CN113716619B - Preparation method of large-particle spherical doped cobalt carbonate with uniform particle size distribution - Google Patents
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Abstract
The invention discloses a preparation method of large-particle spherical doped cobalt carbonate with uniform particle size distribution. According to the invention, cobalt salt is used as a raw material, carbonate is used as a precipitator, soluble aluminum, magnesium, nickel and manganese salts are used as doping sources, the particle size of cobalt carbonate is controlled to be steadily increased by precisely setting the rotating speed, the flow speed and the pH value of different feeding stages, so that small particles are avoided to be generated, and finally, the large-particle spherical doped cobalt carbonate with uniform particle size distribution is obtained, the D50 of the obtained cobalt carbonate is 20.0-25.0 mu m, the QD is less than 0.4, the particle size distribution is uniform, the electron microscope shows no small particles, and the doping content of each element in the cobalt carbonate is 0.05% -0.6%.
Description
Technical Field
The invention belongs to the field of precursors of lithium cobalt oxide serving as a positive electrode material of a lithium ion battery, and relates to a preparation method of large-particle spherical doped cobalt carbonate with uniform particle size distribution.
Background
Lithium Cobalt Oxide (LCO) is the most mature positive electrode material at present and is widely applied to the field of 3C consumer electronic products. In recent years, with the rise of 5G mobile phones, consumers have put higher demands on the capacity of batteries. Research shows that the battery capacity can be effectively improved by improving the charge cut-off voltage. For example, increasing the voltage from 4.45V to 4.48V, the energy density of the corresponding LCO cell can be increased by about 3.5%. However, increasing the voltage causes the crystalline structure of the material to collapse, resulting in a rapid capacity fade. The element doping can effectively solve the stability problem of the crystal structure of the material. Al, mg, ni, mn and the like can effectively improve the cycle performance of LCO under high voltage. The traditional method for obtaining the doped lithium aluminum cobaltate is to calcine the mixture of doped metal salt, cobaltosic oxide and lithium carbonate simultaneously to obtain the doped lithium aluminum cobaltate. At present, most of doped cobaltosic oxide is obtained by synthesizing doped cobalt carbonate through wet coprecipitation and then calcining and decomposing. However, in the process of preparing doped cobalt carbonate by adopting a liquid phase precipitation method, the following problems exist:
in the process of preparing doped cobalt carbonate by adopting a liquid phase precipitation method, the following problems exist:
(1) When the batch method is adopted to prepare the aluminum-doped large-particle cobalt carbonate, the batch kettle (half of materials are separated) is easy to adhere after feeding, and the sphericity of the cobalt carbonate is affected.
(2) Ion precipitation is not synchronized due to the large difference in concentration of each dopant ion and cobalt ion. When the granularity grows to a certain extent, the doped ions are easy to independently generate new nuclei to become new growth sites, so that small particles are generated, and the granularity distribution is influenced.
Disclosure of Invention
In order to overcome the problems in the existing preparation process of the doped cobalt carbonate, the invention provides a preparation method of large-particle spherical doped cobalt carbonate with uniform particle size, which takes cobalt salt as a raw material and carbonate as a precipitator, and soluble aluminum, magnesium, nickel and manganese salts as doping sources.
The technical scheme adopted by the invention is as follows: a preparation method of large-particle spherical doped cobalt carbonate with uniform particle size distribution comprises the following steps:
1. preparation of raw and auxiliary materials
Uniformly mixing soluble cobalt salt and soluble doping salt to prepare solution A, and then preparing carbonate solution B for the subsequent steps II and III;
2. preparation of cobalt carbonate seed
Adding the carbonate solution B into a reaction kettle as a base solution, and simultaneously adding the solution A and the carbonate solution B into the reaction kettle at a constant speed under the stirring condition of 100-350rpm to gradually reduce the pH value of the system to 7.0-8.0, thereby obtaining cobalt carbonate with the D50 of 5.5-7.5 mu m; settling, pumping supernatant, and circularly feeding until D50 reaches 8.0-12.0 mu m, and completing preparation of cobalt carbonate seed crystal;
3. cobalt carbonate growth
Dividing the seed crystal slurry in the second step into two parts to two reaction kettles for growth, circularly feeding for a plurality of times, and ending the growth in the first stage when the cobalt carbonate D50 reaches 12.0-15.0 mu m; after the first-stage growth is finished, uniformly dividing the slurry in each reaction kettle into two parts to two reaction kettles for second-stage growth, and circularly feeding for a plurality of times to ensure that the cobalt carbonate is 15.0-18.0 mu m, wherein the second-stage growth is finished; after the second-stage growth is finished, uniformly dividing the slurry in each reaction kettle into two parts to two reaction kettles for third-stage growth, and circularly feeding for a plurality of times until the cobalt carbonate D50 reaches 20.0-25.0 mu m, wherein the third-stage growth is finished; the flow speed, the rotating speed and the pH value of the cobalt liquid at each stage are controlled in the whole growth process, so that the cobalt carbonate grows steadily, and the generation of small particles is avoided;
and washing, drying and sieving the synthesized cobalt carbonate seed crystal to obtain the large-particle spherical doped cobalt carbonate with uniform particle size distribution.
