CN112142120A - Method for producing cobaltosic oxide by calcining aluminum and manganese doped small-particle-size cobalt carbonate - Google Patents
Method for producing cobaltosic oxide by calcining aluminum and manganese doped small-particle-size cobalt carbonate Download PDFInfo
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- CN112142120A CN112142120A CN202011053708.5A CN202011053708A CN112142120A CN 112142120 A CN112142120 A CN 112142120A CN 202011053708 A CN202011053708 A CN 202011053708A CN 112142120 A CN112142120 A CN 112142120A
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 20
- 238000001354 calcination Methods 0.000 title claims abstract description 17
- 229910021446 cobalt carbonate Inorganic materials 0.000 title claims abstract description 16
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 16
- 229910052748 manganese Inorganic materials 0.000 title claims description 16
- 239000011572 manganese Substances 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 aluminum-manganese Chemical compound 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for producing cobaltosic oxide by calcining aluminum and manganese-doped small-particle-size cobalt carbonate.
Description
Technical Field
The invention relates to the field of production of precursors of battery materials, in particular to a method for producing cobaltosic oxide by calcining aluminum and manganese-doped cobalt carbonate with small particle size.
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 260h A/kg, the actual specific capacity is 130h A/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 4.5-4.6V, the structural stability of the material during high voltage charge and discharge can be improved by doping aluminum at present, and the conductivity of the material can be improved by doping a small amount of magnesium, so that the capacity of the material during charge and discharge can be further improved.
However, when the small-particle (4-5 microns) cobalt carbonate doped with aluminum and manganese (aluminum 6000-8000 ppm; manganese 1000-2000ppm) is calcined into cobaltosic oxide, the physicochemical properties and the morphology of the small-particle after calcination are greatly influenced by the distribution of heat supply because the particle size of the small-particle is relatively small, and the small-particle cobalt carbonate is usually calcined by two different methods: 1. calcining in a roller kiln/pushed slab kiln static method; 2. and (4) calcining in a rotary kiln. The first method is convenient to operate, but the product obtained by the first method has uneven appearance due to uneven heating in the roller kiln and different contact areas with air; the second method is directly calcined and uniformly heated, but the moisture of the product corrodes equipment under the condition of high temperature due to the direct calcination, so that the content of the magnetic foreign matters in the product is greatly increased, and the product cannot be used.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for producing cobaltosic oxide by doping aluminum and manganese with cobalt carbonate with small particle size.
The invention is realized by the following technical scheme.
A method for producing cobaltosic oxide by calcining aluminum and manganese doped small-particle-size cobalt carbonate, which is characterized by comprising the following steps of:
(1) loading cobalt carbonate doped with aluminum and manganese into a burning boat;
(2) placing the burning boat into a roller kiln for low-temperature calcination;
(3) and putting the cobaltosic oxide obtained by low-temperature calcination into a rotary kiln for high-temperature calcination to obtain the required cobaltosic oxide product.
Further, the step (2) is low-temperature calcination: after the temperature of the burning boat is kept at 100-300 ℃ for 3-5 hours, the temperature is raised to 300-500 ℃ for 5-7 hours in 1-3 hours.
Further, the step (3) is high-temperature calcination: the temperature is 700-750 ℃, and the heat preservation time is 3-5 hours.
The method for producing the cobaltosic oxide by calcining the aluminum and manganese (aluminum 6000-.
Drawings
FIG. 1 is a diagram showing the morphology of cobaltosic oxide prepared in example 1 of the present invention.
Fig. 2 is a morphology chart of the cobaltosic oxide prepared in comparative example 1.
Fig. 3 is a morphology chart of the cobaltosic oxide prepared in comparative example 2.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
Loading small-particle-size (4-micron) cobalt carbonate doped with aluminum and manganese (aluminum 6000 ppm; manganese 1000ppm) into a burning boat; setting the temperature of the roller kiln as 2-stage method: feeding at 200 ℃ in the first stage, keeping the temperature for 4 hours, heating to 400 ℃ for 2 hours, keeping the temperature for 6 hours, discharging, and then putting into a rotary kiln, wherein the temperature of the rotary kiln is set to 710 ℃, parameters are adjusted to ensure that particles stay in the kiln for 4 hours, and finally, an aluminum-manganese-doped cobaltosic oxide product is obtained, and has uniform appearance, as shown in figure 1, the tap density is 2.20, the specific surface area is 3.45, and the magnetic foreign matter is 50 ppb.
