CN109179516B - Aluminum-doped small-particle spherical cobaltosic oxide and preparation method thereof - Google Patents
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Abstract
The invention relates to the field of battery materials, in particular to aluminum-doped small-particle spherical cobaltosic oxide and a preparation method thereof. The preparation method of the intermittent aluminum-doped small-particle spherical cobaltosic oxide comprises the following steps: mixing a metal solution containing aluminum and cobalt and a precipitant solution in a volume ratio of 1: mixing at a ratio of 0.8-1.5, and performing crystallization reaction at 30-60 deg.C for several times to obtain crystal grains with required granularity; then separating to obtain supernatant and final slurry; and then sintering the final slurry in stages to obtain the aluminum-doped small-particle spherical cobaltosic oxide. The synthesis process is simple, the reaction is easy to control, the reaction process is pollution-free, and the industrial production is easy to realize. The prepared cobaltosic oxide has the advantages of uniform distribution of aluminum elements, regular surface appearance, good sphericity and high tap density.
Description
Technical Field
The invention relates to the field of battery materials, in particular to aluminum-doped small-particle spherical cobaltosic oxide and a preparation method thereof.
Background
In the positive electrode material of lithium ion battery, LiCoO2Has been dominated by LiCoO2The lithium ion battery is very suitable for the insertion and the desorption of lithium ions, has the advantages of high voltage, stable discharge, high specific energy, good cycle performance, simple preparation process and the like, and can adapt to large-current charge and discharge. The small-particle cobaltosic oxide is mainly used for preparing high-rate lithium cobaltate. The common small-particle cobaltosic oxide in the market at present has the defects of low tap density, poor sphericity and uneven distribution of doping elements, so that the poor cycle performance and poor stability of the lithium ion battery can be caused.
Disclosure of Invention
The invention provides a preparation method of intermittent aluminum-doped small-particle spherical cobaltosic oxide, which has the advantages of simple synthesis process, easy control of reaction, no pollution in the reaction process and easy industrial production.
The invention also provides aluminum-doped small-particle spherical cobaltosic oxide, and the product has the advantages of uniform aluminum element distribution, regular surface appearance, good sphericity and high tap density.
The invention is realized by the following steps:
a method for preparing intermittent aluminum-doped small-particle spherical cobaltosic oxide comprises the following steps:
mixing a metal solution containing aluminum and cobalt and a precipitant solution in a volume ratio of 1: mixing at a ratio of 0.8-1.5, and performing crystallization reaction at 30-60 deg.C for several times to obtain crystal grains with required granularity;
then separating to obtain supernatant and final slurry;
and then sintering the final slurry in stages to obtain the aluminum-doped small-particle spherical cobaltosic oxide.
The aluminum-doped small-particle spherical cobaltosic oxide is prepared by the preparation method of the intermittent aluminum-doped small-particle spherical cobaltosic oxide.
The invention has the beneficial effects that: the preparation method of the intermittent aluminum-doped small-particle spherical cobaltosic oxide has the advantages of uniform aluminum element distribution, regular surface appearance, good sphericity, high tap density and the like by controlling the reaction temperature, the proportion of reaction raw materials and the calcining mode. Meanwhile, the process flow is simple, the reaction is easy to control, the reaction process is pollution-free, and the industrial production is easy to realize. And lithium cobaltate prepared from the synthesized small-particle spherical cobaltosic oxide is overcharge-resistant, and has the advantages of high cycle capacity retention rate, good stability, good electrochemical performance and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments will be briefly described below.
FIG. 1 is a particle size distribution diagram of cobaltosic oxide provided in example 2;
FIG. 2 is an EDS diagram of cobaltosic oxide provided in example 1;
FIG. 3 is an EDS map of cobaltosic oxide provided in example 2;
FIG. 4 is an EDS map of cobaltosic oxide provided in example 3;
FIG. 5 is an EDS map of cobaltosic oxide provided in comparative example 1;
FIG. 6 is an EDS map of cobaltosic oxide provided in comparative example 2;
FIG. 7 is an EDS map of cobaltosic oxide provided in comparative example 3;
FIG. 8 is an EDS map of cobaltosic oxide provided in comparative example 4;
FIG. 9 is an EDS map of cobaltosic oxide provided in comparative example 5;
figure 10 is an EDS plot of the cobaltosic oxide provided in comparative example 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The aluminum-doped small-particle spherical cobaltosic oxide and the preparation method thereof according to the embodiments of the present invention will be specifically described below.