The obtained cobalt carbonate D50 is 20.0-25.0 mu m, the QD ((D90-D10)/D50) is less than 0.4, the granularity distribution is uniform, the electron microscope shows no small particles, and the doping content of elements in the cobalt carbonate is 0.05-0.6%.
The principle of the invention is as follows:
(1) In order to prevent adhesion generated by feeding after kettle separation, the flow rate of cobalt liquid is reduced, the rotating speed is increased, the increasing speed of the granularity of cobalt carbonate is controlled, and the sphericity is ensured.
(2) In order to prevent small particles from being generated, the pH value of a synthesis system is controlled after the particle size is increased to a certain degree, the flow rate of cobalt liquid is further reduced, the precipitation rate of doped ions is reduced, and the generation of small particles caused by the generation of new nuclei is avoided.
In the first step, the soluble cobalt salt is one or a mixture of a plurality of cobalt chloride, cobalt sulfate and cobalt nitrate.
In the first step, the soluble doping salt is one or a mixture of a plurality of soluble sulfate, nitrate and chloride corresponding to aluminum, magnesium, nickel and manganese.
Further, in the first step, in the solution A, the concentration of the cobalt solution is 80-160 g/L, and the mass concentration ratio of the doping element to the cobalt is (0.0010-0.0125) 1; the carbonate solution B is ammonium carbonate or ammonium bicarbonate solution with the concentration of 180-230 g/L.
Further, in the third step, the flow rate of the first stage is 15-45mL/min, the cyclic feeding is 8-12 times, the pH is 6.5-7.8, the rotating speed is 100-250r/min, the flow rate of the first stage is 15-45mL/min, the cyclic feeding is 8-12 times, the pH is 6.5-7.8, and the rotating speed is 100-250r/min; the flow rate of the second stage is 70-80% of the flow rate of the first stage, the cyclic feeding is 7-12 times, the pH value is 0.2-0.5 lower than that of the first stage, and the rotating speed is 1.2-1.5 times that of the first stage; the flow rate of the third stage is 30-50% of that of the second stage, the cyclic feeding is 5-9 times, the pH value is 0.2-0.4 lower than that of the second stage, and the rotating speed is 1.2-1.5 times that of the second stage.
The invention has the following beneficial effects: the invention can control the particle size increase speed of the cobalt carbonate and ensure sphericity; the invention can effectively control the precipitation rate of doped ions in the synthesis process, avoid the generation of small particles and obtain the large-particle spherical doped cobalt carbonate with uniform particle size distribution.
Drawings
FIG. 1 is a scanning electron microscope image of the product prepared in example 1 of the present invention;
FIG. 2 is a graph showing the particle size distribution of the product prepared in example 1 of the present invention.
Detailed Description
The following describes the detailed procedure of the present invention by way of examples, which are provided for ease of understanding and are in no way intended to limit the invention.
Example 1
1. Preparation of raw and auxiliary materials
The mass concentration ratio of the prepared aluminum to the cobalt is (0.0098-0.0102): 1, the cobalt concentration is 117g/L, the aluminum concentration is 1.17g/L, and 226g/L ammonium bicarbonate solution B is configured for the subsequent steps two and three.
2. Preparation of cobalt carbonate seed
Adding the carbonate solution B into a reaction kettle as a base solution, and simultaneously adding the solution A and the carbonate solution B into the reaction kettle at a constant speed under the stirring condition of 250rpm to gradually reduce the pH value of the system to 7.5-7.8, thereby obtaining the cobalt carbonate with the D50 of 6.1 mu m. Settling, pumping supernatant, and circularly feeding until D50 reaches 10.5 mu m, and completing seed crystal preparation.
