CN112978806A - Sectional calcination method of large-particle cobaltosic oxide containing doping elements - Google Patents
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Abstract
The invention belongs to the technical field of lithium ion battery anode materials, and discloses a sectional calcination method of large-particle cobaltosic oxide containing doping elements, which comprises the following steps: firstly, placing large-particle cobalt carbonate containing doping elements in a calcining furnace at 150-250 ℃ for primary calcining; secondly, raising the temperature of the calcining furnace to 300-400 ℃ at a heating rate of 1-3 ℃/min for secondary calcining, and raising the temperature of the calcining furnace to 500-600 ℃ at a heating rate of 1-2 ℃/min for tertiary calcining; and finally, raising the temperature of the calcining furnace to 650-750 ℃ at a temperature raising speed of 1-1.5 ℃/min, and carrying out four-time calcination to obtain large-particle cobaltosic oxide containing doping elements. The invention can solve the problems of serious cracking of spheres and poor sphericity in the existing calcining method of large-particle cobaltosic oxide doped with metal elements.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a sectional calcination method of large-particle cobaltosic oxide containing doping elements.
Background
The cobaltosic oxide is a main raw material of lithium cobaltate and is mainly applied to the field of 3C electronic products. The lithium cobalt oxide in the current use has the problems that the theoretical voltage is more than 4.2V, but the average voltage is only 3.6V at present, the maximum voltage is not more than 4.0V, the theoretical specific capacity is 260hA/kg, the actual specific capacity is 130hA/kg, and the capacity is reduced along with the increase of the cycle number. In order to release higher energy in a smaller space, lithium cobaltate can release more lithium ions from a crystal structure under the high voltage developed towards the direction of high voltage of 4.5V-4.6V, and the structural stability of the material during high voltage charge and discharge can be improved by doping aluminum at present.
However, when the large-particle cobalt carbonate doped with the metal element is calcined into cobaltosic oxide, carbon dioxide gas released by decomposition of the cobalt carbonate and diffusion of the metal element cause serious cracking of the spheres of the large-particle cobaltosic oxide, so that the diffusivity and sphericity of lithium ions in the subsequent process of calcining lithium cobaltate are affected, and the electrochemical stability and cycle performance of the lithium cobaltate are seriously affected finally.
Disclosure of Invention
In view of the above, the present application provides a sectional calcination method for large-particle cobaltosic oxide containing a doping element, so as to solve the problems of severe spherical cracking and poor sphericity in the existing calcination method for large-particle cobaltosic oxide doped with a metal element.
The invention adopts the following scheme: a staged calcination method of large-particle cobaltosic oxide containing doping elements, which comprises the following steps:
s1, placing the large-particle cobalt carbonate containing the doping elements in a calcining furnace at the temperature of 150-250 ℃, preserving the heat for 3.5-4.5 h, and carrying out primary calcining;
s2, after the primary calcining, raising the temperature of the calcining furnace to 300-400 ℃ at a temperature raising speed of 1-3 ℃/min, and preserving the heat for 3.5-4.5 h to carry out secondary calcining;
s3, after the secondary calcining and sintering, raising the temperature of the calcining furnace to 500-600 ℃ at a temperature raising speed of 1-2 ℃/min, and preserving the heat for 1.5-2.5 h to carry out tertiary calcining;
and S4, after the third calcination, raising the temperature of the calciner to 650-750 ℃ at a temperature raising speed of 1-1.5 ℃/min, preserving the heat for 3.5-4.5 h, and carrying out four-time calcination to obtain large-particle cobaltosic oxide containing the doping elements.
Preferably, the method comprises the steps of:
s1, placing large-particle cobalt carbonate containing doping elements in a calcining furnace at 200 ℃, preserving heat for 4 hours, and carrying out primary calcining;
s2, after the primary calcination, raising the temperature of the calciner to 350 ℃ at a temperature raising speed of 2.25 ℃/min, and preserving the heat for 4 hours to carry out secondary calcination;
s3, after the secondary calcining and sintering, raising the temperature of the calcining furnace to 550 ℃ at the temperature raising speed of 1.7 ℃/min, preserving the heat for 2h, and carrying out tertiary calcining;
and S4, after the third calcination, raising the temperature of the calciner to 700 ℃ at a temperature raising speed of 1.25 ℃/min, preserving the heat for 4h, and carrying out four-time calcination to obtain large-particle cobaltosic oxide containing the doping elements.
