CN105399148A - Preparation method of large-particle-size and high-density spherical cobalt oxide - Google Patents
Preparation method of large-particle-size and high-density spherical cobalt oxide Download PDFInfo
- Publication number
- CN105399148A CN105399148A CN201510881580.4A CN201510881580A CN105399148A CN 105399148 A CN105399148 A CN 105399148A CN 201510881580 A CN201510881580 A CN 201510881580A CN 105399148 A CN105399148 A CN 105399148A
- Authority
- CN
- China
- Prior art keywords
- density
- reactor
- large stone
- preparation
- cobaltous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of large-particle-size and high-density spherical cobalt oxide. The preparation method aims at achieving the purposes that the median particle size D50 of the cobalt oxide is larger than or equal to 15 microns, particle size distribution is uniform, compacting density (TD) is larger than or equal to 2.2 g/cm<3>, and the large-particle-size and high-density spherical cobalt oxide can meet the development requirement of high-voltage lithium cobaltate. The preparation method of the cobalt oxide includes the cobalt carbonate synthesis stage and the spherical cobalt carbonate thermal decomposition stage. In the cobalt carbonate synthesis stage, a cobalt carbonate precursor prepared through many times of cyclic crystallization is compact and uniform in particle size distribution; due to the segmented thermal decomposition, cobalt carbonate is locally decomposed in the low-temperature pre-decomposing stage, a micro hole channel is formed, release of CO2 gas during subsequent decomposition is facilitated, and particles are prevented from crazing or being broken; in the high-temperature thermal decomposition stage, the particle surface is compact, and therefore the large-particle-size and high-density spherical cobalt oxide is prepared.
Description
Technical field
The present invention relates to a kind of preparation method of tricobalt tetroxide, particularly a kind of preparation method of Large stone high-density spherical cobaltic-cobaltous oxide.
Background technology
3C electronic product requires light, small and exquisite, and corresponding battery needs to possess high-energy-density.Be widely used at present in 3C electronic product with the small-scale lithium ion cell that cobalt acid lithium is first-selected positive electrode material.The pole piece compaction density of spherical lithium cobalt can reach 4.1g/cm
3, not only have higher tap density, and due to its outstanding mobility and processing characteristics, be extremely conducive to the coating of electrode slice, become the important directions that cobalt acid lithium material improves.Another means improving anode material for lithium-ion batteries energy density improve the operating voltage of material, and the charge cutoff voltage of current cobalt acid lithium material can reach 4.35V.Key prepared by cobalt acid lithium is to prepare satisfactory spheroidization presoma by liquid phase reaction, and Large stone high-density cobaltosic oxide meets the growth requirement of high-voltage cobalt acid lithium just.
At present, world market proposes following performance requriements to Large stone tricobalt tetroxide: (1): more than D50>=15 μm, even particle size distribution, i.e. QD=(D
90-D
10)/(D
10+ D
90)≤0.3; (2): Electronic Speculum display is without small-particle, and nothing ftractures and fragmentation; (3): tap density (TD)>=2.2g/cm
3, even>=2.5g/cm
3.Meet above-mentioned requirements, there is following difficulty: when first grow crystal particles is to certain particle diameter, especially more than 15 μm are reached, be difficult to continue again to grow up, the simultaneous speed of growth is slack-off, very easily occur that partial concn is uneven, degree of supersaturation increases and instantaneous burst nucleation, produces a large amount of small-particles; Its secondary acquisition high-density cobaltosic oxide, needs to obtain finer and close cobaltous carbonate presoma in the Moist chemical synthesis stage, but this kind of Large stone cobaltous carbonate, in the thermolysis stage, fierce chemical reaction occurs, and can discharge a large amount of CO
2gas, easily causes product grain to ftracture or fragmentation.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of Large stone high-density spherical cobaltic-cobaltous oxide is provided.Tricobalt tetroxide median particle diameter D50>=15 μm that the inventive method prepares, even particle size distribution, tap density (TD)>=2.2g/cm
3, the growth requirement of high-voltage cobalt acid lithium can be met.
