CN114684865B - Preparation method of aluminum-doped cobalt carbonate particles - Google Patents
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Abstract
The invention provides a preparation method of aluminum-doped cobalt carbonate particles, which comprises the steps of firstly preparing the aluminum-doped cobalt carbonate particles by adopting alkali and aluminum-cobalt salt solution, then coating the aluminum-doped cobalt carbonate particles with aluminum-free cobalt salt, and finally preparing the aluminum-doped cobalt carbonate particles through post-treatment. The preparation method of the aluminum-doped cobalt carbonate particles is simple, the precipitation and aggregation of aluminum elements in the aluminum-doped cobalt carbonate particles are effectively reduced by a coating method, the aluminum elements are distributed more uniformly in the cobalt carbonate particles in yield, and the prepared aluminum-doped cobalt carbonate particles have good sphericity and uniform particle size distribution.
Description
Technical Field
The invention relates to a preparation method of a precursor, in particular to a preparation method of a cobalt carbonate precursor for battery-grade cobaltosic oxide.
Background
Lithium cobalt oxide (LiCoO) 2 ) The positive electrode material plays a vital role in the field of portable electronic products, and LiCoO was first used by Sony corporation since 1991 2 The commercial lithium ion battery is prepared by taking the anode material and the graphite as the cathode material, and the lithium ion battery is innovatedThe appearance of the portable electronic product. LiCoO, especially in the field of high-end electronics 2 The lithium ion battery anode material is still the most competitive commercial lithium ion battery anode material in 3C consumer electronic products at present due to the advantages of high working voltage, high first coulomb efficiency, good cycle stability, high volume energy density and the like.
By increasing LiCoO 2 And the charging voltage of the lithium ion battery to obtain more specific capacity becomes an important research direction for developing a lithium ion battery with high energy density. In the development of high-voltage lithium cobaltate materials, doping is one of important key technologies of cobaltosic oxide precursors, and along with the continuous increase of the charge cut-off voltage, research on the types and doping amounts of doping elements of cobaltosic oxide is underway, such as Al, mg, ti, zr, la, ce and the like. The precursor product has very high upgrading speed, and the high-voltage lithium cobalt oxide is prepared by doping certain metal elements into the lithium cobalt oxide, so that the crystal structure stability of the lithium cobalt oxide under high voltage is improved, and the doped lithium cobalt oxide has high specific capacity and good cycle performance under high voltage, wherein the doped Al is the key point of research and development. The preparation of aluminum-doped cobaltosic oxide by adopting a cobalt carbonate system wet method has the outstanding problems that the higher the aluminum doping amount is, the more uneven the aluminum doping is, the more easily the aluminum is separated out on the surface, and Hua Yougu (Tian Li et Al) adopts ammonium bicarbonate as a detergent in patent CN108011101A, and the hydrolysis precipitation of Al element in the washing process is inhibited by introducing carbonate into washing water. However, the addition of ammonium bicarbonate increases the cost of production of the product and adversely affects the environment.
Disclosure of Invention
Based on the technical background, the inventor makes a keen approach, and found that: the method effectively prevents independent precipitation and aggregation of aluminum in the prepared precursor by coating cobalt salt without aluminum on the surface of aluminum-doped cobalt carbonate particles, solves the problems of growth of particle size and uneven particle size distribution, and ensures that the prepared aluminum-doped cobalt carbonate precursor particles have better sphericity.
The invention provides a preparation method of aluminum-doped cobalt carbonate particles, which comprises the following steps:
step 1, preparing aluminum-doped cobalt carbonate particles;
step 2, coating the aluminum-doped cobalt carbonate particles prepared in the step 1;
and 3, carrying out post-treatment on the product prepared in the step 2.
In a second aspect, the present invention provides aluminium doped cobalt carbonate particles obtainable by the process according to the first aspect of the present invention.