Preferably, the large-particle cobalt carbonate containing the doping element is aluminum-doped large-particle cobalt carbonate, titanium-doped large-particle cobalt carbonate or zirconium-doped large-particle cobalt carbonate.
Preferably, the large-particle cobalt carbonate containing the doping element is large-particle cobalt carbonate wrapping the oxide of the doping element.
Preferably, the large-particle cobalt carbonate coated with the doped element oxide is prepared by the following method:
step 1, mixing a suspension of doped element oxide with a cobalt salt solution to obtain a mixed solution;
and 2, adding the mixed solution obtained in the step 1 and a precipitator solution containing carbonic acid ions into a reaction device in a cocurrent mode for coprecipitation reaction to obtain large-particle cobalt carbonate wrapping the doped element oxide.
Preferably, in the step 1, the mass ratio of the doping element oxide to the cobalt ions in the mixed solution is (0.2-5): 100; the pH value of the mixed solution is 0.5-1.5.
Preferably, in the step 1, the concentration of the doped element oxide in the suspension of the doped element oxide is 0.01-0.05 mol/L, and the concentration of the cobalt ion in the cobalt salt solution is 0.4-2.0 mol/L.
Preferably, in the step 2, the feeding amount of the mixed solution is 30-60 ml/min; the precipitant solution is ammonium bicarbonate solution or ammonium carbonate solution with the concentration of 1-3 mol/L, and the feeding amount of the precipitant solution is 10-50 ml/min.
Preferably, in the step 2, the reaction temperature of the coprecipitation is 30-50 ℃, and the reaction time is 48-72 hours.
Preferably, the step of S1 includes:
loading large-particle cobalt carbonate containing doping elements into a burning boat, putting the burning boat into a roller kiln at the temperature of 150-250 ℃, preserving heat for 3.5-4.5 h, and carrying out primary calcination.
Compared with the prior art, the invention adopting the scheme has the beneficial effects that:
the large-particle cobaltosic oxide containing doping elements is subjected to four-stage treatment by adopting the methodThe product prepared by calcining has the tap density as high as 2.5g/cm3The specific surface area is as high as 3.7m2(ii)/g; and the surface of the product almost has no cracking phenomenon, and the sphericity degree is relatively good.
Drawings
FIG. 1 is a scanning electron microscope image of aluminum-doped large-particle cobaltosic oxide prepared in example 1 of the present invention, which is magnified 1000 times;
FIG. 2 is a scanning electron microscope image of the aluminum-doped large-particle cobaltosic oxide prepared in comparative example 1 at 1000 times magnification;
FIG. 3 is a scanning electron microscope image of the aluminum-doped large-particle cobaltosic oxide prepared in comparative example 2 at 1000 times magnification.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following provides a preparation process of large-particle cobalt carbonate containing doping elements:
the large-grained cobalt carbonate containing a doping element used in the following examples was aluminum-doped large-grained cobalt carbonate, titanium-doped large-grained cobalt carbonate, or zirconium-doped large-grained cobalt carbonate.
Wherein, the aluminum-doped large-particle cobalt carbonate can be large-particle cobalt carbonate wrapping nano aluminum oxide;
the titanium-doped large-particle cobalt carbonate can be large-particle cobalt carbonate wrapping nano titanium dioxide;
the zirconium-doped large-particle cobalt carbonate may be a large-particle cobalt carbonate comprising nano zirconium dioxide.
Example 1
The embodiment provides a preparation method of large-particle cobalt carbonate wrapped with nano aluminum oxide, which comprises the following steps:
step 1, mixing a suspension solution of nano aluminum oxide with a cobalt salt solution to obtain a mixed solution;
the mass ratio of the nano aluminum oxide to the cobalt ions in the mixed solution is 0.2: 100; the pH value of the mixed solution is 0.5-1.5;
the concentration of the nano-alumina in the suspension of the nano-alumina is 0.01mol/L, the concentration of cobalt ions in the cobalt salt solution is 0.4mol/L, and the cobalt salt solution is cobalt chloride.
Step 2, adding the mixed solution obtained in the step 1 and a precipitator solution containing carbonic acid ions into a reaction device in a parallel flow mode for coprecipitation reaction to obtain large-particle cobalt carbonate wrapping nano-alumina;
wherein the feeding amount of the mixed solution is 30 ml/min; the precipitant solution is ammonium bicarbonate solution with the concentration of 1mol/L, and the feeding amount of the precipitant solution is 10 ml/min;
the reaction temperature of the coprecipitation is 30 ℃, and the reaction time is 72 h.