A method for preparing intermittent aluminum-doped small-particle spherical cobaltosic oxide comprises the following steps:
s1, preparing a metal solution and a precipitant solvent respectively:
respectively dissolving a cobalt source and an aluminum source by using water, and then mixing the cobalt source solution and the aluminum source solution to obtain a metal solution containing aluminum and cobalt. The cobalt source and the aluminum source are respectively dissolved to obtain a solution, so that the cobalt source and the aluminum source are more favorably and uniformly mixed, the prepared cobaltosic oxide is ensured to be uniformly distributed, the sphericity is good, and the performance is improved.
Further, the mass ratio of the cobalt to the aluminum in the metal solution is 100: 0.01-2.5. The mass ratio of cobalt to aluminum in the metal solution can ensure that the cobalt and aluminum content in the prepared cobaltosic oxide is proper by adopting the proportion, and further ensure that the cobaltosic oxide has good performance.
Further, the cobalt source is a cobalt salt selected from any one or at least two of cobalt sulfate, cobalt chloride and cobalt nitrate.
The aluminum source is aluminum salt selected from any one or at least two of aluminum nitrate, aluminum sulfate and aluminum chloride.
The precipitant solution is a solution obtained by mixing a precipitant with water, preferably, the precipitant is a carbonate, and more preferably, the carbonate is any one or at least two of ammonium bicarbonate, ammonium carbonate, sodium carbonate, and sodium bicarbonate.
The concentration of the precipitant solution is 200-300g/L, and the adoption of the concentration can ensure that the precipitant can well form precipitate with cobalt and aluminum, thereby ensuring the yield.
S2, crystallization reaction;
the metal solution and the precipitant solution are mixed in parallel flow, and then crystallization reaction is carried out under the conditions that the stirring speed is 200-600rpm and the temperature is 30-60 ℃ to obtain the reaction with the particle size of 2.0-3.0 microns. Specifically, 500-1000L of precipitator solution is added into a reaction kettle to serve as a base solution, so that the precipitation effect is improved, then the temperature is raised to 30-60 ℃, the metal solution and the precipitator solution are mixed in a parallel flow mode, the mixed solution is stirred in the mixing process until the reaction kettle is full, then feeding is stopped, and continuous stirring and heat preservation are carried out, so that particles with a certain particle size are obtained.
The metal solution and the precipitator solution are mixed in a parallel flow mode, so that the carbonate ions in the precipitator solution can be further ensured to be fully and uniformly mixed with the cobalt and the aluminum in the metal solution, and the aluminum element in the prepared cobaltosic oxide is further ensured to be uniformly distributed.
Simultaneously, adopt above-mentioned stirring speed not only can make the crystal nucleus carry out good parcel to aluminium, cobalt, promote the homogeneity of parcel, reduce the damage of crystal nucleus simultaneously, guarantee growing up of crystal nucleus, guarantee the integrality of the spherical structure of the cobaltosic oxide that follow-up preparation obtained. And the crystallization reaction can be ensured to have good speed in the temperature range, and then the structural integrity of the prepared crystal nucleus can be ensured.
Further, the volume ratio of the metal solution to the precipitant solution is 1: 0.8-1.5, the proportion of the metal solution and the precipitator solution is controlled, the precipitation effect is improved, and the yield is improved.
Further, the flow rate of the metal solution is 400-900L/h, and the flow rate of the precipitant solution is 500-900L/h. The flow of the metal solution and the precipitant solution is controlled, the crystal nucleus forming and growing speed can be effectively controlled, the stable and continuous growth of the crystal nucleus is further ensured, and the cobaltosic oxide obtained by subsequent preparation is ensured to have a good spherical shape and a regular surface appearance.
And then when the grain size of the crystal nucleus obtained by the first crystallization reaction is 2.0-3.0 microns, separating to obtain supernatant and first slurry, wherein the grains in the first slurry are only grains with small grain size, and the surfaces of the grains are relatively rough and irregular. Therefore, the first slurry needs to be subjected to multiple cyclic crystallization reactions to promote the growth of the particles in the first slurry, specifically, the first slurry is mixed with the metal solution and the precipitant solution to perform a second crystallization reaction, i.e., a first cyclic crystallization reaction, the flow rate and the ratio of the metal solution and the precipitant solution of the second crystallization reaction are consistent with those of the first crystallization reaction, so that crystal nuclei can grow, after the particle size of the crystal nuclei obtained by the first cyclic crystallization reaction is increased by 0.1 to 0.3 microns relative to the crystal nuclei obtained by the first crystallization reaction, the crystal nuclei are separated to obtain a second slurry, and the second slurry is subjected to the second cyclic crystallization, and the cycle is repeated until the particle size of the crystal nuclei in the finally obtained slurry is the desired particle size of the crystal nuclei.