The preparation method of the aluminum-doped cobalt carbonate particles provided by the invention has the following advantages:
(1) The preparation method solves the problems of uneven particle size growth and particle size distribution of a hydroxide system;
(2) The preparation method aims at solving the problem that aluminum doping is easy to be unevenly doped in a cobalt carbonate system, and the problem is solved from the source, and aluminum-free cobalt salt is coated on the surface to prevent aluminum compounds from being separated out and aggregated independently.
Drawings
FIG. 1 shows a high magnification scanning electron microscope photograph of the aluminum-doped cobalt carbonate particles produced in example 4 of the present invention;
FIG. 2 shows a scanning electron micrograph of the aluminum-doped cobalt carbonate particles produced in example 4 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
A first aspect of the present invention provides a method for preparing aluminium doped cobalt carbonate particles, the method comprising the steps of:
step 1, preparing aluminum-doped cobalt carbonate particles;
step 2, coating the aluminum-doped cobalt carbonate particles prepared in the step 1;
and 3, carrying out post-treatment on the product prepared in the step 2.
This step is specifically described and illustrated below.
And step 1, preparing aluminum-doped cobalt carbonate particles.
The aluminum-doped cobalt carbonate particles are mainly prepared by mixing a salt solution and an alkali solution, and optionally adding a complexing agent.
Cobalt salt and aluminum salt are added into water to prepare mixed salt solution. In the present invention, the cobalt salt is selected from water-soluble cobalt salts, preferably, cobalt salts are selected from one or more of cobalt sulfate, cobalt nitrate, cobalt chloride, and cobalt acetate, and more preferably, cobalt salts are cobalt sulfate, cobalt nitrate, or cobalt chloride.
The aluminum salt is selected from water-soluble aluminum salts, preferably, the aluminum salt is selected from one or more of aluminum sulfate, aluminum chloride, aluminum nitrate and aluminum acetate, and more preferably, the aluminum salt is one or two of aluminum sulfate and aluminum chloride.
According to the invention, the mass ratio of the cobalt salt to the aluminum salt is (50-1550): 1, preferably the mass ratio is (50-1000): 1, more preferably (60-200): 1.
The concentration of the aluminum-cobalt mixed salt solution is 0.1 to 10mol/L, preferably 0.5 to 5mol/L, and more preferably 1 to 3mol/L.
Experiments show that the concentration of the aluminum-cobalt mixed salt solution can influence the morphology and particle size distribution of the finally prepared precursor, and the precursor prepared by selecting 0.1-10 mol/L of the aluminum-cobalt mixed salt solution has better sphericity and larger and more uniform particle size.
According to the invention, the preparation is carried out in a reaction vessel, in which water, complexing agent or base is first added as a base solution, the pH of which is 7 to 10, preferably 7.5 to 9, more preferably 8. The water in the bottom liquid is added, and the complexing agent and the alkali are added into the reaction kettle in an alternative or common adding mode.
The complexing agent is selected from one or more of ammonia water, ammonium sulfate, ethylenediamine tetraacetic acid, oxalic acid, sodium bicarbonate, ammonium chloride, ammonium bicarbonate, diethylenetriamine pentacarboxylate, sodium hexametaphosphate and triethanolamine, preferably one or more of ammonia water, ammonium sulfate, ethylenediamine tetraacetic acid, sodium bicarbonate, ammonium bicarbonate and ammonium chloride, more preferably one or more of ammonia water, ammonium sulfate, ammonium bicarbonate and ethylenediamine tetraacetic acid.
The alkali is selected from one or more of ammonium bicarbonate, sodium carbonate and ammonium carbonate, preferably one or two of ammonium bicarbonate and ammonium carbonate, more preferably ammonium bicarbonate. In the present invention, ammonium bicarbonate can act as both a precipitant and a pH adjuster.
In the present invention, the mass ratio of the sum of the masses of the base and the complexing agent in the base solution to water is (0.001 to 0.5): 1, preferably (0.003 to 0.1): 1, and more preferably (0.005 to 0.05): 1.