Example 2
The preparation process of the large-particle cobalt carbonate coated with the nano titanium dioxide comprises the following steps:
step 1, mixing a suspension solution of nano titanium dioxide with a cobalt salt solution to obtain a mixed solution;
the mass ratio of the nano titanium dioxide to the cobalt ions in the mixed solution is 3: 100; the pH value of the mixed solution is 0.5-1.5;
the concentration of the nano titanium dioxide in the suspension of the nano titanium dioxide is 0.03mol/L, the concentration of cobalt ions in the cobalt salt solution is 1mol/L, and the cobalt salt solution is cobalt nitrate.
Step 2, adding the mixed solution obtained in the step 1 and a precipitator solution containing carbonic acid ions into a reaction device in a cocurrent manner for coprecipitation reaction to obtain large-particle cobalt carbonate wrapping the nano titanium dioxide;
wherein the feeding amount of the mixed solution is 45 ml/min; the precipitant solution is ammonium carbonate solution with the concentration of 2mol/L, and the feeding amount of the precipitant solution is 30 ml/min;
the reaction temperature of the coprecipitation is 40 ℃, and the reaction time is 60 h.
Example 3
The preparation process of the large-particle cobalt carbonate of the nano zirconium dioxide comprises the following steps:
step 1, mixing a suspension solution of nano zirconium dioxide with a cobalt salt solution to obtain a mixed solution;
the mass ratio of the nano zirconium dioxide to the cobalt ions in the mixed solution is 5: 100; the pH value of the mixed solution is 0.5-1.5;
the concentration of the nano zirconium dioxide in the suspension of the nano zirconium dioxide is 0.05mol/L, the concentration of cobalt ions in the cobalt salt solution is 2mol/L, and the cobalt salt solution is cobalt nitrate.
Step 2, adding the mixed solution obtained in the step 1 and a precipitator solution containing carbonic acid ions into a reaction device in a cocurrent manner for coprecipitation reaction to obtain large-particle cobalt carbonate wrapping the nano zirconium dioxide;
wherein the feeding amount of the mixed solution is 60 ml/min; the precipitant solution is ammonium carbonate solution with the concentration of 3mol/L, and the feeding amount of the precipitant solution is 50 ml/min;
the reaction temperature of the coprecipitation is 50 ℃, and the reaction time is 48 h.
The following examples were conducted to prepare cobaltosic oxide by stepwise calcination using the large-particle cobalt carbonate containing the doping element prepared in examples 1 to 3 as a starting material.
Example 4
This example provides a staged calcination method for large particle cobaltosic oxide containing doping elements, which comprises the following steps:
s1, loading the large-particle cobalt carbonate wrapped with nano-alumina prepared in the embodiment 1 into a burning boat, placing the burning boat into a roller kiln at the temperature of 200 ℃ for heat preservation for 4 hours, and carrying out primary calcination;
s2, after the primary calcination, raising the temperature of the roller kiln to 350 ℃ at the temperature raising speed of 2.25 ℃/min, preserving the heat for 4h, and carrying out secondary calcination;
s3, after the secondary calcining, raising the temperature of the roller kiln to 550 ℃ at the temperature raising speed of 1.7 ℃/min, preserving the heat for 2 hours, and carrying out tertiary calcining;
and S4, after the third calcination, raising the temperature of the roller kiln to 700 ℃ at the temperature rise speed of 1.25 ℃/min, preserving the heat for 4h, carrying out fourth calcination, and naturally cooling to obtain the aluminum-doped large-particle cobaltosic oxide.
In order to verify whether the aluminum-doped large-particle cobaltosic oxide prepared by the embodiment cracks, the aluminum-doped large-particle cobaltosic oxide prepared by the embodiment is detected by a scanning electron microscope, as shown in fig. 1, as can be seen from fig. 1, the sphericity of the aluminum-doped large-particle cobaltosic oxide of the embodiment is relatively standard, and particles with grape bunch structures hardly exist; more importantly, the particles of the aluminum-doped large-particle cobaltosic oxide of the embodiment do not crack, which shows that the sectional calcination method of the embodiment can effectively solve the problems of serious cracking of spheres and poor sphericity in the existing calcination method of the metal-doped large-particle cobaltosic oxide.