In order to achieve the above object, the preparation method of a kind of Large stone high-density spherical cobaltic-cobaltous oxide of the present invention, comprises the steps:
Step one, cobaltous carbonate synthesis phase:
1. first a certain amount of ammonium carbonate salt solution is injected reactor as end liquid, flood the stirring rake in reactor;
2. be warming up to 40 ~ 80 DEG C, under agitation cobalt salt solution and ammonium carbonate salt solution added in reactor simultaneously and precipitin reaction occurs, feed in raw material process control reacting solution pH value in 6.5 ~ 8.5 scopes, until reactor filled it up with by material; Reinforced complete, stop stirring, after solid-liquid layering, taken away by supernatant liquor, vacating space continues reinforced, makes crystal continued growth;
3. repeat to feed in raw material, stratification, draw up clear liquid, continue reinforced working cycle 6 ~ 12 times, now crystal growth reaches 9 ~ 12 μm to crystal seed particle diameter;
4. reactor material is carried out first time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out quick growth response, and circulation feeds intake 6 ~ 12 times, and now crystal particle diameter reaches 13 ~ 17 μm;
5. reactor material is carried out second time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out repairing growth reaction, and circulation feeds intake 6 ~ 12 times, and now crystal particle diameter reaches 18 ~ 23 μm, feeds intake complete;
Step 2, spherical cobaltous carbonate thermolysis stage:
By reacted for step one slurry after washing and drying, the thermolysis on pushed bat kiln or rotary kiln of gained spherical cobaltous carbonate is obtained Large stone high-density spherical cobaltic-cobaltous oxide.
As preferably, described cobalt salt is the mixture of one or more in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, and the concentration of cobalt salt solution is 80 ~ 160g/L.
As preferably, described ammonium carbonate salts is bicarbonate of ammonia or volatile salt, and the concentration of ammonium carbonate salt solution is 180 ~ 230g/L.
As preferably, described spherical cobaltous carbonate thermolysis divides two sections: the predecomposition of first paragraph low temperature, and temperature is 200 ~ 400 DEG C, cobaltous carbonate exploded, forms micro channel; Second segment high temperature thermal decomposition, temperature is 500 ~ 800 DEG C, particle surface densification, forms Large stone high-density spherical cobaltic-cobaltous oxide.
As preferably, the median particle diameter D50 of described Large stone high-density spherical cobaltic-cobaltous oxide is 15 ~ 21 μm, and tap density TD is 2.2 ~ 3.0g/cm
3.
As preferably, described reactor is furnished with pumping pipe, after solid-liquid layering, pump supernatant liquor.
The present invention is finer and close by the cobaltous carbonate presoma that repeatedly circulation crystallization is obtained at cobaltous carbonate synthesis phase, even particle size distribution; By sectional type thermolysis, make cobaltous carbonate exploded in the low temperature predecomposition stage, form micro channel, be convenient to CO when subsequent decomposition reacts
2the release of gas, prevents particle fracture or fragmentation; In the high temperature thermal decomposition stage, particle surface densification, thus prepare Large stone high-density spherical cobaltic-cobaltous oxide.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 1 products obtained therefrom.
Fig. 2 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 2 products obtained therefrom.
Fig. 3 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 3 products obtained therefrom.
Embodiment
Embodiment 1
1. a certain amount of ammonium bicarbonate soln is injected reactor as end liquid, flood stirring rake;
2. be warming up to 50 DEG C, the ammonium bicarbonate soln of to be under agitation the cobalt chloride solution of 80g/L and concentration by concentration be 180g/L adds in reactor simultaneously precipitin reaction occurs, and reinforced process control reacting solution pH value is 7.0, until reactor filled it up with by material; Reinforced complete, stop stirring, after solid-liquid layering, taken away by supernatant liquor, vacating space continues reinforced, makes crystal continued growth;
3. repeat to feed in raw material, stratification, draw up clear liquid, continue reinforced working cycle 9 times, now crystal growth reaches 9.4 μm to crystal seed particle diameter;
4. reactor material is carried out first time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out quick growth response, and circulation feeds intake 7 times, and now crystal particle diameter reaches 14.5 μm;
5. reactor material is carried out second time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out repairing growth reaction, and circulation feeds intake 8 times, and now crystal particle diameter reaches 18.5 μm, feeds intake complete;
6. by reacted slurry through washing and drying after, by the thermolysis on pushed bat kiln of gained spherical cobaltous carbonate, first paragraph low temperature predecomposition temperature is 300 DEG C, and second segment high temperature thermal decomposition is 600 DEG C, obtains Large stone high-density spherical cobaltic-cobaltous oxide.