In step 1 of the present invention, an alkali solution is prepared by dissolving an alkali in water, the concentration of the alkali solution being 100 to 400g/L, preferably 120 to 300g/L, more preferably 150 to 250g/L.
According to the present invention, after preparing the base solution, the alkali solution and the cobalt-aluminum mixed salt solution are added to the reaction vessel to which the base solution is added, preferably continuously, more preferably continuously, at a constant rate by a peristaltic pump. The continuous addition allows the reaction to proceed more completely.
The ratio of the adding speed of the alkali solution to the adding speed of the mixed salt solution is (0.5-5): 1, preferably (1 to 4): 1, more preferably (1.5 to 3): 1.
The inventor discovers that the precursor prepared by adopting the addition speed ratio has good sphericity, larger particle size and more uniformity.
In the present invention, the reaction temperature is 30 to 100 ℃, preferably 40 to 70 ℃, more preferably 45 to 60 ℃.
In the preparation process of the precursor, the shape of the finally prepared precursor can be directly influenced by the high and low reaction temperature, and the precursor can be oxidized due to the excessively high reaction temperature.
The reaction in step 1 is carried out with stirring at a speed of 500 to 1500r/min, preferably 600 to 1200r/min, more preferably 700 to 1000r/min.
The stirring speed can directly influence the tap density of the prepared precursor, and the precursor prepared by the stirring speed in the range has higher tap density.
During the reaction, the pH of the reaction system should be controlled to 7 to 10, preferably 7.1 to 9, more preferably 7.1 to 8. In the present invention, the pH of the reaction system is controlled by adjusting the flow rate of the base.
The pH of the precursor reaction system also affects the morphology of the prepared precursor, and the inventor discovers that the pH control of the reaction system in the above range is more beneficial to forming the precursor with good sphericity and uniform particle size, and the prepared precursor has higher tap density.
When the aluminum-doped cobalt carbonate particles grow to a certain particle size, the stirring speed of the reaction kettle is properly reduced, preferably the aluminum-doped cobalt carbonate particles grow to 5-15 mu m, more preferably the aluminum-doped cobalt carbonate particles grow to 12-15 mu m, and the stirring speed of the reaction kettle is reduced.
The stirring speed after the reduction is 500 to 1000r/min, preferably 600 to 900r/min, more preferably 600 to 800r/min.
The stirring speed is reduced in the invention to prevent the generation of small particles, so that the particle size of the prepared precursor is more uniform, the nucleation tendency is enhanced along with the growth of the particles in the preparation process, the growth tendency of the particles is weakened, and if the stirring speed is not reduced, the particle size of the finally prepared aluminum-doped cobalt carbonate is smaller and the particle sizes are different.
And 2, coating the aluminum-doped cobalt carbonate particles prepared in the step 1.
According to the invention, the cobalt aluminum carbonate particles to be doped are coated with the replacement salt solution by growing the particle size of the cobalt aluminum carbonate to 10 to 20. Mu.m, preferably 15 to 19. Mu.m, more preferably 16 to 18. Mu.m.
The inventor discovers that the coating of the surface of the prepared aluminum-doped cobalt carbonate can inhibit the precipitation and aggregation of aluminum, and compared with the prior art, the aluminum-doped cobalt carbonate prepared by the coating method has the advantages that the preparation cost is lower, the preparation process is simplified, adverse effects on the environment are avoided, meanwhile, the aluminum precipitated and aggregated on the surface of the prepared aluminum-doped cobalt carbonate is less, and the aluminum is distributed in the aluminum-doped cobalt carbonate more uniformly.
In the invention, the particles of cobalt carbonate to be doped with aluminum grow to 10-20 mu m, and the cobalt-aluminum mixed salt solution is replaced by the cobalt salt solution without aluminum for adding and continuing the reaction.
The cobalt salt is water-soluble cobalt salt, preferably one or more selected from cobalt sulfate, cobalt nitrate, cobalt chloride and cobalt acetate, and more preferably cobalt sulfate, cobalt nitrate or cobalt chloride.
