CN113772745A - Preparation method of aluminum uniformly-doped large-particle-size cobaltosic oxide - Google Patents
Preparation method of aluminum uniformly-doped large-particle-size cobaltosic oxide Download PDFInfo
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Abstract
The invention discloses a preparation method of aluminum uniformly doped cobaltosic oxide with large particle size, which comprises the following steps: preparing a cobalt-aluminum solution and an ammonium bicarbonate solution; preparing a base solution in a first crystal seed kettle; simultaneously adding a cobalt aluminum solution and an ammonium bicarbonate solution into a first crystal seed kettle, and reacting to obtain first crystal seeds; half of the material in the first crystal seed kettle is separated into a second crystal seed kettle, and a cobalt-aluminum solution and an ammonium bicarbonate solution are simultaneously added into the second crystal seed kettle to react to obtain a second crystal seed; half of the material in the second crystal kettle is separated into a finished product kettle, an ammonium bicarbonate solution is added into the finished product kettle, a cobalt-aluminum solution and the ammonium bicarbonate solution are simultaneously added into the finished product kettle, and a primary finished product is obtained through reaction; and sequentially carrying out centrifugal washing and calcination on the primary finished product to obtain the product of the invention. The product prepared by the method has more uniform aluminum distribution, larger specific surface area and better sphericity.
Description
Technical Field
The invention belongs to the technical field of lithium battery materials, and particularly relates to a preparation method of aluminum uniformly-doped large-particle-size cobaltosic oxide.
Background
Lithium cobaltate has higher specific capacity and cycle performance as one of the important anode materials of the lithium ion battery, and the lithium cobaltate is widely applied to the 3C digital field as the anode material at present, such as digital cameras, mobile phones, unmanned aerial vehicles, wireless earphones and the like. However, with the development of society, higher requirements are put forward on the performance of products in the 3C digital field, and the lithium ion battery develops 4.35V, 4.45V and even 4.5V from the traditional 3.0V voltage, and is especially important as cobaltosic oxide which is one of the raw materials of lithium cobaltate. At present, the most common cobaltosic oxide is a cobaltosic oxide of an undoped substance and aluminum-doped system, and the existing process for synthesizing the cobaltosic oxide has the problems of instability, non-uniform aluminum doping and the like, thereby seriously influencing the stability of the product. Just because of the uneven aluminum doping and the serious influence on the high voltage characteristic of lithium cobaltate, aluminum is taken as a common element in nature, can form coprecipitation with cobalt carbonate uniformly, improves the impedance characteristic of the material, and is widely evaluated as a material of a special lithium battery.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of uniformly-distributed and better-sphericity aluminum-doped cobaltosic oxide with large particle size.
The invention adopts the following technical scheme:
a preparation method of aluminum uniformly doped cobaltosic oxide with large particle size is characterized by comprising the following steps:
(1) preparing a cobalt-aluminum solution and preparing an ammonium bicarbonate solution;
(2) adding pure water and the ammonium bicarbonate solution obtained in the step (1) into the first crystal seed kettle to prepare a base solution, stirring the base solution, and controlling the pH value of the base solution to be 7.5-8.5;
(3) adding the cobalt-aluminum solution and the ammonium bicarbonate solution in the step (1) into a first seed crystal kettle simultaneously, keeping the pH of the material in the first seed crystal kettle to be 7.2-7.6, controlling the growth speed of the material in the first seed crystal kettle to be 0.55-0.75 μm per 8 hours, and stopping the reaction when the granularity D50 of the material in the first seed crystal kettle is 6.0-7.0 μm to obtain a first seed crystal;
(4) dividing half of the material in the first seed crystal kettle into a second seed crystal kettle, adding the ammonium bicarbonate solution obtained in the step (1) into the second seed crystal kettle, controlling the pH of the material in the second seed crystal kettle to be 7.6-7.8, simultaneously adding the cobalt aluminum solution and the ammonium bicarbonate solution obtained in the step (1) into the second seed crystal kettle, keeping the pH of the material in the second seed crystal kettle to be 7.2-7.6, controlling the growth speed of the material in the second seed crystal kettle to be 0.65-0.95 mu m per 8 hours, and stopping the reaction when the granularity D50 of the material in the second seed crystal kettle is 11.0-12.0 mu m to obtain a second seed crystal;
(5) half of the material in the second crystal kettle is separated into a finished product kettle, the ammonium bicarbonate solution in the step (1) is added into the finished product kettle, the pH of the material in the finished product kettle is controlled to be 7.6-7.8, the cobalt aluminum solution and the ammonium bicarbonate solution in the step (1) are simultaneously added into the finished product kettle, the pH of the material in the finished product kettle is kept to be 7.2-7.6, the growth speed of the material in the finished product kettle is controlled to be 0.65-0.95 mu m per 8 hours, the reaction is stopped when the granularity D50 of the material in the finished product kettle is 19.0-23.0 mu m, and a primary finished product is obtained;
(6) and sequentially carrying out centrifugal washing and calcination on the primary finished product to obtain the aluminum-uniformly-doped cobaltosic oxide with large particle size.