Example 2
Loading small particle size (5 micron) cobalt carbonate doped with aluminum and manganese (aluminum 7000 ppm; manganese 2000ppm) into the boat; setting the temperature of the roller kiln as 2-stage method: feeding at 100 ℃ in the first stage, keeping the temperature for 3 hours, heating to 500 ℃ for 7 hours after 1 hour, discharging, and putting into a rotary kiln, wherein the temperature of the rotary kiln is set to 700 ℃, parameters are adjusted to ensure that particles stay in the kiln for 5 hours, and finally, an aluminum-manganese doped cobaltosic oxide product is obtained, and has uniform appearance, tap density of 2.06, specific surface area of 3.97 and magnetic foreign matter of 40 ppb.
Example 3
Loading small-particle-size (4-micron) cobalt carbonate doped with aluminum and manganese (aluminum 8000 ppm; manganese 1000ppm) into a burning boat; setting the temperature of the roller kiln as 2-stage method: feeding at 300 ℃ in the first stage, keeping the temperature for 5 hours, heating to 300 ℃ for 3 hours, keeping the temperature for 5 hours, discharging, and then putting into a rotary kiln, wherein the temperature of the rotary kiln is set to 750 ℃, parameters are adjusted to ensure that particles stay in the kiln for 3 hours, and finally, an aluminum-manganese-doped cobaltosic oxide product is obtained, and has uniform appearance, tap density of 2.33, specific surface area of 2.41 and magnetic foreign matter of 45 ppb.
Comparative example 1
The roller kiln temperature is set to be 3-stage method, feeding is carried out at 200 ℃ in the first stage, the heat preservation time is 4 hours, the temperature is raised to 400 ℃ for 6 hours after 2 hours, the temperature is raised to 710 ℃ for 4 hours after 2 hours, and finally the aluminum manganese doped cobaltosic oxide is obtained, the sintering is serious and the appearance is not uniform, the original roller kiln calcines the small-particle cobalt carbonate at high temperature, the appearance of the particle is not uniform, the distribution of doping elements is not uniform, and the electrochemical performance after the cobalt oxide is burnt is affected, as shown in figure 2, the tap density is 2.14, the specific surface area is 4.27, and the magnetic foreign matter is 90 ppb.
Comparative example 2
The temperature of the rotary kiln is set to 710 ℃, parameters are adjusted to ensure that the particles stay in the kiln for 4 hours, and finally the aluminum-manganese doped cobaltosic oxide with uniform appearance is obtained, as shown in figure 3, the tap density is 2.35, the specific surface area is 3.1, and the magnetic foreign matter is 4210 ppb.
The original rotary kiln calcines the small-particle cobalt carbonate at high temperature, so that the moisture corrodes equipment at high temperature, the magnetic foreign matters of the product are very high, the iron removal cost is greatly improved, and the magnetic difference data are shown in table 1.
| Numbering | Magnetic foreign matter ppb |
| Example 1 | 50 |
| Example 2 | 40 |
| Example 3 | 45 |
| Comparative example 1 | 90 |
| Comparative example 2 | 4210 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the 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 (3)
1. A method for producing cobaltosic oxide by calcining aluminum and manganese doped small-particle-size cobalt carbonate, which is characterized by comprising the following steps of:
(1) loading cobalt carbonate doped with aluminum and manganese into a burning boat;
(2) placing the burning boat into a roller kiln for low-temperature calcination;
(3) and putting the cobaltosic oxide obtained by low-temperature calcination into a rotary kiln for high-temperature calcination to obtain the required cobaltosic oxide product.
2. The method of claim 1, wherein the step (2) comprises low-temperature calcination: after the temperature of the burning boat is kept at 100-300 ℃ for 3-5 hours, the temperature is raised to 300-500 ℃ for 5-7 hours in 1-3 hours.
3. The method of claim 1, wherein the step (3) comprises high-temperature calcination: the temperature is 700-750 ℃, and the heat preservation time is 3-5 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112299492A (en) * | 2020-10-30 | 2021-02-02 | 湖南德景源科技有限公司 | Preparation method of battery-grade cobaltosic oxide |
| CN114804222A (en) * | 2022-06-16 | 2022-07-29 | 荆门市格林美新材料有限公司 | Nickel-manganese bimetal doped large-particle cobalt carbonate and preparation method and application thereof |
| WO2024016469A1 (en) * | 2022-07-22 | 2024-01-25 | 广东邦普循环科技有限公司 | Manganese-doped cobaltosic oxide, and preparation method therefor and use thereof |
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Patent Citations (7)
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Cited By (3)
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| WO2024016469A1 (en) * | 2022-07-22 | 2024-01-25 | 广东邦普循环科技有限公司 | Manganese-doped cobaltosic oxide, and preparation method therefor and use thereof |
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