In the present invention, the addition rate of the cobalt salt solution containing no aluminum is preferably the same as that of the cobalt aluminum mixed salt solution in step 1, and the addition rate of the base is preferably the same as that of the base in step 1.
The alkali solution used in step 2 of the present invention is the same as the alkali solution used in step 1, and is also prepared by dissolving alkali in water, wherein the alkali is selected from one or more of ammonium bicarbonate, sodium carbonate and ammonium carbonate, preferably one or two of ammonium bicarbonate and ammonium carbonate, and more preferably ammonium bicarbonate.
The concentration of the alkali solution is 100 to 400g/L, preferably 120 to 300g/L, more preferably 150 to 250g/L.
The concentration of the metal cobalt in the cobalt salt solution is 20-130 g/L, preferably the concentration of the cobalt salt is 60-120 g/L, and more preferably the concentration of the cobalt salt solution is the same as the concentration of the aluminum cobalt mixed salt solution added in the step 1.
The inventor discovers that aluminum-doped cobalt carbonate particles with cobalt salt coating layers on the surfaces can be prepared by replacing an aluminum-cobalt mixed salt solution with cobalt salt in the preparation process, and particularly the coating layers on the surfaces of the aluminum-doped cobalt carbonate particles prepared when the concentration of the cobalt salt is in the range are uniformly coated, so that the precipitation and aggregation of aluminum can be better inhibited.
The cobalt carbonate to be doped with aluminum is grown to a median particle diameter of 15 to 25 μm, preferably 16 to 22 μm, more preferably 17 to 20 μm, and the feed is stopped, and then the resulting product is subjected to post-treatment.
And 3, carrying out post-treatment on the product prepared in the step 2.
The post-treatment includes dewatering, washing, filtering and drying.
The filtration in step 3 of the present invention is preferably suction filtration or pressure filtration, more preferably pressure filtration.
The detergent is water, preferably pure water at 75-95 ℃, more preferably pure water at 90 ℃, hot water is favorable for removing sulfate radical in gaps of cobalt carbonate particles and reducing the content of sulfate radical impurities in the product, so that the cobalt carbonate is washed by hot pure water at more than 75 ℃.
The above washed matter is dried in a vacuum oven at a drying temperature of preferably 80 to 120 ℃, more preferably 100 ℃.
In a second aspect, the present invention provides aluminium doped cobalt carbonate particles obtainable by the process according to the first aspect of the present invention.
The thickness of the coating layer of the aluminum-doped cobalt carbonate particles prepared by the method is 0.1-3 mu m, the particle diameter is 15-40 mu m, and the tap density of the aluminum-doped cobalt carbonate particles is 1.98g/cm 3 ～2.10g/cm 3 Specific surface area of 2.1-4.1 m 2 And/g, the aluminum doping amount of the aluminum-doped cobalt carbonate is 500-10000 ppm, preferably, the aluminum doping amount of the aluminum-doped cobalt carbonate is 500-6500 ppm.
The invention has the beneficial effects that:
(1) The preparation method of the aluminum-doped cobalt carbonate particles is simple, and the prepared aluminum-doped cobalt carbonate particles are coated with a coating layer with the thickness of 0.1-3 mu m;
(2) According to the preparation method of the aluminum-doped cobalt carbonate particles, the surface of the aluminum-doped cobalt carbonate particles is coated with the coating layer, so that precipitation and aggregation of aluminum elements in the aluminum-doped cobalt carbonate particles are reduced, and the doped aluminum elements are more uniform;
(3) The aluminum-doped cobalt carbonate particles prepared by the preparation method disclosed by the invention have the advantages of good sphericity and uniform particle size distribution.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
CoSO is carried out 4 And Al 2 (SO 4 ) 3 Preparing a cobalt-aluminum mixed solution with pH=4 with the aid of sulfuric acid according to the mass ratio of 120:1, preparing 200g/L ammonium bicarbonate with the total concentration of 2.2mol/L, adding 20g of ammonium bicarbonate and 2L of pure water into a 5L reaction kettle as base solution, respectively pumping the cobalt-aluminum mixed salt solution and the ammonium bicarbonate into the reaction kettle at the flow rates of 3ml/min and 6ml/min by using peristaltic pumps, reacting at 50 ℃ in a stirring state with the rotation speed of 1000r/min, and controlling the pH=7.8-8.0 by adjusting the flow rate of alkali (ammonium bicarbonate).