In addition, tests on tap density and specific surface area of the aluminum-doped large-particle cobaltosic oxide prepared in the example were carried out, and the tap density of the aluminum-doped large-particle cobaltosic oxide prepared in the example is 2.53g/cm3Specific surface area 3.37m2/g。
Comparative example 1
The present comparative example provides a method for one-time calcination of large-particle cobaltosic oxide containing a doping element, which comprises the steps of:
and (2) loading the large-particle cobalt carbonate wrapped with the nano-alumina prepared in the example 1 into a burning boat, putting the burning boat into a roller kiln at the temperature of 200 ℃, heating the roller kiln to 700 ℃ at the heating speed of 5 ℃/min, and preserving heat for 4h to obtain the aluminum-doped large-particle cobaltosic oxide.
In order to verify whether the aluminum-doped large-particle cobaltosic oxide prepared by the comparative example cracks or not, scanning electron microscope detection is carried out on the aluminum-doped large-particle cobaltosic oxide prepared by the comparative example, as shown in fig. 2, as can be seen from fig. 2, the sphericity of the aluminum-doped large-particle cobaltosic oxide of the comparative example is relatively standard, but a large amount of cracking phenomena exist on the particle surface of the aluminum-doped large-particle cobaltosic oxide.
In addition, the aluminum prepared by the comparative example is doped with large-particle cobaltosic oxideTap density and specific surface area of the aluminum-doped large-particle cobaltosic oxide of the comparative example were measured, and the tap density was 2.14g/cm3Specific surface area 6.27m2/g。
It is apparent that the aluminum-doped large-particle cobaltosic oxide particles prepared by the primary calcination method of comparative example 1 have a severe cracking phenomenon, compared to example 4.
Comparative example 2
The comparative example provides a staged calcination process for large particle cobaltosic oxide with dopant elements, comprising the steps of:
s1, loading the large-particle cobalt carbonate wrapped with nano-alumina prepared in the embodiment 1 into a burning boat, putting the burning boat into a roller kiln at room temperature, heating the roller kiln to 200 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, and carrying out primary calcination;
s2, after the primary calcination, raising the temperature of the roller kiln to 350 ℃ at the temperature raising speed of 2.3 ℃/min, preserving the heat for 1h, and carrying out secondary calcination;
and S3, after the secondary calcining and sintering, raising the temperature of the roller kiln to 700 ℃ at the temperature raising speed of 1.5 ℃/min, preserving the heat for 4h, carrying out four-time calcining, and naturally cooling to obtain the aluminum-doped large-particle cobaltosic oxide.
In order to verify whether the aluminum-doped large-particle cobaltosic oxide prepared by the comparative example cracks or not, scanning electron microscope detection is carried out on the aluminum-doped large-particle cobaltosic oxide prepared by the comparative example, as shown in fig. 3, as can be seen from fig. 3, the cracking phenomenon still exists in the particles of the aluminum-doped large-particle cobaltosic oxide prepared by the comparative example, which means that the sectional calcining method of the comparative example cannot effectively solve the problem that the spheres are seriously cracked in the conventional calcining method of the metal-element-doped large-particle cobaltosic oxide; also, as can be seen from fig. 3, a small amount of grape-bunch particles were present in the particles of the present comparative example.
In addition, the tap density and specific surface area of the aluminum-doped large-particle cobaltosic oxide prepared in the comparative example were also tested, and the tap density of the aluminum-doped large-particle cobaltosic oxide in the comparative example was 2.31 g/mlcm3Specific surface area 2.34m2In g, it is apparent that the specific surface area of the aluminum-doped large particle tricobalt tetroxide of comparative example 2 is smaller than that of the aluminum-doped large particle tricobalt tetroxide of example 4 (3.37 m)2/g)。
Example 5
This example provides a staged calcination method for large particle cobaltosic oxide containing doping elements, which comprises the following steps:
s1, loading the large-particle cobalt carbonate coated with the nano titanium dioxide prepared in the embodiment 2 into a burning boat, putting the burning boat into a roller kiln at the temperature of 150 ℃, preserving heat for 3.5 hours, and carrying out primary calcination;
s2, after the primary calcination, raising the temperature of the roller kiln to 300 ℃ at a temperature raising speed of 3 ℃/min, preserving the heat for 3.5 hours, and carrying out secondary calcination;
s3, after the secondary calcining and sintering, raising the temperature of the roller kiln to 500 ℃ at the temperature raising speed of 2 ℃/min, preserving the heat for 1.5h, and carrying out tertiary calcining;
and S4, after the third calcination, raising the temperature of the roller kiln to 650 ℃ at the temperature rise speed of 1.5 ℃/min, preserving the heat for 3.5 hours, carrying out fourth calcination, and naturally cooling to obtain the titanium-doped large-particle cobaltosic oxide.