The preparation method of the uniformly aluminum-doped large-particle-size cobaltosic oxide is characterized in that the cobalt-aluminum solution in the step (1) contains cobalt ions and aluminum ions, the concentration of the cobalt ions in the cobalt-aluminum solution is 100g/L-140g/L, and the concentration of the aluminum ions in the cobalt-aluminum solution is 0.5g/L-1.5 g/L; the concentration of the ammonium bicarbonate solution in the step (1) is 200g/L-280 g/L.
The preparation method of the aluminum uniformly doped large-particle-size cobaltosic oxide is characterized in that the concentration of ammonium bicarbonate in the base solution in the step (2) is 10g/L-30g/L, and the ratio of the volume of pure water added into the first seed crystal kettle to the volume of the first seed crystal kettle is 0.5-0.7; the temperature of the base solution in the step (2) is 30-50 ℃, and the stirring speed for stirring the base solution is 150-300 r/min.
The preparation method of the aluminum uniformly doped cobaltosic oxide with large particle size is characterized in that in the step (3), the feeding flow rates of the cobalt aluminum solution and the ammonium bicarbonate solution which are simultaneously added into the first seed crystal kettle are respectively 250L/h-500L/h and 500L/h-1000L/h.
The preparation method of the uniformly aluminum-doped large-particle-size cobaltosic oxide is characterized in that the adding amount of the ammonium bicarbonate solution added into the second seed crystal kettle in the step (4) is 0.1m3-0.5m3(ii) a In the step (4), the stirring speed of the second crystal seed kettle is controlled to be 50r/min-150 r/min; in the step (4), the feeding flow rates of the cobalt aluminum solution and the ammonium bicarbonate solution which are simultaneously added into the second crystal seed kettle are respectively 100L/h-500L/h and 150L/h-1000L/h.
The preparation method of the uniformly aluminum-doped large-particle-size cobaltosic oxide is characterized in that the adding amount of the ammonium bicarbonate solution added into the finished product kettle in the step (5) is 0.1m3-0.5m3(ii) a Controlling the stirring speed of the finished product kettle to be 30r/min-100r/min in the step (5); in the step (5), the feeding flow rates of the cobalt aluminum solution and the ammonium bicarbonate solution which are simultaneously added into the finished product kettle are respectively 100L/h-500L/h and 150L/h-1000L/h.
According to the preparation method of the uniformly aluminum-doped large-particle-size cobaltosic oxide, the method is characterized in that a stirring mechanism of the first crystal seed kettle adopts a double-layer stirring blade; and the stirring mechanism of the second crystal seed kettle adopts a double-layer stirring paddle.
The preparation method of the uniformly aluminum-doped large-particle-size cobaltosic oxide is characterized in that in the step (6), a primary finished product is centrifugally washed by a centrifuge, and the washing process adopts a pure water washing mode, wherein the temperature of pure water is 50-70 ℃; and (6) centrifugally washing the primary finished product, then sending the primary finished product into a rotary kiln, and calcining the centrifugally washed primary finished product at the temperature of 600-800 ℃.