The stirring speed of the reaction kettle is reduced to 800r/min along with the growth of the particles to 15 mu m, and the salt solution is replaced by CoSO with the concentration of 2.2mol/L after the growth of the particles to 18 mu m 4 The solution is added into a reaction kettle to react for a period of time instead of the cobalt-aluminum mixed salt solution, and the feeding is stopped when the granularity D50 of the cobalt carbonate grows to 19 mu m, and the thickness of the coating layer is 1 mu m.
Filtering the materials in the reaction kettle, washing with pure water at 90 ℃, and drying at 100 ℃ to obtain the aluminum-doped cobalt carbonate. Through test, the tap density of the aluminum-doped cobalt carbonate is 1.98g/cm 3 Specific surface area 4.01m 2 /g。
Example 2
CoCl is to be processed 2 And AlCl 3 According to the mass ratio of 100:1, preparing 230g/L ammonium bicarbonate with the total concentration of 2.0mol/L, adding 10mL of ammonia water and 2L of pure water as base solution into a 5L reaction kettle, respectively pumping cobalt-aluminum mixed salt solution and ammonium bicarbonate into the reaction kettle at the flow rate of 5mL/min and 7.5mL/min by a peristaltic pump, and reacting at 48 ℃ under the stirring state with the stirring speed of 800r/min.
Controlling the pH value of the solution to be 7.6-7.8, reducing the stirring speed of the reaction kettle to 700r/min along with the growth of the particles to 14 mu m, replacing the salt solution when the growth of the particles to 16 mu m, and using CoCl with the concentration of 2.0mol/L 2 The solution, instead of the cobalt-aluminum mixed salt solution, is continuously added into a reaction kettle to react for a period of time, and the feeding is stopped when the granularity D50 of the cobalt carbonate grows to 17 mu m, and the thickness of the coating layer is 1 mu m.
Filtering the materials in the reaction kettle, washing with pure water at 90 ℃, and drying at 100 ℃ to obtain the aluminum-doped cobalt carbonate. Through test, the tap density of the aluminum-doped cobalt carbonate is 2.02g/cm 3 Specific surface area 3.25m 2 /g。
Example 3
Cobalt nitrate and aluminum chloride are mixed according to the mass ratio of 60:1 preparing a cobalt-aluminum mixed solution with the total concentration of 1.6mol/L, preparing 2mol/L ammonium bicarbonate, adding 2L pure water and 10g ammonium bicarbonate serving as base solution into a reaction kettle, adjusting the flow rate of ammonium bicarbonate to be 7.1-7.3, and reacting at 48 ℃ under the stirring state of the stirring speed of 1000r/min, wherein the salt flow rate is 2mL/min, and the ammonium bicarbonate flow rate is 6 mL/min.
And (3) reducing the stirring speed of the reaction kettle to 600r/min along with the growth of the particles to 14 mu m, changing the cobalt-aluminum mixed salt solution into a cobalt nitrate solution when the growth of the particles to 16 mu m, keeping the concentration of the cobalt nitrate to be 1.6mol/L, continuing the reaction until the growth of the cobalt carbonate particle size D50 to 17.5 mu m, stopping feeding, and enabling the thickness of the coating layer to be 1.5 mu m.
