is produced continuously (material solution is continuously added into the reaction kettle, and qualified products continuously flow out from an overflow port) and stably (the particle size of D50 of the nickel-cobalt-manganese ternary precursor fluctuates between 0.95 and 1.05 times of the preset particle size of D50) by a single reaction kettle.
Compared with the prior art, the beneficial effects of the utility model are that:
(1) the main material flow and the auxiliary material flow of the utility model are led into the reaction kettle according to a certain proportion, and a certain alkali flow is led into the reaction kettle, so that the pH value in the reaction kettle is kept at a lower level, and crystal nuclei grow up; the auxiliary material flow is close to the alkali flow, the concentration of the alkali is higher, and the auxiliary material and the alkali meet to quickly nucleate; the crystal nucleus flows to a region with lower pH of the reaction kettle along with stirring, and at the moment, the material of the main material tube is deposited on the crystal nucleus and grows up to form a secondary ball; after the system is stable, the particles in the reaction kettle have a stable particle size value, and when the proportion of the main material and the auxiliary material is adjusted, the particle size value is changed; the proportion of the main material and the auxiliary material is increased, and the granularity is increased; otherwise, the particle size decreases; after the system is stabilized, continuous production can be realized without other subsequent operations through the adjustment, the operation is simple and convenient, and the industrial production is convenient;
(2) the utility model can stably perform nucleation and growth of small particles in the reaction process under the premise of controlling the pH in the reaction kettle to be stable, thereby achieving the purpose of stably controlling the particle size;
(3) the utility model discloses the D50 particle diameter of the nickel cobalt manganese ternary precursor that the preparation obtained fluctuates between 0.95 ~ 1.05 times of the D50 granularity of predetermineeing, and the D50 granularity fluctuation of ternary precursor is less.
Drawings
FIG. 1 is a graph showing the particle size and pH change of a ternary precursor in the preparation process of example 1;
FIG. 2 is a graph showing the particle size and pH change of a ternary precursor in the preparation process of example 2;
FIG. 3 is a graph showing the particle size and pH change of the ternary precursor in the preparation process of example 3;
FIG. 4 is a schematic structural view of a ternary precursor production apparatus according to embodiment 4;
FIG. 5 is a schematic piping diagram (top view) of a ternary precursor manufacturing apparatus according to example 4;
FIG. 6 is a schematic view showing the discharge direction of the flows of the alkali solution and the auxiliary materials in the ternary precursor preparing apparatus according to example 4;
FIG. 7 is a graph showing the particle size and pH change of the ternary precursor in the preparation process of comparative example 1.
The corresponding part names for the various reference numbers in the figures are:
1-a reaction kettle; 2-kettle body; 3-a kettle cover; 4-stirring shaft; 5, a motor; 6-stirring paddle; 7-a main material pipe; 8-auxiliary material pipe; 9-alkali liquor tube; 10-complexing agent tube; 11-an air inlet pipe; 12-a main feed pipe; 13-a paddle; 14-baffle.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It should be understood that these examples are for further illustration of the present invention only, and are not intended to limit the scope of the present invention. It should be further understood that after reading the above description of the present invention, those skilled in the art will make certain insubstantial changes or modifications to the present invention, and shall still fall within the scope of the present invention.