After testing, its median particle diameter D50 is 17.3 μm to gained Large stone high-density spherical cobaltic-cobaltous oxide, and tap density TD is 2.45g/cm
3, surface sweeping Electronic Speculum is shown in accompanying drawing 1, spheroid flawless, without broken, without fine particle.
Embodiment 2
1. a certain amount of sal volatile is injected reactor as end liquid, flood stirring rake;
2. be warming up to 70 DEG C, the sal volatile of to be under agitation the cobalt sulfate solution of 125g/L and concentration by concentration be 210g/L adds in reactor simultaneously precipitin reaction occurs, and reinforced process control reacting solution pH value is 8.2, until reactor filled it up with by material; Reinforced complete, stop stirring, after solid-liquid layering, taken away by supernatant liquor, vacating space continues reinforced, makes crystal continued growth;
3. repeat to feed in raw material, stratification, draw up clear liquid, continue reinforced working cycle 12 times, now crystal growth reaches 11.8 μm to crystal seed particle diameter;
4. reactor material is carried out first time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out quick growth response, and circulation feeds intake 12 times, and now crystal particle diameter reaches 15.9 μm;
5. reactor material is carried out second time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out repairing growth reaction, and circulation feeds intake 12 times, and now crystal particle diameter reaches 22.7 μm, feeds intake complete;
6. by reacted slurry through washing and drying after, by the thermolysis on pushed bat kiln of gained spherical cobaltous carbonate, first paragraph low temperature predecomposition temperature is 400 DEG C, and second segment high temperature thermal decomposition is 800 DEG C, obtains Large stone high-density spherical cobaltic-cobaltous oxide.
After testing, its median particle diameter D50 is 20.6 μm to gained Large stone high-density spherical cobaltic-cobaltous oxide, and tap density TD is 2.63g/cm
3, surface sweeping Electronic Speculum is shown in accompanying drawing 2, spheroid flawless, without broken, without fine particle.
Embodiment 3
1. a certain amount of ammonium bicarbonate soln is injected reactor as end liquid, flood stirring rake;
2. be warming up to 80 DEG C, the sal volatile of to be under agitation the cobalt nitrate solution of 160g/L and concentration by concentration be 230g/L adds in reactor simultaneously precipitin reaction occurs, and reinforced process control reacting solution pH value is 6.7, until reactor filled it up with by material; Reinforced complete, stop stirring, after solid-liquid layering, taken away by supernatant liquor, vacating space continues reinforced, makes crystal continued growth;
3. repeat to feed in raw material, stratification, draw up clear liquid, continue reinforced working cycle 10 times, now crystal growth reaches 10.3 μm to crystal seed particle diameter;
4. reactor material is carried out first time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out quick growth response, and circulation feeds intake 10 times, and now crystal particle diameter reaches 15.4 μm;
5. reactor material is carried out second time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out repairing growth reaction, and circulation feeds intake 10 times, and now crystal particle diameter reaches 20.6 μm, feeds intake complete;
6. by reacted slurry through washing and drying after, by the thermolysis on pushed bat kiln of gained spherical cobaltous carbonate, first paragraph low temperature predecomposition temperature is 250 DEG C, and second segment high temperature thermal decomposition is 750 DEG C, obtains Large stone high-density spherical cobaltic-cobaltous oxide.
After testing, its median particle diameter D50 is 18.7 μm to gained Large stone high-density spherical cobaltic-cobaltous oxide, and tap density TD is 2.54g/cm3, and surface sweeping Electronic Speculum is shown in accompanying drawing 3, spheroid flawless, without broken, without fine particle.