Filtering the materials in the reaction kettle, washing with pure water at 90 ℃, and drying at 100 ℃ to obtain the aluminum-doped cobalt carbonate. Through test, the tap density of the aluminum-doped cobalt carbonate is 2.05g/cm 3 Specific surface area 2.15m 2 /g。
Example 4
CoSO is carried out 4 And Al 2 (SO 4 ) 3 Preparing 200g/L ammonium bicarbonate according to the mass ratio of 80:1 and the total concentration of 2.0mol/L, adding 10g ammonium bicarbonate, 10mL ammonia water and 2L pure water into a 5L reaction kettle as base solution, respectively mixing cobalt and aluminum mixed salt solution with peristaltic pump, and respectively adding the ammonium bicarbonate according to the mass ratio of 1:2 (respectively 3ml/min and 6 ml/min) are simultaneously injected into a reaction kettle, the reaction is carried out at 55 ℃ under the stirring state with the rotating speed of 800r/min, and the pH=7.5-7.8 of the solution is controlled by adjusting the flow rate of alkali (ammonium bicarbonate solution).
The stirring speed of the reaction kettle is reduced to 600r/min along with the growth of the particles to 14 mu m, and the salt solution is replaced by 2.0mol/L CoSO after the growth of the particles to 16 mu m 4 The solution was reacted in place of the cobalt aluminium mixed salt solution until the cobalt carbonate particle size D50 grew to 18 μm and the feed was stopped and the coating layer thickness was 2 μm.
Filtering the materials in the reaction kettle, washing with pure water at 90 ℃, and drying at 100 ℃ to obtain the aluminum-doped cobalt carbonate. Through test, the tap density of the aluminum-doped cobalt carbonate is 1.98g/cm 3 Specific surface area 3.55m 2 /g。
Example 5
The aluminum-doped cobalt carbonate particles prepared in example 4 are sieved and then are placed in a carbonization furnace for sintering, the sintering temperature is 800 ℃, the sintering atmosphere is air, and the cobaltosic oxide is obtained after sintering.
And mixing the obtained cobaltosic oxide with lithium carbonate according to the lithium-cobalt ratio of 1:1.05, and sintering at 1000 ℃ to obtain the lithium cobaltate anode material.
The lithium cobalt oxide positive electrode material was fabricated into a half cell and tested, and the coulombic efficiency was 95.15%, and the capacity retention after 50 weeks of cycle was 97.16%.
Comparative example
Comparative example 1
The procedure of example 1 was repeated, except that: in the preparation process, cobalt-aluminum mixed salt solution is always used for reaction, and aluminum-free cobalt carbonate coating is not carried out on aluminum-doped cobalt carbonate particles. The tap density of the obtained cobalt carbonate is 1.96m 2 Per gram, specific surface area of 5.23m 2 /g。
Comparative example 2
The procedure of example 4 was repeated, with the only difference that: filtering the materials in the reaction kettle, washing with normal-temperature pure water, and drying at 100 ℃ to obtain the aluminum-doped cobalt carbonate.
Sieving the aluminum-doped cobalt carbonate particles, and then placing the sieved aluminum-doped cobalt carbonate particles in a carbonization furnace for sintering at the sintering temperature of 800 ℃ in the air atmosphere to obtain the cobaltosic oxide.
And mixing the obtained cobaltosic oxide with lithium carbonate according to the lithium-cobalt ratio of 1:1.05, and sintering at 1000 ℃ to obtain the lithium cobaltate anode material.
The lithium cobalt oxide positive electrode material was fabricated into a half cell and tested, and the coulombic efficiency was 93.83%, and the capacity retention after 50 weeks of cycle was 94.42%. Compared with the positive electrode material prepared in example 5, the positive electrode material prepared in comparative example 2 has lower coulombic efficiency and capacity retention rate, which indicates that sulfate radical in the precursor can be more effectively removed by washing with hot water, and the obtained positive electrode material has better electrochemical performance.
Experimental example
Experimental example 1 scanning electron microscope test
The aluminum-doped cobalt carbonate prepared in example 4 was subjected to scanning electron microscopy, and the test results are shown in fig. 1 and 2, wherein fig. 1 is a high-magnification scanning electron microscopy photograph of the aluminum-doped cobalt carbonate particles.