Compared with the prior art, the invention has the beneficial technical effects that: the method comprises the following steps: preparing cobalt-aluminum solution and ammonium bicarbonate solution with different concentrations; synthesizing seed crystals through a reaction kettle and controlling the growth of a finished product; will be provided withWashing the cobalt carbonate product by a centrifugal machine to remove harmful components, namely chloride ions; directly calcining wet cobalt carbonate in a rotary kiln to obtain cobaltosic oxide; and (4) mixing the materials, screening, removing iron and packaging. The large aluminum particles doped with cobaltosic oxide with different contents prepared by the method are uniform in distribution, free of sintering agglomeration, uniform in distribution among particles, free of small particles and the like, and easy to industrialize. The aluminum in the aluminum-doped large-particle cobaltosic oxide prepared by the invention is uniformly distributed; the aluminum-doped cobaltosic oxide prepared by the invention can be produced in batch, and compared with the existing aluminum-doped cobaltosic oxide, the aluminum distribution in the cobaltosic oxide product prepared by the invention is more uniform, and the specific surface area is larger (3-5 m)2G) better sphericity and more concentrated particle size distribution.
Drawings
FIG. 1 is an electron microscope image of the aluminum-doped cobaltosic oxide obtained in example 1 of the present invention and a distribution diagram of aluminum in the aluminum-doped cobaltosic oxide;
FIG. 2 is an electron microscope image of the aluminum-doped cobaltosic oxide obtained in example 2 of the present invention and a distribution diagram of aluminum in the aluminum-doped cobaltosic oxide;
FIG. 3 is an electron microscope image of the doped tricobalt tetroxide obtained in example 3 of the present invention and a distribution diagram of aluminum in the doped tricobalt tetroxide.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.
A preparation method of aluminum uniformly doped cobaltosic oxide with large particle size comprises the following steps:
(1) preparing a cobalt-aluminum solution and preparing an ammonium bicarbonate solution; the cobalt-aluminum solution contains cobalt ions and aluminum ions, the concentration of the cobalt ions in the cobalt-aluminum solution is 100g/L-140g/L, and the concentration of the aluminum ions in the cobalt-aluminum solution is 0.5g/L-1.5 g/L; the concentration of the ammonium bicarbonate solution is 200g/L-280 g/L.
(2) Adding pure water and an ammonium bicarbonate solution into the first crystal seed kettle to prepare a base solution, stirring the base solution at the stirring speed of 150-300 r/min, wherein a stirring mechanism of the first crystal seed kettle adopts a double-layer stirring blade. Controlling the pH value of the base solution to be 7.5-8.5; the concentration of ammonium bicarbonate in the base solution is 10g/L-30g/L, and the ratio of the volume of pure water added into the first crystal seed kettle to the volume of the first crystal seed kettle is 0.5-0.7; the temperature of the base solution is 30-50 ℃.
(3) Simultaneously adding a cobalt aluminum solution and an ammonium bicarbonate solution into a first seed crystal kettle at feeding flow rates of 250L/h-500L/h and 500L/h-1000L/h respectively, keeping the pH of a material in the first seed crystal kettle to be 7.2-7.6, controlling the growth speed of the material in the first seed crystal kettle to be 0.55 mu m-0.75 mu m per 8 hours, and stopping reaction when the granularity D50 of the material in the first seed crystal kettle is 6.0 mu m-7.0 mu m to obtain first seed crystals.
(4) Half of the material in the first crystal seed kettle is separated into a second crystal seed kettle, and 0.1m ammonium bicarbonate solution is added into the second crystal seed kettle3-0.5m3Controlling the pH value of the material in the second crystal seed kettle to be 7.6-7.8, controlling the stirring speed of the second crystal seed kettle to be 50r/min-150r/min, and adopting a double-layer stirring blade for a stirring mechanism of the second crystal seed kettle. And simultaneously adding the cobalt aluminum solution and the ammonium bicarbonate solution into a second seed crystal kettle at the feeding flow rates of 100L/h-500L/h and 150L/h-1000L/h respectively, keeping the pH of the material in the second seed crystal kettle to be 7.2-7.6, controlling the growth speed of the material in the second seed crystal kettle to be 0.65-0.95 mu m per 8 hours, and stopping the reaction when the granularity D50 of the material in the second seed crystal kettle is 11.0-12.0 mu m to obtain second seed crystals.
(5) Half of the material in the second crystal kettle is separated into a finished product kettle, and 0.1m ammonium bicarbonate solution is added into the finished product kettle3-0.5m3Controlling the pH value of the material in the finished product kettle to be 7.6-7.8, and controlling the stirring speed of the finished product kettle to be 30-100 r/min; adding cobalt aluminum solution and ammonium bicarbonate solution into a finished product kettle at the same time at feeding flow rates of 100L/h-500L/h and 150L/h-1000L/h respectively, keeping the pH of the material in the finished product kettle at 7.2-7.6, controlling the growth speed of the material in the finished product kettle at 0.65-0.95 μm per 8 hours, and stopping reaction when the granularity D50 of the material in the finished product kettle is 19.0-23.0 μm to obtain a primary finished product.