Example 1
A preparation method of a nickel-cobalt-manganese ternary precursor with stable particle size comprises the following steps:
(1) preparation conditions are as follows: at 5m3Adding deionized water into a reaction kettle until the volume is about 20cm below an overflow port, starting stirring, adding a NaOH solution until the pH value is 10.9-11.2, adding ammonia water until the concentration of ammonia water in the system is 0.5-0.6 mol/L, introducing nitrogen into the reaction kettle, wherein the flow rate of the nitrogen is 5-10 m3Heating to 59.5-60.5 ℃ at the same time;
(2) start-up to prepare 10 μm NCM811 precursor: after the conditions are met, introducing 8mol/L NaOH solution into the reaction kettle, controlling the flow of NaOH to be 56-61L/h, gradually diffusing the NaOH solution in the aqueous solution in the reaction kettle, gradually diluting the concentration of the NaOH solution, and forming a high-pH environment before the NaOH solution is not completely diluted, wherein the pH is more than 11.4; forming a low pH environment by using the completely diluted NaOH solution, wherein the pH is 10.65-11.05; continuously introducing 1.5mol/L sulfate Ni of a main stream into a low-pH environment0.8Co0.1Mn0.1SO4Introducing 10mol/L ammonia water into the solution until the ammonia water concentration of the system is 0.5-0.6 mol/L, controlling the main material flow to be 150L/h, the auxiliary material flow to be 0, the ammonia water flow to be 10-15L/h, the stirring speed to be 150-200 rpm, and carrying out coprecipitation reaction on the feed liquid in the reaction kettle to generate nickel-cobalt-manganese ternary precursor particles;
(3) growing: measuring the granularity of the generated nickel-cobalt-manganese ternary precursor particles at intervals of 2 h; when the nickel cobalt manganese ternary precursor is started, the particle size is small, the D50 is 2.68 mu m, the particle size is increased to 9.5 mu m after the precursor grows for 96 hours and belongs to a qualified range, the auxiliary material is started for 8L/h, the main material is reduced to 142L/h, the pH value of the low-pH environment is maintained to fluctuate within the range of 10.74 +/-0.07, the particle size is measured at intervals of 2 hours, and the particle size test result shows that after the auxiliary material is started, the expansion speed of D10 and D50 is reduced and stabilized, the fluctuation of D50 is small, when the particle size of the nickel cobalt manganese ternary precursor is stabilized within 10.00 +/-0.35 mu m, the flow speed of the auxiliary material flow is maintained, and the nickel cobalt manganese ternary precursor with stable particle size is.
Example 2
A preparation method of a nickel-cobalt-manganese ternary precursor with stable particle size comprises the following steps:
(1) preparation conditions are as follows: at 5m3Adding deionized water into a reaction kettle until the volume is about 20cm below an overflow port, starting stirring, adding a NaOH solution until the pH value is 11.3-11.6, adding ammonia water until the concentration of ammonia water in the system is 0.3-0.4 mol/L, introducing nitrogen into the reaction kettle, wherein the flow rate of the nitrogen is 5-10 m3Heating to 59.5-60.5 ℃ at the same time;
(2) preparation of 3 μm NCM811 precursor on start-up: after the conditions are met, introducing 8mol/L NaOH solution into the reaction kettle, controlling the flow of NaOH to be 58-62L/h, gradually diffusing the NaOH solution in the aqueous solution in the reaction kettle, gradually diluting the concentration of the NaOH solution, and forming a high-pH environment by the NaOH solution before the NaOH solution is not completely diluted, wherein the pH is more than 11.4; forming a low pH environment by using the completely diluted NaOH solution, wherein the pH is 11.05-11.40; continuously introducing 1.5mol/L sulfate Ni of a main stream into a low-pH environment0.8Co0.1Mn0.1SO4Introducing 10mol/L ammonia water into the solution until the ammonia water concentration of the system is 0.3-0.4 mol/L, controlling the main material flow to be 150L/h, the auxiliary material flow to be 0, the ammonia water flow to be 5-10L/h, the stirring speed to be 150-200 rpm, and carrying out coprecipitation reaction on the feed liquid in the reaction kettle to generate nickel-cobalt-manganese ternary precursor particles;
(3) growing: measuring the granularity of the generated nickel-cobalt-manganese ternary precursor particles at intervals of 2 h; when the nickel cobalt manganese ternary precursor is started, the particle size is small, the D50 is 1.42 mu m, the particle size is increased to 2.9 mu m after the growth is 60 hours, the particle size belongs to a qualified range, the starting auxiliary material is 13L/h, the main material is reduced to 137L/h, the pH value of a low pH environment is maintained to fluctuate within the range of 11.08 +/-0.05, the particle size is measured at intervals of 2 hours, and the particle size test result shows that the rising speed of D50 is reduced and stabilized after the auxiliary material is started, the fluctuation of D50 is small, when the particle size of the nickel cobalt manganese ternary precursor is stabilized within the range of 3.05 +/-0.10 mu m, the flow speed of the auxiliary material flow is maintained, and the nickel cobalt manganese ternary precursor with stable particle.