3. Cobalt carbonate growth
Uniformly dividing the seed crystal slurry in the second step into two parts to two reaction kettles for growth; the flow rate of the first stage is 35mL/min, the pH is 7.4-7.7, and the rotating speed is 130r/min. And (3) after 10 times of cyclic feeding, when the cobalt carbonate grows to a D50 of 13.2 mu m, ending the first stage. After the growth of the first stage is finished, the slurry in each reaction kettle is equally divided into two parts to two reaction kettles for the growth of the second stage, the flow is 70% of that of the first stage, namely 25mL/min, the pH is 0.2 to 7.5 lower than that of the first stage, and the rotating speed is 1.25 times that of the first stage, namely 150r/min. The cobalt carbonate is added for 8 times to ensure that the thickness of the cobalt carbonate is 17.0 mu m, and the growth of the second stage is finished. After the second stage is finished, the slurry in each reaction kettle is equally divided into two parts to two reaction kettles for third stage growth, the flow rate of the third stage is 50% of the flow rate of the second stage, namely 12mL/min, the cyclic feeding is 7 times, the pH value is 0.4, namely 6.8-7.3, and the rotating speed is 1.2 times of the rotating speed of the second stage, namely 180r/min. Until reaching the D50 of 20.8 mu m of the cobalt carbonate, and ending the growth of the third stage.
And washing, drying and sieving the synthesized aluminum-doped cobalt carbonate material to obtain the aluminum-doped spherical cobalt carbonate. The D50 is 20.8 μm and the diameter distance QD, namely (D90-D10)/d50=0.38, the particle size distribution is uniform, the electron microscope shows no small particles, and the aluminum content in the cobalt carbonate is 0.45%.
Example 2
1. Preparation of raw and auxiliary materials
Cobalt sulfate and aluminum sulfate octadecatrienal, magnesium sulfate, nickel sulfate and manganese sulfate solution are prepared into aluminum, magnesium, nickel, manganese and cobalt with mass concentration ratio of (0.0080-0.090): 1, (0.0015-0.0025): 1, (0.0015-0.0020): 1, (0.0020-0.0030): 1, the cobalt concentration of the mixed solution A is 118g/L, and 223g/L of ammonium bicarbonate solution B is prepared for the subsequent steps two and three.
2. Preparation of cobalt carbonate seed
Adding the carbonate solution B into a reaction kettle as a base solution, and simultaneously adding the solution A and the carbonate solution B into the reaction kettle at a constant speed under the stirring condition of 200rpm to gradually reduce the pH value of the system to 7.6-7.8, thereby obtaining the cobalt carbonate with the D50 of 6.8 mu m. Settling, pumping supernatant, and circularly feeding until D50 reaches 10.5 mu m, and completing seed crystal preparation;
3. cobalt carbonate growth
Uniformly dividing the seed crystal slurry in the second step into two parts to two reaction kettles for growth; the flow rate of the first stage is 40mL/min, the pH is 7.3-7.6, and the rotating speed is 110r/min. And (3) after 10 times of cyclic feeding, when the cobalt carbonate grows to reach the D50 of 14.3 mu m, ending the first stage. After the growth of the first stage is finished, the slurry in each reaction kettle is equally divided into two parts to two reaction kettles for the growth of the second stage, the flow is 80% of that of the first stage, namely 32mL/min, the pH is 0.3, namely 7.0-7.5, lower than that of the first stage, and the rotating speed is 1.3 times that of the first stage, namely 145r/min. The cobalt carbonate is added for 8 times to 18.0 mu m, and the growth of the second stage is finished. After the second stage is finished, the slurry in each reaction kettle is equally divided into two parts to two reaction kettles for the third stage growth. The flow rate of the third stage is 30% of the flow rate of the second stage, namely 10mL/min, the pH is 0.2 lower than that of the second stage, namely 6.8-7.3, and the rotating speed is 1.4 times that of the second stage, namely 200r/min. And 7 times of material feeding are circularly carried out until the D50 of the cobalt carbonate reaches 21.5 mu m, and the growth of the third stage is finished.
And washing, drying and sieving the synthesized aluminum-doped cobalt carbonate material to obtain the aluminum-doped spherical cobalt carbonate. The D50 is 21.8 μm, the diameter distance QD is (D90-D10)/d50=0.32, the granularity is uniformly distributed, the electron microscope shows no small particles, and the contents of aluminum, magnesium, nickel and manganese in the cobalt carbonate are respectively 0.38%, 0.08% and 0.17%.