(6) Centrifugally washing the primary finished product by using a centrifugal machine, wherein the washing process adopts a pure water washing mode, and the temperature of pure water is 50-70 ℃; and (3) centrifugally washing the primary finished product, then sending the washed primary finished product into a rotary kiln, and calcining the centrifugally washed primary finished product at the temperature of 600-800 ℃ to obtain the aluminum-uniformly-doped large-particle-size cobaltosic oxide.
Example 1
Preparing a cobalt-aluminum solution and preparing an ammonium bicarbonate solution; the cobalt-aluminum solution contains cobalt ions and aluminum ions, wherein the concentration of the cobalt ions in the cobalt-aluminum solution is 110g/L, and the concentration of the aluminum ions in the cobalt-aluminum solution is 1.2 g/L; the concentration of the ammonium bicarbonate solution was 220 g/L.
Adding pure water and an ammonium bicarbonate solution into the first crystal seed kettle to prepare a base solution, stirring the base solution at the stirring speed of 220r/min, wherein a stirring mechanism of the first crystal seed kettle adopts a double-layer stirring paddle. Controlling the pH value of the base solution to be 8.4; the concentration of ammonium bicarbonate in the base solution is 15g/L, and the ratio of the volume of pure water added into the first crystal seed kettle to the volume of the first crystal seed kettle is 0.6; the temperature of the base solution was 40 ℃.
And simultaneously adding a cobalt aluminum solution and an ammonium bicarbonate solution into the first seed crystal kettle at feeding flow rates of 450L/h and 800L/h respectively, keeping the pH of the material in the first seed crystal kettle at 7.5, controlling the growth speed of the material in the first seed crystal kettle to be 0.55 mu m of growth per 8 hours, and stopping the reaction when the granularity D50 of the material in the first seed crystal kettle is 7.0 mu m to obtain the first seed crystal.
Half of the material in the first crystal seed kettle is separated into a second crystal seed kettle, and 0.4m ammonium bicarbonate solution is added into the second crystal seed kettle3Controlling the pH value of the material in the second crystal seed kettle to be 7.8, controlling the stirring speed of the second crystal seed kettle to be 150r/min, and adopting a double-layer stirring paddle blade for a stirring mechanism of the second crystal seed kettle. And simultaneously adding the cobalt aluminum solution and the ammonium bicarbonate solution into a second crystal seed kettle at feed flow rates of 450L/h and 800L/h respectively, keeping the pH of the material in the second crystal seed kettle at 7.5, controlling the growth speed of the material in the second crystal seed kettle to be 0.9 mu m per 8 hours, and stopping the reaction when the granularity D50 of the material in the second crystal seed kettle is 12 mu m to obtain second crystal seeds.
Half of the material in the second crystal kettle is separated into a finished product kettle, and 0.4m ammonium bicarbonate solution is added into the finished product kettle3Controlling the pH value of the material in the finished product kettle to be 7.8, and controlling the stirring speed of the finished product kettle to be 100 r/min; the cobalt aluminum solution and the ammonium bicarbonate solution are simultaneously fed at the feed flow rates of 450L/h and 800L/h respectivelyAdding into a finished product kettle, keeping the pH of the material in the finished product kettle at 7.5, controlling the growth speed of the material in the finished product kettle to be 0.95 μm every 8 hours, and stopping reaction when the granularity D50 of the material in the finished product kettle is 23.0 μm to obtain a primary finished product.
Centrifugally washing the primary finished product by using a centrifugal machine, wherein a pure water washing mode is adopted in the washing process, and the temperature of the pure water is 60 ℃; and (3) centrifugally washing the primary finished product, then sending the washed primary finished product into a rotary kiln, and calcining the centrifugally washed primary finished product at 800 ℃ to obtain the aluminum-uniformly-doped cobaltosic oxide with large particle size. FIG. 1 is an electron micrograph of the aluminum-doped tricobalt tetroxide obtained in example 1 and a distribution diagram of aluminum in the aluminum-doped tricobalt tetroxide obtained in example 1.