Example 3
A preparation method of a nickel-cobalt-manganese ternary precursor with stable particle size comprises the following steps:
(1) preparation conditions are as follows: at 5m3Adding deionized water into the reaction kettle until the distance between the deionized water and the overflow port is about 20cm, starting stirring, adding NaOH solution until the pH value is 10.90-11.00, and adding ammonia water until the pH value is 10.90-11.00The ammonia water concentration of the system is 0.5-0.6 mol/L, nitrogen is introduced into the reaction kettle, and the flow rate of the nitrogen is 5-10 m3Heating to 59.5-60.5 ℃ at the same time;
(2) preparing a 15-micron NCM9055 precursor by starting up: after the conditions are met, introducing 8mol/L NaOH solution into the reaction kettle, controlling the flow of NaOH to be 55-60L/h, gradually diffusing the NaOH solution in the aqueous solution in the reaction kettle, gradually diluting the concentration of the NaOH solution, and forming a high-pH environment before the NaOH solution is not completely diluted, wherein the pH is more than 11.4; forming a low pH environment by using the completely diluted NaOH solution, wherein the pH is 10.48-11.02; continuously introducing 1.5mol/L sulfate Ni of a main stream into a low-pH environment0.9Co0.05Mn0.05SO4Introducing 10mol/L ammonia water into the solution until the ammonia water concentration of the system is 0.5-0.6 mol/L, controlling the main material flow to be 150L/h, the auxiliary material flow to be O, the ammonia water flow to be 20L/h, and the stirring speed to be 150-200 rpm, and carrying out coprecipitation reaction on the feed liquid in the reaction kettle to generate nickel-cobalt-manganese ternary precursor particles;
(3) growing: measuring the granularity of the generated nickel-cobalt-manganese ternary precursor particles at intervals of 2 h; when the nickel cobalt manganese ternary precursor is started, the particle size is small, the D50 is 4.50 micrometers, the particle size is increased to 14.8 micrometers after the growth is carried out for 106 hours, the particle size belongs to a qualified range, at the moment, the auxiliary material is started to be 6L/h, the main material is reduced to 144L/h, the pH value of a low pH environment is maintained to fluctuate within the range of 10.55 +/-0.05, the particle size is measured at intervals of 2 hours, and the particle size test result shows that after the auxiliary material is started, the expansion speed of D50 is reduced and stabilized, the fluctuation of D50 is small, when the particle size of the nickel cobalt manganese ternary precursor is stabilized within 15 +/-0.4 micrometers, the flow speed of the auxiliary material flow is maintained, and the nickel cobalt manganese ternary.
Example 4
A nickel-cobalt-manganese ternary precursor preparation device with stable particle size, as shown in fig. 4-6, comprising a reaction kettle 1; the reaction kettle 1 comprises a kettle body 2, a kettle cover 3 arranged at the top of the kettle body 2, a stirring shaft 4 arranged inside the kettle body 2, a motor 5 arranged outside the kettle body 2 and connected with one end of the stirring shaft 4 in a matching manner, and a stirring paddle 6 arranged inside the kettle body 2 and connected with the other end of the stirring shaft 4 in a matching manner; the kettle cover 3 is provided with a main material pipe 7, an auxiliary material pipe 8, an alkali liquor pipe 9, a complexing agent pipe 10 and an air inlet pipe 11; the liquid outlet of the main material pipe 7 is far away from the liquid outlet of the alkali liquor pipe 9; the liquid outlet of the auxiliary material pipe 8 is close to the liquid outlet of the alkali liquor pipe 9; the distance between the liquid outlet of the main material pipe 7 and the liquid outlet of the alkali liquor pipe 9 is larger than the distance between the liquid outlet of the auxiliary material pipe 8 and the liquid outlet of the alkali liquor pipe 9.