The crystal nucleus obtained by the first crystallization reaction has relatively large granularity, so that the formation of the crystal nucleus and the growth of subsequent crystal nuclei are convenient to observe, then the cyclic crystallization reaction is carried out at the speed of 0.1-0.3 micron/time to repeatedly wrap the crystal nucleus of the raw material, the growth of the crystal nucleus is promoted, the structural integrity of the prepared crystal nucleus is ensured, crystal grains with the required granularity are finally obtained, and the amplitude of each granularity is consistent.
And then separating to obtain final slurry, washing and centrifuging the final slurry to remove ions or solvent remained on the surface of solid matters in the slurry, and removing redundant aqueous solution in the slurry.
S3, sintering in stages;
and then sintering the centrifuged final slurry in stages, specifically, sintering the final slurry at the temperature of 300-550 ℃ for 2-4 hours, and then sintering the final slurry at the temperature of 700-1000 ℃ for 4-7 hours. The staged sintering can release moisture and oxygen in stages, avoids sudden heating to high temperature to release water vapor and carbon dioxide quickly, and a large amount of water vapor and oxygen impact the crystal nucleus with complete structure, so that the surface of the crystal nucleus is easy to crack, and the structure of the obtained cobaltosic oxide is damaged. Therefore, by adopting staged sintering, water vapor and oxygen can be released slowly in stages, the damage of gas to the structure of the cobaltosic oxide is reduced, and the prepared cobaltosic oxide is ensured to have regular surface appearance, good sphericity and high tap density.
Specifically, the sintering at the temperature of 300-550 ℃ can change the moisture in the crystal nucleus into water vapor, then slowly overflow the crystal nucleus, then remove the moisture, and the sintering of the crystal nucleus at the temperature of 700-1000 ℃ can generate decomposition reaction to produce carbon dioxide and cobaltosic oxide.
The embodiment of the invention also provides the aluminum-doped small-particle spherical cobaltosic oxide which is prepared by the preparation method of the intermittent aluminum-doped small-particle spherical cobaltosic oxide.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of intermittent aluminum-doped small-particle spherical cobaltosic oxide, which comprises the following steps:
s1, preparing a metal solution and a precipitant solvent respectively:
respectively dissolving aluminum sulfate and cobalt chloride by using deionized water, and then mixing an aluminum sulfate solution and a cobalt chloride solution to obtain a metal solution containing aluminum and cobalt, wherein cobalt ions and aluminum ions in the metal solution are respectively 100g/L and 0.68 g/L. Ammonium bicarbonate was dissolved in deionized water to give a precipitant solution concentration of 230 g/L.
S2, crystallization reaction;
at 10m3Adding 500L of ammonium bicarbonate solution into a reaction kettle, heating to 46 ℃, mixing the metal solution and the precipitant solution in a parallel flow mode, wherein the flow rate of the metal solution is 400L/h, the flow rate of the precipitant solution is 560L/h, the stirring speed is 450rpm until the reaction kettle is full, stopping feeding, continuously stirring and preserving heat, and the granularity of the first crystallization reaction is 2.0-2.5 um; filtering to obtain first slurry after the granularity meets the requirement, then mixing the first slurry with a metal solution and a precipitant solution, wherein the flow rate of the metal solution is 400L/h, the flow rate of the precipitant solution is 560L/h, the stirring speed is 450rpm, carrying out a first circulation crystallization reaction, filtering to obtain second slurry after the particle size is increased by 0.1-0.2 micron, fully carrying out the first circulation crystallization reaction on the second slurry until the particle size is the target granularity, separating to obtain final slurry, washing and centrifuging the final slurry.
S3, sintering in stages;
sintering the final slurry at the temperature of 350-450 ℃ for 3.5 hours, and then sintering the final slurry at the temperature of 700-800 ℃ for 4 hours to finally obtain the cobaltosic oxide.