Example 2
Preparing a cobalt-aluminum solution and preparing an ammonium bicarbonate solution; the cobalt-aluminum solution contains cobalt ions and aluminum ions, wherein the concentration of the cobalt ions in the cobalt-aluminum solution is 110g/L, and the concentration of the aluminum ions in the cobalt-aluminum solution is 1.2 g/L; the concentration of the ammonium bicarbonate solution was 220 g/L.
Adding pure water and an ammonium bicarbonate solution into the first crystal seed kettle to prepare a base solution, stirring the base solution at the stirring speed of 200r/min, wherein a stirring mechanism of the first crystal seed kettle adopts a double-layer stirring paddle. Controlling the pH value of the base solution to be 8.4; the concentration of ammonium bicarbonate in the base solution is 25g/L, and the ratio of the volume of pure water added into the first crystal seed kettle to the volume of the first crystal seed kettle is 0.6; the temperature of the base solution was 45 ℃.
And simultaneously adding a cobalt aluminum solution and an ammonium bicarbonate solution into the first seed crystal kettle at feeding flow rates of 450L/h and 800L/h respectively, keeping the pH of the material in the first seed crystal kettle at 7.5, controlling the growth speed of the material in the first seed crystal kettle to be 0.55 mu m of growth per 8 hours, and stopping the reaction when the granularity D50 of the material in the first seed crystal kettle is 7.0 mu m to obtain the first seed crystal.
Half of the material in the first crystal seed kettle is separated into a second crystal seed kettle, and 0.4m ammonium bicarbonate solution is added into the second crystal seed kettle3Controlling the pH value of the material in the second crystal seed kettle to be 7.8, controlling the stirring speed of the second crystal seed kettle to be 100r/min, and adopting a double-layer stirring paddle blade for a stirring mechanism of the second crystal seed kettle. Respectively mixing cobalt aluminum solution and ammonium bicarbonate solutionAdding the materials into a second crystal seed kettle at the same time at feeding flow rates of 450L/h and 800L/h, keeping the pH of the materials in the second crystal seed kettle at 7.5, controlling the growth speed of the materials in the second crystal seed kettle at 0.6 mu m per 8 hours, and stopping the reaction when the granularity D50 of the materials in the second crystal seed kettle is 12.0 mu m to obtain second crystal seeds.
Half of the material in the second crystal kettle is separated into a finished product kettle, and 0.4m ammonium bicarbonate solution is added into the finished product kettle3Controlling the pH value of the material in the finished product kettle to be 7.8, and controlling the stirring speed of the finished product kettle to be 50 r/min; and simultaneously adding a cobalt aluminum solution and an ammonium bicarbonate solution into a finished product kettle at feed flow rates of 450L/h and 800L/h respectively, keeping the pH of the material in the finished product kettle at 7.5, controlling the growth speed of the material in the finished product kettle to be 0.65 mu m per 8 hours, and stopping the reaction when the granularity D50 of the material in the finished product kettle is 23.0 mu m to obtain a primary finished product.
Centrifugally washing the primary finished product by using a centrifugal machine, wherein a pure water washing mode is adopted in the washing process, and the temperature of the pure water is 60 ℃; and (3) centrifugally washing the primary finished product, then sending the washed primary finished product into a rotary kiln, and calcining the centrifugally washed primary finished product at 760 ℃ to obtain the aluminum-uniformly-doped cobaltosic oxide with large particle size. FIG. 2 is an electron micrograph of the aluminum-doped cobaltosic oxide obtained in example 2 and a distribution diagram of aluminum in the aluminum-doped cobaltosic oxide obtained in example 2.
Example 3
Preparing a cobalt-aluminum solution and preparing an ammonium bicarbonate solution; the cobalt-aluminum solution contains cobalt ions and aluminum ions, wherein the concentration of the cobalt ions in the cobalt-aluminum solution is 110g/L, and the concentration of the aluminum ions in the cobalt-aluminum solution is 1.2 g/L; the concentration of the ammonium bicarbonate solution was 220 g/L.