Embodiment 4
1. a certain amount of ammonium bicarbonate soln is injected reactor as end liquid, flood stirring rake;
2. be warming up to 40 DEG C, the ammonium bicarbonate soln of to be under agitation the cobalt chloride solution of 100g/L and concentration by concentration be 200g/L adds in reactor simultaneously precipitin reaction occurs, and reinforced process control reacting solution pH value is 8.5, until reactor filled it up with by material; Reinforced complete, stop stirring, after solid-liquid layering, taken away by supernatant liquor, vacating space continues reinforced, makes crystal continued growth;
3. repeat to feed in raw material, stratification, draw up clear liquid, continue reinforced working cycle 6 times, now crystal growth reaches 9 μm to crystal seed particle diameter;
4. reactor material is carried out first time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out quick growth response, and circulation feeds intake 6 times, and now crystal particle diameter reaches 13 μm;
5. reactor material is carried out second time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out repairing growth reaction, and circulation feeds intake 6 times, and now crystal particle diameter reaches 18 μm, feeds intake complete;
6. by reacted slurry through washing and drying after, by the thermolysis on pushed bat kiln of gained spherical cobaltous carbonate, first paragraph low temperature predecomposition temperature is 200 DEG C, and second segment high temperature thermal decomposition is 500 DEG C, obtains Large stone high-density spherical cobaltic-cobaltous oxide.
After testing, its median particle diameter D50 is 15.0 μm to gained Large stone high-density spherical cobaltic-cobaltous oxide, and tap density TD is 2.20g/cm
3.
Embodiment 5
1. a certain amount of ammonium bicarbonate soln is injected reactor as end liquid, flood stirring rake;
2. be warming up to 60 DEG C, the ammonium bicarbonate soln of to be under agitation the cobalt chloride solution of 120g/L and concentration by concentration be 190g/L adds in reactor simultaneously precipitin reaction occurs, and reinforced process control reacting solution pH value is 6.5, until reactor filled it up with by material; Reinforced complete, stop stirring, after solid-liquid layering, taken away by supernatant liquor, vacating space continues reinforced, makes crystal continued growth;
3. repeat to feed in raw material, stratification, draw up clear liquid, continue reinforced working cycle 8 times, now crystal growth reaches 12 μm to crystal seed particle diameter;
4. reactor material is carried out first time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out quick growth response, and circulation feeds intake 8 times, and now crystal particle diameter reaches 17 μm;
5. reactor material is carried out second time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out repairing growth reaction, and circulation feeds intake 9 times, and now crystal particle diameter reaches 23 μm, feeds intake complete;
6. by reacted slurry through washing and drying after, by the thermolysis on pushed bat kiln of gained spherical cobaltous carbonate, first paragraph low temperature predecomposition temperature is 350 DEG C, and second segment high temperature thermal decomposition is 700 DEG C, obtains Large stone high-density spherical cobaltic-cobaltous oxide.
After testing, its median particle diameter D50 is 21.0 μm to gained Large stone high-density spherical cobaltic-cobaltous oxide, and tap density TD is 3.00g/cm
3.
Claims (9)
1. a preparation method for Large stone high-density spherical cobaltic-cobaltous oxide, is characterized in that: comprise the steps:
Step one, cobaltous carbonate synthesis phase:
1. first a certain amount of ammonium carbonate salt solution is injected reactor as end liquid, flood the stirring rake in reactor;
2. be warming up to 40 ~ 80 DEG C, under agitation cobalt salt solution and ammonium carbonate salt solution added in reactor simultaneously and precipitin reaction occurs, feed in raw material process control reacting solution pH value in 6.5 ~ 8.5 scopes, until reactor filled it up with by material; Reinforced complete, stop stirring, after solid-liquid layering, taken away by supernatant liquor, vacating space continues reinforced, makes crystal continued growth;
3. repeat to feed in raw material, stratification, draw up clear liquid, continue reinforced working cycle 6 ~ 12 times, now crystal growth reaches 9 ~ 12 μm to crystal seed particle diameter;
4. reactor material is carried out first time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out quick growth response, and circulation feeds intake 6 ~ 12 times, and now crystal particle diameter reaches 13 ~ 17 μm;
5. reactor material is carried out second time point still, be transferred to ageing tank by half material, stay half to continue to feed intake at reactor, 2. repeating step, makes crystal carry out repairing growth reaction, and circulation feeds intake 6 ~ 12 times, and now crystal particle diameter reaches 18 ~ 23 μm, feeds intake complete;
Step 2, spherical cobaltous carbonate thermolysis stage:
By reacted for step one slurry after washing and drying, the thermolysis on pushed bat kiln or rotary kiln of gained spherical cobaltous carbonate is obtained Large stone high-density spherical cobaltic-cobaltous oxide.