The embodiment also provides cobaltosic oxide prepared by the preparation method of the intermittent aluminum-doped small-particle spherical cobaltosic oxide, wherein the particle size distribution of the cobaltosic oxide is shown in figure 1, and the specific properties are as follows: d50 ═ 3.52um, tap density 2.02g/cm3。
Examples 2 to 6
The preparation method of the batch type aluminum-doped small-particle spherical cobaltosic oxide provided in examples 2 to 6 is basically identical to the preparation method of the batch type aluminum-doped small-particle spherical cobaltosic oxide provided in example 1 in operation, except that specific operating conditions are changed.
Example 2
The cobalt source is cobalt chloride, the aluminum source is aluminum sulfate, the cobalt ions and the aluminum ions in the metal solution are respectively 100g/L and 0.68g/L, the precipitator is sodium carbonate, and the concentration of the precipitator solution is 230 g/L.
The quantity of the precipitant solution of the base solution is 800L, the temperature is 46 ℃, the flow rate of the metal solution is 500L/h, the flow rate of the precipitant solution is 700L/h, the stirring speed is 400rpm, the granularity of the first crystallization reaction is controlled to be 2.5-2.8um, and the fluctuation of the granularity of each time of the multiple circulation crystallization reactions is 0.2-0.3 micron/time.
The staged sintering is as follows: the first sintering temperature is 350-550 ℃, the sintering time is 3.5 hours, the second sintering temperature is 700-900 ℃, and the sintering time is 7 hours.
Properties of the resulting cobaltosic oxide: d50 ═ 4.31um, tap density 2.11g/cm3And the particle size distribution thereof is detected.
Example 3
The cobalt source is cobalt chloride, the aluminum source is aluminum sulfate, the cobalt ions and the aluminum ions in the metal solution are respectively 100g/L and 0.68g/L, the precipitator is sodium carbonate, and the concentration of the precipitator solution is 230 g/L.
The quantity of the precipitant solution of the base solution is 900L, the temperature is 46 ℃, the flow rate of the metal solution is 600L/h, the flow rate of the precipitant solution is 840L/h, the stirring speed is 350rpm, the granularity of the first crystallization reaction is controlled to be 3.0-3.5um, and the fluctuation of the granularity of each time of the multiple circulation crystallization reactions is 0.1-0.3 micron/time.
The staged sintering is as follows: the first sintering temperature is 350-550 ℃, the sintering time is 3.5 hours, the second sintering temperature is 700-900 ℃, and the sintering time is 6 hours.
Properties of the resulting cobaltosic oxide: d50 ═ 5.03um, tap density 2.22g/cm3。
Example 4
The cobalt source is cobalt nitrate, the aluminum source is aluminum chloride, the cobalt ions and the aluminum ions in the metal solution are respectively 100g/L and 2.5g/L, the precipitator is sodium carbonate, and the concentration of the precipitator solution is 200 g/L.
The quantity of the precipitant solution of the base solution is 600L, the temperature is 60 ℃, the flow rate of the metal solution is 450L/h, the flow rate of the precipitant solution is 675L/h, the stirring speed is 600rpm, the granularity of the first crystallization reaction is controlled to be 2.0-3.0um, and the fluctuation of the granularity of each time of the multiple circulation crystallization reactions is 0.2-0.25 micron/time.
The staged sintering is as follows: the first sintering temperature is 300-550 ℃, the sintering time is 2 hours, the second sintering temperature is 700-1000 ℃, and the sintering time is 5 hours.
Properties of the resulting cobaltosic oxide: d50 ═ 5.8um, tap density 2.3g/cm3。
Example 5
The cobalt source is cobalt sulfate, the aluminum source is aluminum nitrate, the cobalt ions and the aluminum ions in the metal solution are respectively 100g/L and 0.01g/L, the precipitator is sodium carbonate, and the concentration of the precipitator solution is 300 g/L.
The quantity of the precipitant solution of the base solution is 1000L, the temperature is 30 ℃, the flow rate of the metal solution is 700L/h, the flow rate of the precipitant solution is 560L/h, the stirring speed is 200rpm, the granularity of the first crystallization reaction is controlled to be 2.2-2.7um, and the fluctuation of the granularity of each time of the multiple circulation crystallization reactions is 0.15-0.2 micron/time.
The staged sintering is as follows: the first sintering temperature is 400-450 ℃, the sintering time is 4 hours, the second sintering temperature is 850-950 ℃, and the sintering time is 6.5 hours.