Adding pure water and an ammonium bicarbonate solution into the first crystal seed kettle to prepare a base solution, stirring the base solution at the stirring speed of 150r/min, wherein a stirring mechanism of the first crystal seed kettle adopts a double-layer stirring paddle. Controlling the pH value of the base solution to be 8.4; the concentration of ammonium bicarbonate in the base solution is 30g/L, and the ratio of the volume of pure water added into the first crystal seed kettle to the volume of the first crystal seed kettle is 0.6; the temperature of the base solution was 50 ℃.
And simultaneously adding a cobalt aluminum solution and an ammonium bicarbonate solution into the first seed crystal kettle at feeding flow rates of 450L/h and 800L/h respectively, keeping the pH of the material in the first seed crystal kettle at 7.5, controlling the growth speed of the material in the first seed crystal kettle to be 0.65 mu m per 8 hours of growth, and stopping the reaction when the granularity D50 of the material in the first seed crystal kettle is 7.0 mu m to obtain the first seed crystal.
Half of the material in the first crystal seed kettle is separated into a second crystal seed kettle, and 0.4m ammonium bicarbonate solution is added into the second crystal seed kettle3Controlling the pH value of the material in the second crystal seed kettle to be 7.8, controlling the stirring speed of the second crystal seed kettle to be 80r/min, and adopting a double-layer stirring paddle blade for a stirring mechanism of the second crystal seed kettle. And simultaneously adding the cobalt aluminum solution and the ammonium bicarbonate solution into a second crystal seed kettle at feed flow rates of 450L/h and 800L/h respectively, keeping the pH of the material in the second crystal seed kettle at 7.5, controlling the growth speed of the material in the second crystal seed kettle to be 0.85 mu m per 8 hours, and stopping the reaction when the granularity D50 of the material in the second crystal seed kettle is 12.0 mu m to obtain second crystal seeds.
Half of the material in the second crystal kettle is separated into a finished product kettle, and 0.4m ammonium bicarbonate solution is added into the finished product kettle3Controlling the pH value of the material in the finished product kettle to be 7.8, and controlling the stirring speed of the finished product kettle to be 50 r/min; and simultaneously adding a cobalt aluminum solution and an ammonium bicarbonate solution into a finished product kettle at feed flow rates of 450L/h and 800L/h respectively, keeping the pH of the material in the finished product kettle at 7.5, controlling the growth speed of the material in the finished product kettle to be 0.95 mu m in growth per 8 hours, and stopping reaction when the granularity D50 of the material in the finished product kettle is 23.0 mu m to obtain a primary finished product.
Centrifugally washing the primary finished product by using a centrifugal machine, wherein a pure water washing mode is adopted in the washing process, and the temperature of the pure water is 60 ℃; and (3) centrifugally washing the primary finished product, then sending the washed primary finished product into a rotary kiln, and calcining the centrifugally washed primary finished product at 720 ℃ to obtain the aluminum-uniformly-doped cobaltosic oxide with large particle size. FIG. 3 is an electron micrograph of the aluminum-doped cobaltosic oxide obtained in example 3 and a distribution diagram of aluminum in the aluminum-doped cobaltosic oxide obtained in example 3.
The above description is only for the preferred embodiment of the present invention and does not limit the scope of the present invention. It should be noted that other equivalent modifications can be made by those skilled in the art in light of the teachings of the present invention, and all such modifications can be made as are within the scope of the present invention.