2. the preparation method of a kind of Large stone high-density spherical cobaltic-cobaltous oxide according to claim 1, it is characterized in that: described spherical cobaltous carbonate thermolysis divides two sections: the predecomposition of first paragraph low temperature, temperature is 200 ~ 400 DEG C, cobaltous carbonate exploded, forms micro channel; Second segment high temperature thermal decomposition, temperature is 500 ~ 800 DEG C, particle surface densification, forms Large stone high-density spherical cobaltic-cobaltous oxide.
3. the preparation method of a kind of Large stone high-density spherical cobaltic-cobaltous oxide according to claim 1 and 2, it is characterized in that: described cobalt salt is the mixture of one or more in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, the concentration of cobalt salt solution is 80 ~ 160g/L.
4. the preparation method of a kind of Large stone high-density spherical cobaltic-cobaltous oxide according to claim 1 and 2, is characterized in that: described ammonium carbonate salts is bicarbonate of ammonia or volatile salt, the concentration of ammonium carbonate salt solution is 180 ~ 230g/L.
5. the preparation method of a kind of Large stone high-density spherical cobaltic-cobaltous oxide according to claim 3, is characterized in that: described ammonium carbonate salts is bicarbonate of ammonia or volatile salt, the concentration of ammonium carbonate salt solution is 180 ~ 230g/L.
6. the preparation method of a kind of Large stone high-density spherical cobaltic-cobaltous oxide according to claim 1,2 or 5, is characterized in that: the median particle diameter D50 of described Large stone high-density spherical cobaltic-cobaltous oxide is 15 ~ 21 μm, and tap density TD is 2.2 ~ 3.0g/cm
3.
7. the preparation method of a kind of Large stone high-density spherical cobaltic-cobaltous oxide according to claim 3, is characterized in that: the median particle diameter D50 of described Large stone high-density spherical cobaltic-cobaltous oxide is 15 ~ 21 μm, and tap density TD is 2.2 ~ 3.0g/cm
3.
8. the preparation method of a kind of Large stone high-density spherical cobaltic-cobaltous oxide according to claim 4, is characterized in that: the median particle diameter D50 of described Large stone high-density spherical cobaltic-cobaltous oxide is 15 ~ 21 μm, and tap density TD is 2.2 ~ 3.0g/cm
3.
9. the preparation method of a kind of Large stone high-density spherical cobaltic-cobaltous oxide according to claim 1, is characterized in that: described reactor is furnished with pumping pipe, after solid-liquid layering, pumps supernatant liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510881580.4A CN105399148B (en) | 2015-12-07 | 2015-12-07 | Preparation method of large-particle-size and high-density spherical cobalt oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510881580.4A CN105399148B (en) | 2015-12-07 | 2015-12-07 | Preparation method of large-particle-size and high-density spherical cobalt oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105399148A true CN105399148A (en) | 2016-03-16 |
| CN105399148B CN105399148B (en) | 2017-01-25 |
Family
ID=55464961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510881580.4A Active CN105399148B (en) | 2015-12-07 | 2015-12-07 | Preparation method of large-particle-size and high-density spherical cobalt oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105399148B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776356A (en) * | 2016-03-22 | 2016-07-20 | 阳江市联邦金属化工有限公司 | Preparation method of spherical compact tricobalt tetroxide |
| CN105800699A (en) * | 2016-04-20 | 2016-07-27 | 湖南海纳新材料有限公司 | Method for preparing high-sphericity-degree and large-particle cobaltosic oxide |
| CN106882843A (en) * | 2017-01-19 | 2017-06-23 | 衢州华友钴新材料有限公司 | A kind of preparation method of fine and close crystal formation cobaltosic oxide |