As can be seen from FIG. 1, the aluminum-doped cobalt carbonate particles prepared by the method have good sphericity and larger particle size, the particle size is 15-40 mu m, and as can be seen from FIG. 2, the aluminum-doped cobalt carbonate particles prepared by the method have uniform particle size.
Experimental example 2 tap density and specific surface area test
The aluminum-doped cobalt carbonates prepared in example 1, example 2, example 3, example 4 and comparative example 1 were subjected to tap density and specific surface area tests, and the test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the tap density of the aluminum-doped cobalt carbonate obtained in example 1 was 1.98g/cm 3 Example 2 the tap density of the aluminum-doped cobalt carbonate was 2.02g/cm 3 Example 3 the tap density of the aluminum-doped cobalt carbonate was 2.05g/cm 3 Example 4 the tap density of the aluminum-doped cobalt carbonate was 1.98g/cm 3 The tap density of the aluminum-doped cobalt carbonate particles prepared by the invention is 1.98-2.1 g/cm 3 Comparative example 1 the tap density of the aluminum-doped cobalt carbonate was 1.96m 2 And/g. The aluminum-doped cobalt carbonate prepared by the preparation method has higher tap density.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (8)
1. A method for preparing aluminum-doped cobalt carbonate particles, which is characterized by comprising the following steps:
step 1, preparing aluminum-doped cobalt carbonate particles;
step 2, coating the aluminum-doped cobalt carbonate particles prepared in the step 1;
step 3, carrying out post-treatment on the product prepared in the step 2;
in the step 1, cobalt salt and aluminum salt are added into water to prepare cobalt-aluminum mixed salt solution, alkali solution and cobalt-aluminum mixed salt solution are added into a reaction kettle added with base solution, the cobalt salt is selected from cobalt salt which can be dissolved in water, and the aluminum salt is selected from aluminum salt which can be dissolved in water;
the mass ratio of the cobalt salt to the aluminum salt is (50-1550): 1, a step of;
the concentration of the mixed salt solution is 0.1-10 mol/L;
in the step 2, the particle size of the aluminum-doped cobalt carbonate grows to 10-20 mu m, and the cobalt-aluminum mixed salt solution is replaced by cobalt salt solution for reaction.
2. The method according to claim 1, wherein in step 1,
dissolving alkali in water to prepare alkali solution, wherein the alkali is selected from one or more of ammonium bicarbonate, sodium carbonate and ammonium carbonate,
the concentration of the alkali solution is 100-400 g/L.
3. The method according to claim 2, wherein in step 1,
the ratio of the adding speed of the alkali solution to the adding speed of the mixed salt solution is (0.5-5): 1,
the reaction temperature is 30-100 ℃,
the reaction is carried out under stirring, the stirring speed is 500-1500 r/min,
the pH of the reaction system is controlled to 7-10.
4. The method according to claim 1, wherein in step 2,
the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate, cobalt chloride and cobalt acetate,
the addition rate of the cobalt salt solution is the same as that of the cobalt aluminum mixed salt solution in the step 1.
5. The method according to claim 1, wherein in step 3,
the post-treatment comprises dewatering, washing, filtering and drying,
the detergent is water.
6. The method according to claim 5, wherein in step 3, the detergent is purified water at 75 to 95 ℃.
7. An aluminum-doped cobalt carbonate particle produced by the method of any one of claims 1 to 6, having a coating layer thickness of 0.1 to 3 μm and a particle diameter of 15 to 40 μm, and having a tap density of 1.98g/cm 3 ～2.10g/cm 3 Specific surface area of 2.1-4.1 m 2 And/g, wherein the aluminum doping amount of the aluminum-doped cobalt carbonate is 500-10000 ppm.
8. The aluminum-doped cobalt carbonate particles according to claim 7, wherein the aluminum-doped cobalt carbonate has an aluminum content of 500 to 6500ppm.
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