The liquid outlet of the main material pipe 7 and the liquid outlet of the alkali liquor pipe 9 face the stirring shaft 4 respectively.
The horizontal connecting line of the main material pipe 7 and the stirring shaft 4 and the horizontal connecting line of the alkali liquor pipe 9 and the stirring shaft 4 form an angle of 180 degrees.
The horizontal connecting line of the main material pipe 7 and the stirring shaft 4 and the horizontal connecting line of the complexing agent pipe 10 and the stirring shaft 4 form a 90-degree angle.
The horizontal connecting line of the air inlet pipe 11 and the stirring shaft 4 and the horizontal connecting line of the complexing agent pipe 1O and the stirring shaft 4 form an angle of 180 degrees.
The horizontal distance between the main pipe 7 and the stirring shaft 4, the horizontal distance between the alkali liquor pipe 9 and the stirring shaft 4, the horizontal distance between the complexing agent pipe 10 and the stirring shaft 4, and the horizontal distance between the air inlet pipe 11 and the stirring shaft 4 are equal.
The distance between the liquid outlet of the auxiliary material pipe 8 and the liquid outlet of the alkali liquor pipe 9 is 2-5 cm, and granulation is facilitated.
The extension line of the liquid outlet of the auxiliary material pipe 8 and the extension line of the liquid outlet of the alkaline liquid pipe 9 form an included angle of 90 degrees, so that better granulation is facilitated.
The liquid inlet end of the main material pipe 7 and the liquid inlet end of the auxiliary material pipe 8 form a main material pipe 12; the auxiliary material pipe 8 is provided with a flowmeter (not shown in the figure) and a valve (not shown in the figure); the pH can be conveniently kept unchanged by controlling the nickel-cobalt-manganese sulfate material flow (main material flow + auxiliary material flow) in the main material pipe 12 and the alkali flow in the alkali liquor pipe 9 to be unchanged.
The stirring paddle 6 is of a single-layer propelling type.
The stirring paddle 6 is provided with three paddles 13.
The lateral wall of reation kettle 1 sets up overflow mouth (not shown in the figure), the overflow mouth with kettle cover 3's vertical distance is 15 ~ 20 cm.
A baffle plate 14 is arranged in the kettle body 2.
The operation process of this embodiment is as follows:
(1) as shown in fig. 4 and 5, a main material pipe 7, an auxiliary material pipe 8, an alkali liquor pipe 9, a complexing agent pipe 10 and an air inlet pipe 11 are installed in a reaction kettle 1, and main material nickel cobalt manganese sulfate, auxiliary material nickel cobalt manganese sulfate, alkali liquor, ammonia water and nitrogen are respectively introduced into the reaction kettle 1; the main material pipe 7, the alkali liquor pipe 9, the complexing agent pipe 10 and the air inlet pipe 11 are arranged in a mode of forming a central angle of 90 degrees with each other, and the liquid outlet directions of the main material pipe 7, the alkali liquor pipe 9 and the complexing agent pipe 10 in the reaction kettle 1 are aligned to the circle center of the reaction kettle 1; a branch pipe, namely an auxiliary material pipe 8, is added on the main material pipe 7 and is positioned 2-5 cm near the alkali liquor pipe 9, the liquid outlet direction of the branch pipe and the alkali liquor outlet direction form 90 degrees (as shown in figure 6), the flow of the auxiliary material pipe 8 is controlled by a valve, a liquid inlet end of the main material pipe 7 and a liquid inlet end of the auxiliary material pipe 8 form a main material pipe 12, the nickel cobalt manganese sulfate material flow (the main material flow and the auxiliary material flow) in the main material pipe 12 and the alkali flow are controlled to be unchanged, and the pH is unchanged;
(2) adding clear water into the reaction kettle 1 to a position 20cm below an overflow port, then introducing a certain amount of alkali and ammonia water, and starting to continuously introduce nickel-cobalt-manganese sulfate, alkali, ammonia water and nitrogen gas for coprecipitation reaction after a system is stable;
(3) when the granularity is qualified, the auxiliary material valve is opened, the opening degree is 3-10%, and then the size of the auxiliary material flow is adjusted according to the granularity size, wherein the auxiliary material flow is as follows: after the flow of the auxiliary material is turned on,
a. if the particle size of the material is continuously reduced, the auxiliary material flow is higher, the generated small particles are excessive, and at the moment, the opening of an auxiliary material valve needs to be reduced, so that the number of the small particles is reduced;
b. if the particle size of the material is continuously increased, the auxiliary material flow is low, the generated small particles are few, and at the moment, the opening of an auxiliary material valve needs to be increased, so that the number of the small particles is increased;
in the adjusting process, the change of the granularity is slow, large fluctuation can not be caused, and the continuous and stable production of the nickel-cobalt-manganese ternary precursor by a single reaction kettle is finally realized.