Claims (5)
1. The preparation method of the large-particle spherical doped cobalt carbonate with uniform particle size distribution is characterized by comprising the following steps:
1. preparation of raw and auxiliary materials
Uniformly mixing soluble cobalt salt and soluble doping salt to prepare solution A, and then preparing carbonate solution B for the subsequent steps II and III;
2. preparation of cobalt carbonate seed
Adding the carbonate solution B into a reaction kettle as a base solution, and simultaneously adding the solution A and the carbonate solution B into the reaction kettle at a constant speed under the stirring condition of 100-350rpm to gradually reduce the pH value of the system to 7.0-8.0, thereby obtaining cobalt carbonate with the D50 of 5.5-7.5 mu m; settling, pumping supernatant, and circularly feeding until D50 reaches 8.0-12.0 mu m, and completing preparation of cobalt carbonate seed crystal;
3. cobalt carbonate growth
Dividing the seed crystal slurry in the second step into two parts to two reaction kettles for growth, circularly feeding for a plurality of times, and ending the growth in the first stage when the cobalt carbonate D50 reaches 12.0-15.0 mu m; after the first-stage growth is finished, uniformly dividing the slurry in each reaction kettle into two parts to two reaction kettles for second-stage growth, and circularly feeding for a plurality of times to ensure that the cobalt carbonate is 15.0-18.0 mu m, wherein the second-stage growth is finished; after the second-stage growth is finished, uniformly dividing the slurry in each reaction kettle into two parts to two reaction kettles for third-stage growth, and circularly feeding for a plurality of times until the cobalt carbonate D50 reaches 20.0-25.0 mu m, wherein the third-stage growth is finished; the flow speed, the rotating speed and the pH value of the cobalt liquid at each stage are controlled in the whole growth process, so that the cobalt carbonate grows steadily, and the generation of small particles is avoided;
washing, drying and sieving the synthesized cobalt carbonate seed crystal to obtain large-particle spherical doped cobalt carbonate with uniform particle size distribution;
in the third step, the flow rate of the first stage is 15-45mL/min, the cyclic feeding is 8-12 times, the pH is 6.5-7.8, and the rotating speed is 100-250r/min; the flow of the second stage is 70-80% of the flow of the first stage, the cyclic feeding is carried out for 7-12 times, the pH value is 0.2-0.5 lower than that of the first stage, and the rotating speed is 1.2-1.5 times that of the first stage; the flow rate of the third stage is 30-50% of that of the second stage, the cyclic feeding is 5-9 times, the pH value is 0.2-0.4 lower than that of the second stage, and the rotating speed is 1.2-1.5 times that of the second stage.
2. The method for preparing large-particle spherical doped cobalt carbonate with uniform particle size distribution according to claim 1, wherein in the first step, the soluble cobalt salt is one or a mixture of a plurality of cobalt chloride, cobalt sulfate and cobalt nitrate.
3. The method for preparing large-particle spherical doped cobalt carbonate with uniform particle size distribution according to claim 1, wherein in the first step, the soluble doped salt is one or a mixture of a plurality of sulfate, nitrate and chloride salts corresponding to aluminum, magnesium, nickel and manganese.
4. The method for preparing large-particle spherical doped cobalt carbonate with uniform particle size distribution according to claim 1, wherein in the first step, the concentration of cobalt solution in the solution A is 80-160 g/L, and the mass concentration ratio of doping element to cobalt is (0.0010-0.0125): 1.
5. The method for preparing large-particle spherical doped cobalt carbonate with uniform particle size distribution according to claim 1, wherein in the first step, the carbonate solution B is ammonium carbonate or ammonium bicarbonate solution with the concentration of 180-230 g/L.
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| CN114751465B (en) * | 2022-05-24 | 2023-06-27 | 荆门市格林美新材料有限公司 | Method for preparing high Al uniform cobaltosic oxide by replacing staged elements |
| CN114940515B (en) * | 2022-06-15 | 2023-11-03 | 荆门市格林美新材料有限公司 | Aluminum-doped cobalt carbonate and preparation method and application thereof |
| CN114804222A (en) * | 2022-06-16 | 2022-07-29 | 荆门市格林美新材料有限公司 | Nickel-manganese bimetal doped large-particle cobalt carbonate and preparation method and application thereof |
| CN115417457A (en) * | 2022-08-12 | 2022-12-02 | 广东邦普循环科技有限公司 | Manganese-doped cobalt carbonate and preparation method and application thereof |
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| CN107540024A (en) * | 2017-09-14 | 2018-01-05 | 湖南雅城新材料有限公司 | Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide |
| CN113307308A (en) * | 2021-06-25 | 2021-08-27 | 湖南杉杉能源科技有限公司 | Doped large-particle cobalt carbonate and preparation method thereof |
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| CN107540024A (en) * | 2017-09-14 | 2018-01-05 | 湖南雅城新材料有限公司 | Preparation method, process units and the spherical cobaltic-cobaltous oxide of spherical cobaltic-cobaltous oxide |
| CN113307308A (en) * | 2021-06-25 | 2021-08-27 | 湖南杉杉能源科技有限公司 | Doped large-particle cobalt carbonate and preparation method thereof |
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