Properties of the resulting cobaltosic oxide: d50 ═ 3.14um, tap density 2.0g/cm3。
Example 6
The cobalt source is cobalt chloride, the aluminum source is aluminum chloride, the cobalt ions and the aluminum ions in the metal solution are respectively 100g/L and 1.5g/L, the precipitator is sodium carbonate, and the concentration of the precipitator solution is 265 g/L.
The quantity of the precipitant solution of the base solution is 750L, the temperature is 50 ℃, the flow rate of the metal solution is 900L/h, the flow rate of the precipitant solution is 900L/h, the stirring speed is 550rpm, the granularity of the first crystallization reaction is controlled to be 2.3-2.6um, and the fluctuation of the granularity of each time of the multiple circulation crystallization reactions is 0.16-0.25 micron/time.
The staged sintering is as follows: the first sintering temperature is 370-550 ℃, the sintering time is 2.5 hours, the second sintering temperature is 800-950 ℃, and the sintering time is 5.5 hours.
Obtained fourProperties of cobaltosic oxide: d50 ═ 5.1um, tap density 2.25g/cm3。
Comparative example 1: tricobalt tetroxide was prepared in the manner provided in example 1, except that sintering was carried out at a temperature of 350-450 ℃ for 7.5 hours.
Comparative example 2: tricobalt tetroxide was prepared in the manner provided in example 1, except that sintering was carried out at a temperature of 700 ℃ and 800 ℃ for 7.5 hours.
Comparative example 3: tricobalt tetraoxide was prepared in the manner provided in example 1, except that the temperature of the multiple crystallization reaction was 100 ℃.
Comparative example 4: tricobalt tetraoxide was prepared in the manner provided in example 1, except that the temperature of the multiple crystallization reaction was 10 ℃.
Comparative example 5: tricobalt tetraoxide was prepared in the manner provided in example 1, except that the stirring speed for the multiple crystallization reaction was 1000 rpm.
Comparative example 6: tricobalt tetraoxide was prepared in the manner provided in example 1, except that the stirring speed for the multiple crystallization reaction was 50 rpm.
The average particle diameter and tap density of the cobaltosic oxide prepared in comparative examples 1 to 6 were measured, and the specific test results are shown in table 1.
TABLE 1 test results
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| D50 | 3.52 | 4.8 | 4.12 | 6.8 | 3.89 | 3.72 | 8.7 |
| Tap density | 2.02 | 1.89 | 1.91 | 1.84 | 1.76 | 1.98 | 1.65 |
As can be seen from Table 1, the particle size and tap density control is unstable without staged calcination, the particle size fluctuation is too large by changing the stirring speed in the examples of the present invention, and the particle size is too large or too small and the tap density is too small by changing the reaction temperature in the examples of the present invention.
The tricobalt tetroxide prepared in examples 1-3 and comparative examples 1-6 was subjected to EDS test, and the test results are shown in table 2-table 10 and fig. 2-fig. 10.
TABLE 2 EDS data for cobaltosic oxide of example 1
TABLE 3 EDS data for cobaltosic oxide of example 2
Table 4 tricobalt tetraoxide EDS data for example 3
TABLE 5 EDS data for Cobaltosic oxide of comparative example 1
Comparing the data in tables 2 and 5, it can be seen that the cobalt content in the cobalt oxide is low and the cobalt carbonate is not completely decomposed when the cobalt oxide is sintered at the temperature of 350-450 ℃ for 7.5 hours.
TABLE 6 tricobalt tetraoxide EDS data for comparative example 2
Comparing the data in tables 2 and 6, it can be seen that the distribution of aluminum element is relatively uniform when the temperature is maintained at 800 ℃ for 7.5 hours at 700-.
TABLE 7 EDS data for Cobaltosic oxide of comparative example 3
Comparing the data in tables 2 and 7, it can be seen that the excessive reaction temperature causes the segregation of aluminum element.
TABLE 8 EDS data for Cobaltosic oxide of comparative example 4
It can be seen from the comparison of the data in tables 2 and 8 that too low reaction temperature results in serious segregation of aluminum element and a large difference in the contents.
TABLE 9 EDS data for Cobaltosic oxide of comparative example 5
The data in tables 2 and 9 show that the uniformity of aluminum is good.
TABLE 10 EDS data for Cobaltosic oxide of comparative example 6
Comparing the data in tables 2 and 10, it is understood that the degree of aluminum segregation is large when the stirring speed is low.