Comparative example 1
The method for preparing the ternary precursor with the D50 particle size of 10 mu m by the conventional process comprises the following steps:
(1) preparation conditions are as follows: at 5m3Adding deionized water into a reaction kettle until the volume is about 20cm below an overflow port, starting stirring, adding NaOH solution until the pH value is 10.9-11.2, adding ammonia water to 0.5-0.6 mol/L, introducing nitrogen into the reaction kettle at the flow velocity of 5-10 m3Heating to 59.5-60.5 ℃ at the same time;
(2) start-up to prepare 10 μm NCM811 precursor: after the conditions are met, 8mol/L NaOH solution is introduced into the reaction kettle, the flow of NaOH is controlled to be 56-61L/h, and sulfate Ni with the material flow of 1.5mol/L is continuously introduced0.8Co0.1Mn0.1SO4Controlling the material flow to be 150L/h, controlling the flow of ammonia water to be 10-15L/h, controlling the stirring speed to be 150-200 rpm, and carrying out coprecipitation reaction on the material liquid in the reaction kettle to generate nickel-cobalt-manganese ternary precursor particles;
(3) growing: measuring the granularity of the generated nickel-cobalt-manganese ternary precursor particles at intervals of 2 h; when the nickel cobalt manganese ternary precursor is started, the particle size is small, the D50 is 2.68 mu m, when the particle size is increased to 9.5 mu m after the precursor grows for 96 hours, the alkali flow is increased gradually, the pH is increased, when the pH is over 11.4, small particles are generated in a reaction kettle, when the D10 is decreased, the alkali flow is decreased, the pH is reduced, the pH is maintained at 11.2-11.4, the particle size starts to grow, and the D50 particle size of the finally prepared nickel cobalt manganese ternary precursor has large fluctuation, namely 10.10 +/-1.00 mu m.
Effects of the embodiment
In the embodiment 1, the preset D50 particle size of the nickel-cobalt-manganese ternary precursor is 10 mu m; the particle size fluctuation of the nickel-cobalt-manganese ternary precursor D50 prepared in example 1 is small and is 10.00 +/-0.35 mu m (see FIG. 1); the nickel-cobalt-manganese ternary precursor D50 prepared by the conventional process has large particle size fluctuation, and the particle size fluctuation is 10.10 +/-1.00 mu m (see figure 7).
In the embodiment 2, the preset D50 particle size of the nickel-cobalt-manganese ternary precursor is 3 μm; the particle size fluctuation of the nickel-cobalt-manganese ternary precursor D50 prepared in example 2 is small and is 3.05 +/-0.10 mu m (see FIG. 2); the nickel-cobalt-manganese ternary precursor D50 prepared by the conventional process has large particle size fluctuation, and the particle size fluctuation is 3.10 +/-0.50 mu m.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions, or substitutions can be made without departing from the spirit and scope of the invention.