Claims (8)
1. A preparation method of aluminum uniformly doped cobaltosic oxide with large particle size is characterized by comprising the following steps:
(1) preparing a cobalt-aluminum solution and preparing an ammonium bicarbonate solution;
(2) adding pure water and the ammonium bicarbonate solution obtained in the step (1) into the first crystal seed kettle to prepare a base solution, stirring the base solution, and controlling the pH value of the base solution to be 7.5-8.5;
(3) adding the cobalt-aluminum solution and the ammonium bicarbonate solution in the step (1) into a first seed crystal kettle simultaneously, keeping the pH of the material in the first seed crystal kettle to be 7.2-7.6, controlling the growth speed of the material in the first seed crystal kettle to be 0.55-0.75 μm per 8 hours, and stopping the reaction when the granularity D50 of the material in the first seed crystal kettle is 6.0-7.0 μm to obtain a first seed crystal;
(4) dividing half of the material in the first seed crystal kettle into a second seed crystal kettle, adding the ammonium bicarbonate solution obtained in the step (1) into the second seed crystal kettle, controlling the pH of the material in the second seed crystal kettle to be 7.6-7.8, simultaneously adding the cobalt aluminum solution and the ammonium bicarbonate solution obtained in the step (1) into the second seed crystal kettle, keeping the pH of the material in the second seed crystal kettle to be 7.2-7.6, controlling the growth speed of the material in the second seed crystal kettle to be 0.65-0.95 mu m per 8 hours, and stopping the reaction when the granularity D50 of the material in the second seed crystal kettle is 11.0-12.0 mu m to obtain a second seed crystal;
(5) half of the material in the second crystal kettle is separated into a finished product kettle, the ammonium bicarbonate solution in the step (1) is added into the finished product kettle, the pH of the material in the finished product kettle is controlled to be 7.6-7.8, the cobalt aluminum solution and the ammonium bicarbonate solution in the step (1) are simultaneously added into the finished product kettle, the pH of the material in the finished product kettle is kept to be 7.2-7.6, the growth speed of the material in the finished product kettle is controlled to be 0.65-0.95 mu m per 8 hours, the reaction is stopped when the granularity D50 of the material in the finished product kettle is 19.0-23.0 mu m, and a primary finished product is obtained;
(6) and sequentially carrying out centrifugal washing and calcination on the primary finished product to obtain the aluminum-uniformly-doped cobaltosic oxide with large particle size.
2. The method for preparing aluminum-uniformly-doped large-particle-size cobaltosic oxide according to claim 1, wherein the cobalt-aluminum solution in the step (1) contains cobalt ions and aluminum ions, the concentration of the cobalt ions in the cobalt-aluminum solution is 100g/L-140g/L, and the concentration of the aluminum ions in the cobalt-aluminum solution is 0.5g/L-1.5 g/L; the concentration of the ammonium bicarbonate solution in the step (1) is 200g/L-280 g/L.
3. The method for preparing uniformly aluminum-doped large-particle-size cobaltosic oxide according to claim 1, wherein the ammonium bicarbonate concentration in the base solution in the step (2) is 10g/L to 30g/L, and the ratio of the volume of pure water added to the first seed crystal tank to the volume of the first seed crystal tank is 0.5 to 0.7; the temperature of the base solution in the step (2) is 30-50 ℃, and the stirring speed for stirring the base solution is 150-300 r/min.
4. The method for preparing aluminum-uniformly-doped large-particle-size cobaltosic oxide according to claim 1, wherein the feeding flow rates of the cobalt aluminum solution and the ammonium bicarbonate solution simultaneously added into the first seed crystal tank in the step (3) are 250L/h-500L/h and 500L/h-1000L/h respectively.
5. The method for preparing uniformly aluminum-doped large-particle-size cobaltosic oxide according to claim 1, wherein the ammonium bicarbonate solution added to the second seed crystal tank in the step (4) is added in an amount of 0.1m3-0.5m3(ii) a In the step (4), the stirring speed of the second crystal seed kettle is controlled to be 50r/min-150 r/min; in the step (4), the feeding flow rates of the cobalt aluminum solution and the ammonium bicarbonate solution which are simultaneously added into the second crystal seed kettle are respectively 100L/h-500L/h and 150L/h-1000L/h.
6. The method of claim 1, wherein the ammonium bicarbonate solution is added to the final kettle in the step (5) in an amount of 0.1m3-0.5m3(ii) a Controlling the stirring speed of the finished product kettle to be 30r/min-100r/min in the step (5); in the step (5), the feeding flow rates of the cobalt aluminum solution and the ammonium bicarbonate solution which are simultaneously added into the finished product kettle are respectively 100L/h-500L/h and 150L/h-1000L/h.
7. The method for preparing the aluminum-uniformly-doped large-particle-size cobaltosic oxide as claimed in claim 1, wherein the stirring mechanism of the first seed crystal kettle adopts a double-layer stirring blade; and the stirring mechanism of the second crystal seed kettle adopts a double-layer stirring paddle.
8. The method for preparing the uniformly aluminum-doped large-particle-size cobaltosic oxide according to claim 1, wherein the primary product in the step (6) is centrifugally washed by a centrifuge, and the washing process is carried out by pure water washing at 50-70 ℃; and (6) centrifugally washing the primary finished product, then sending the primary finished product into a rotary kiln, and calcining the centrifugally washed primary finished product at the temperature of 600-800 ℃.
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