In order to verify whether the titanium-doped large-particle cobaltosic oxide prepared by the embodiment cracks, scanning electron microscope detection is performed on the titanium-doped large-particle cobaltosic oxide prepared by the embodiment, and the result shows that the sphericity of the titanium-doped large-particle cobaltosic oxide is relatively standard and particles with grape bunch structures hardly exist; more importantly, the particles of the titanium-doped large-particle cobaltosic oxide in the embodiment do not crack, which shows that the sectional calcination method in the embodiment can effectively solve the problems of serious cracking of spheres and poor sphericity in the existing calcination method of the metal-doped large-particle cobaltosic oxide.
In addition, tests on tap density and specific surface area of the titanium-doped large-particle cobaltosic oxide prepared in the embodiment were also carried out, and the tap density of the titanium-doped large-particle cobaltosic oxide prepared in the embodiment is 2.42g/cm3Specific surface area 3.29m2/g。
Example 6
This example provides a staged calcination method for large particle cobaltosic oxide containing doping elements, which comprises the following steps:
s1, loading the large-particle cobalt carbonate of the nano zirconium dioxide prepared in the embodiment 3 into a burning boat, putting the burning boat into a roller kiln at the temperature of 250 ℃, preserving the heat for 4.5 hours, and carrying out primary calcination;
s2, after the primary calcination, raising the temperature of the roller kiln to 400 ℃ at a temperature raising speed of 1 ℃/min, preserving the heat for 4.5 hours, and carrying out secondary calcination;
s3, after the secondary calcining and sintering, raising the temperature of the roller kiln to 600 ℃ at the temperature raising speed of 1 ℃/min, preserving the heat for 2.5 hours, and carrying out tertiary calcining;
and S4, after the third calcination, raising the temperature of the roller kiln to 750 ℃ at a temperature rise speed of 1 ℃/min, preserving the heat for 4.5 hours, carrying out fourth calcination, and naturally cooling to obtain the zirconium-doped large-particle cobaltosic oxide.
In order to verify whether cracking of the zirconium-doped large-particle cobaltosic oxide prepared by the embodiment occurs, scanning electron microscope detection is performed on the zirconium-doped large-particle cobaltosic oxide prepared by the embodiment, and the result shows that the sphericity of the zirconium-doped large-particle cobaltosic oxide is relatively standard and particles with grape bunch structures hardly exist; more importantly, the particles of the zirconium-doped large-particle cobaltosic oxide in the embodiment do not crack, which shows that the sectional calcination method in the embodiment can effectively solve the problems of serious cracking of spheres and poor sphericity in the existing calcination method of the metal-doped large-particle cobaltosic oxide.
In addition, tests on tap density and specific surface area of the zirconium-doped large-particle cobaltosic oxide prepared in the example were carried out, and the tap density of the zirconium-doped large-particle cobaltosic oxide prepared in the example is 2.69g/cm3Specific surface area 2.60m2/g。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A sectional calcination method of large-particle cobaltosic oxide containing doping elements is characterized by comprising the following steps:
s1, placing the large-particle cobalt carbonate containing the doping elements in a calcining furnace at the temperature of 150-250 ℃, preserving the heat for 3.5-4.5 h, and carrying out primary calcining;
s2, after the primary calcining, raising the temperature of the calcining furnace to 300-400 ℃ at a temperature raising speed of 1-3 ℃/min, and preserving the heat for 3.5-4.5 h to carry out secondary calcining;
s3, after the secondary calcining and sintering, raising the temperature of the calcining furnace to 500-600 ℃ at a temperature raising speed of 1-2 ℃/min, and preserving the heat for 1.5-2.5 h to carry out tertiary calcining;
and S4, after the third calcination, raising the temperature of the calciner to 650-750 ℃ at a temperature raising speed of 1-1.5 ℃/min, preserving the heat for 3.5-4.5 h, and carrying out four-time calcination to obtain large-particle cobaltosic oxide containing the doping elements.