Lithium cobaltate was prepared using the cobaltosic oxides of examples 1 to 3 and comparative examples 1 to 6, respectively, and the prepared lithium cobaltate was prepared by the prior art, and then the electrochemical properties of the lithium cobaltate were measured, and the measurement results of the charge and discharge capacity were shown in table 11 when the measurement voltage was 4.5V.
TABLE 11 electrochemical Properties
As can be seen from Table 11, it can be seen that the present invention has a higher charge capacity and discharge capacity.
In conclusion, the preparation method of the intermittent aluminum-doped small-particle spherical cobaltosic oxide has the advantages of uniform distribution of aluminum elements, regular surface appearance, good sphericity, high tap density and the like by controlling the reaction temperature, the proportion of reaction raw materials and the calcining mode. Meanwhile, the process flow is simple, the reaction is easy to control, the reaction process is pollution-free, and the industrial production is easy to realize. And lithium cobaltate prepared from the synthesized small-particle spherical cobaltosic oxide is overcharge-resistant, and has the advantages of high cycle capacity retention rate, good stability, good electrochemical performance and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing intermittent aluminum-doped small-particle spherical cobaltosic oxide is characterized by comprising the following steps:
mixing a metal solution containing aluminum and cobalt and a precipitant solution in a volume ratio of 1: mixing at a ratio of 0.8-1.5, and performing crystallization reaction at 30-60 deg.C for several times to obtain crystal grains with required granularity;
then separating to obtain supernatant and final slurry;
then sintering the final slurry by stages to obtain the aluminum-doped small-particle spherical cobaltosic oxide;
the multiple crystallization reaction is to mix the metal solution and the precipitant solution, carry out a first crystallization reaction to obtain a first slurry, and mix the first slurry with the metal solution and the precipitant solution to carry out multiple cyclic crystallization reactions; the grain size of the crystal nucleus in the first slurry is 2.0-3.0 microns; each circulation crystallization reaction is that the grain size of the crystal nucleus of the obtained slurry is increased by 0.1-0.3 micron per time until the grain size of the crystal nucleus of the slurry is increased to the grain with the required grain size;
the staged sintering is to sinter the final slurry at the temperature of 300-550 ℃ for 2-4 hours and then at the temperature of 700-1000 ℃ for 4-7 hours.
2. The method as claimed in claim 1, wherein the first crystallization reaction is a reaction in which the metal solution and the precipitant solution are mixed in a cocurrent manner and then reacted at a stirring speed of 200-600rpm and a temperature of 30-60 ℃ to obtain a particle size of 2.0-3.0 μm.
3. The method as claimed in claim 1, wherein the flow rate of the metal solution is 400-900L/h, and the flow rate of the precipitant solution is 500-900L/h.
4. The method of claim 1, wherein the precipitant solution is a solution obtained by mixing a precipitant with water.
5. The method for preparing the batch type aluminum-doped small-particle spherical cobaltosic oxide according to claim 4, wherein the precipitant is carbonate, and the carbonate is any one or at least two of ammonium bicarbonate, ammonium carbonate, sodium carbonate and sodium bicarbonate.
6. The method of claim 1, wherein the metal solution is a mixture of a cobalt source, an aluminum source and water.
7. The method for preparing the intermittent aluminum-doped small-particle spherical cobaltosic oxide as claimed in claim 6, wherein the mass ratio of the cobalt to the aluminum in the metal solution is 100: 0.01-2.5.
8. The method for preparing the intermittent aluminum-doped small-particle spherical cobaltosic oxide as claimed in claim 6, wherein the cobalt source is a cobalt salt, and the cobalt salt is selected from any one or at least two of cobalt sulfate, cobalt chloride and cobalt nitrate;
the aluminum source is an aluminum salt selected from any one or at least two of aluminum nitrate, aluminum sulfate and aluminum chloride.
9. The method of claim 1, wherein the final slurry is washed and centrifuged prior to sintering.
10. An aluminum-doped small-particle spherical cobaltosic oxide, which is prepared by the method for preparing the batch-type aluminum-doped small-particle spherical cobaltosic oxide as claimed in any one of claims 1 to 9.
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| CN113292106B (en) * | 2020-02-24 | 2023-07-25 | 荆门市格林美新材料有限公司 | Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide |
| CN113651366A (en) * | 2020-05-12 | 2021-11-16 | 荆门市格林美新材料有限公司 | Secondary calcination preparation method of small-particle-size aluminum-doped cobaltosic oxide |
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