Claims (10)
1. The device for preparing the nickel-cobalt-manganese ternary precursor with stable particle size is characterized by comprising a reaction kettle (1); the reaction kettle (1) comprises a kettle body (2), a kettle cover (3) arranged at the top of the kettle body (2), a stirring shaft (4) arranged inside the kettle body (2), a motor (5) arranged outside the kettle body (2) and connected with one end of the stirring shaft (4) in a matching manner, and a stirring paddle (6) arranged inside the kettle body (2) and connected with the other end of the stirring shaft (4) in a matching manner; the kettle cover (3) is provided with a main material pipe (7), an auxiliary material pipe (8), an alkali liquor pipe (9), a complexing agent pipe (10) and an air inlet pipe (11); the liquid outlet of the main material pipe (7) is far away from the liquid outlet of the alkali liquor pipe (9); the liquid outlet of the auxiliary material pipe (8) is close to the liquid outlet of the alkali liquor pipe (9); the distance between the liquid outlet of the main material pipe (7) and the liquid outlet of the alkali liquor pipe (9) is larger than the distance between the liquid outlet of the auxiliary material pipe (8) and the liquid outlet of the alkali liquor pipe (9).
2. The apparatus for preparing nickel cobalt manganese ternary precursor with stable particle size according to claim 1, wherein the outlet of the main pipe (7) and the outlet of the alkaline solution pipe (9) are respectively facing the stirring shaft (4).
3. The apparatus for preparing nickel cobalt manganese ternary precursor with stable particle size according to claim 1, wherein the horizontal line between the main pipe (7) and the stirring shaft (4) and the horizontal line between the alkali liquor pipe (9) and the stirring shaft (4) are 180 °.
4. The apparatus for preparing nickel cobalt manganese ternary precursor with stable particle size according to claim 3, wherein the horizontal line connecting the main pipe (7) and the stirring shaft (4) is 90 ° to the horizontal line connecting the complexing agent pipe (10) and the stirring shaft (4).
5. The apparatus for preparing Ni-Co-Mn ternary precursor with stable particle size according to claim 4, wherein the horizontal line of the gas inlet pipe (11) and the stirring shaft (4) is 180 ° with the horizontal line of the complexing agent pipe (10) and the stirring shaft (4).
6. The device for preparing the nickel cobalt manganese ternary precursor with stable particle size according to claim 5, wherein the horizontal distance between the main pipe (7) and the stirring shaft (4), the horizontal distance between the alkali liquor pipe (9) and the stirring shaft (4), the horizontal distance between the complexing agent pipe (10) and the stirring shaft (4), and the horizontal distance between the air inlet pipe (11) and the stirring shaft (4) are all equal.
7. The apparatus for preparing nickel cobalt manganese ternary precursor with stable particle size according to claim 1, wherein the distance between the liquid outlet of the auxiliary pipe (8) and the liquid outlet of the alkaline solution pipe (9) is 2-5 cm.
8. The apparatus for preparing nickel cobalt manganese ternary precursor with stable particle size according to claim 1, wherein the angle between the extension line of the liquid outlet of the auxiliary pipe (8) and the extension line of the liquid outlet of the alkaline liquid pipe (9) is 90 °.
9. The apparatus for preparing nickel cobalt manganese ternary precursor with stable particle size according to claim 1, wherein the inlet of the main material pipe (7) and the inlet of the auxiliary material pipe (8) form a main material pipe (12); the auxiliary material pipe (8) is provided with a flowmeter and a valve.
10. The apparatus for preparing nickel-cobalt-manganese ternary precursor with stable particle size according to claim 1, wherein the stirring paddle (6) is of single-layer propelling type; the stirring paddle (6) is provided with three blades (13).
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| CN111153445A (en) * | 2020-01-22 | 2020-05-15 | 宁波容百新能源科技股份有限公司 | Nickel-cobalt-manganese ternary precursor with stable particle size and preparation method and preparation device thereof |
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| CN111153445A (en) * | 2020-01-22 | 2020-05-15 | 宁波容百新能源科技股份有限公司 | Nickel-cobalt-manganese ternary precursor with stable particle size and preparation method and preparation device thereof |
| CN111153445B (en) * | 2020-01-22 | 2023-10-31 | 湖北容百锂电材料有限公司 | Nickel-cobalt-manganese ternary precursor with stable granularity and preparation method and preparation device thereof |
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