2. The method of staged calcination of large particle cobaltosic oxide with a dopant element of claim 1, wherein the method comprises the steps of:
s1, placing large-particle cobalt carbonate containing doping elements in a calcining furnace at 200 ℃, preserving heat for 4 hours, and carrying out primary calcining;
s2, after the primary calcination, raising the temperature of the calciner to 350 ℃ at a temperature raising speed of 2.25 ℃/min, and preserving the heat for 4 hours to carry out secondary calcination;
s3, after the secondary calcining and sintering, raising the temperature of the calcining furnace to 550 ℃ at the temperature raising speed of 1.7 ℃/min, preserving the heat for 2h, and carrying out tertiary calcining;
and S4, after the third calcination, raising the temperature of the calciner to 700 ℃ at a temperature raising speed of 1.25 ℃/min, preserving the heat for 4h, and carrying out four-time calcination to obtain large-particle cobaltosic oxide containing the doping elements.
3. The method for staged calcination of large granular cobaltosic oxide with a doping element according to claim 1, wherein the large granular cobalt carbonate with a doping element is aluminum-doped large granular cobalt carbonate, titanium-doped large granular cobalt carbonate or zirconium-doped large granular cobalt carbonate.
4. The method of staged calcination for large particle cobaltosic oxide with a dopant element according to claim 1, wherein the large particle cobalt carbonate with a dopant element is a large particle cobalt carbonate coated with an oxide of a dopant element.
5. The staged calcination method for large particle cobaltosic oxide with dopant element as claimed in claim 4, wherein the large particle cobalt carbonate coated with the oxide of dopant element is prepared by the following steps:
step 1, mixing a suspension of doped element oxide with a cobalt salt solution to obtain a mixed solution;
and 2, adding the mixed solution obtained in the step 1 and a precipitator solution containing carbonic acid ions into a reaction device in a cocurrent mode for coprecipitation reaction to obtain large-particle cobalt carbonate wrapping the doped element oxide.
6. The method for calcining large-particle cobaltosic oxide containing doping element according to claim 5, wherein in the step 1, the mass ratio of the doping element oxide to the cobalt ion in the mixed solution is (0.2-5): 100; the pH value of the mixed solution is 0.5-1.5.
7. The method for calcining large-particle doped cobaltosic oxide according to claim 5, wherein in the step 1, the concentration of the doped oxide in the suspension of the doped oxide is 0.01-0.05 mol/L, and the concentration of the cobalt ion in the cobalt salt solution is 0.4-2.0 mol/L.
8. The staged calcination method for large particle cobaltosic oxide with dopant according to claim 5, wherein the mixed solution is fed in an amount of 30 to 60ml/min in the step 2; the precipitant solution is ammonium bicarbonate solution or ammonium carbonate solution with the concentration of 1-3 mol/L, and the feeding amount of the precipitant solution is 10-50 ml/min.
9. The staged calcination method for large particle cobaltosic oxide with dopant according to claim 5, wherein the reaction temperature of the co-precipitation in step 2 is 30-50 ℃ and the reaction time is 48-72 h.
10. The staged calcination process for large particle cobaltosic oxide with a doping element as claimed in any one of claims 1 to 9, wherein the step of S1 comprises:
loading large-particle cobalt carbonate containing doping elements into a burning boat, putting the burning boat into a roller kiln at the temperature of 150-250 ℃, preserving heat for 3.5-4.5 h, and carrying out primary calcination.
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| CN102583585A (en) * | 2012-01-09 | 2012-07-18 | 安徽亚兰德新能源材料股份有限公司 | Preparation technology for spherical lithium cobalt oxide doped with Ti, Mg and Al |
| CN110217832A (en) * | 2019-04-23 | 2019-09-10 | 金川集团股份有限公司 | A kind of bulky grain narrow ditribution mixes the preparation method of aluminium cobaltosic oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102583585A (en) * | 2012-01-09 | 2012-07-18 | 安徽亚兰德新能源材料股份有限公司 | Preparation technology for spherical lithium cobalt oxide doped with Ti, Mg and Al |
| CN110217832A (en) * | 2019-04-23 | 2019-09-10 | 金川集团股份有限公司 | A kind of bulky grain narrow ditribution mixes the preparation method of aluminium cobaltosic oxide |
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Application publication date: 20210618 |