| CN108011101A (en) * | 2017-11-28 | 2018-05-08 | 衢州华友钴新材料有限公司 | A kind of big uniform particle sizes mix the preparation method of aluminium cobaltosic oxide |
| CN108190971A (en) * | 2017-12-25 | 2018-06-22 | 荆门市格林美新材料有限公司 | A kind of method and system for preparing cobalt carbonate |
| CN108439489A (en) * | 2018-05-15 | 2018-08-24 | 厦门钨业股份有限公司 | A kind of preparation method of high jolt ramming battery-grade cobaltosic oxide |
| CN108609666A (en) * | 2018-04-25 | 2018-10-02 | 中南林业科技大学 | A kind of preparation method of the cobaltosic oxide of metallic element grade doping |
| CN109179516A (en) * | 2018-10-30 | 2019-01-11 | 中伟新材料有限公司 | Mix aluminium little particle spherical cobaltic-cobaltous oxide with and preparation method thereof |
| CN109824094A (en) * | 2019-03-20 | 2019-05-31 | 兰州金川新材料科技股份有限公司 | A kind of production method of high voltage cobalt acid lithium bulky grain cobalt carbonate |
| 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 |
| CN110217831A (en) * | 2019-04-23 | 2019-09-10 | 金川集团股份有限公司 | A kind of preparation method of high voltage cobalt acid lithium large granular spherical narrow ditribution cobaltosic oxide |
| CN111082007A (en) * | 2019-12-10 | 2020-04-28 | 衢州华友钴新材料有限公司 | Nano basic aluminum cobalt carbonate/cobalt carbonate composite spherical precursor |
| CN112479264A (en) * | 2019-09-12 | 2021-03-12 | 湖南杉杉能源科技股份有限公司 | Doped large-particle cobalt carbonate and method for preparing same by using waste cobalt acid lithium battery |
| CN112850801A (en) * | 2019-11-28 | 2021-05-28 | 荆门市格林美新材料有限公司 | Preparation method of large-particle cobaltosic oxide |
| CN112897596A (en) * | 2021-04-22 | 2021-06-04 | 衢州华友钴新材料有限公司 | High-purity cobalt carbonate particles and preparation method thereof |
| CN113277568A (en) * | 2021-05-14 | 2021-08-20 | 浙江中金格派锂电产业股份有限公司 | Preparation method of high-conductivity lithium cobalt oxide positive electrode material |
| CN114956197A (en) * | 2022-06-20 | 2022-08-30 | 江西佳纳能源科技有限公司 | Spherical cobalt carbonate, preparation method thereof and lithium ion battery cathode material |
| WO2024066183A1 (en) * | 2022-09-28 | 2024-04-04 | 广东邦普循环科技有限公司 | Aluminum-fluorine co-doped cobaltosic oxide, and preparation method therefor and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11292548A (en) * | 1998-04-13 | 1999-10-26 | Ishihara Sangyo Kaisha Ltd | Tricobalt tetroxide and its production |
| JP2002211930A (en) * | 2001-01-12 | 2002-07-31 | Sumitomo Metal Mining Co Ltd | Method for producing cobalt oxide particles by neutralization method |
| CN101200308A (en) * | 2007-11-09 | 2008-06-18 | 浙江华友钴镍材料有限公司 | Preparation method of cobaltosic oxide for electric battery |
| CN101269848A (en) * | 2008-03-05 | 2008-09-24 | 广州融捷材料科技有限公司 | High-density spherical cobaltic-cobaltous oxide and method for preparing the same |
-
2015
- 2015-12-07 CN CN201510881580.4A patent/CN105399148B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11292548A (en) * | 1998-04-13 | 1999-10-26 | Ishihara Sangyo Kaisha Ltd | Tricobalt tetroxide and its production |
| JP2002211930A (en) * | 2001-01-12 | 2002-07-31 | Sumitomo Metal Mining Co Ltd | Method for producing cobalt oxide particles by neutralization method |
| CN101200308A (en) * | 2007-11-09 | 2008-06-18 | 浙江华友钴镍材料有限公司 | Preparation method of cobaltosic oxide for electric battery |
| CN101269848A (en) * | 2008-03-05 | 2008-09-24 | 广州融捷材料科技有限公司 | High-density spherical cobaltic-cobaltous oxide and method for preparing the same |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776356A (en) * | 2016-03-22 | 2016-07-20 | 阳江市联邦金属化工有限公司 | Preparation method of spherical compact tricobalt tetroxide |
| CN105800699A (en) * | 2016-04-20 | 2016-07-27 | 湖南海纳新材料有限公司 | Method for preparing high-sphericity-degree and large-particle cobaltosic oxide |
| CN106882843A (en) * | 2017-01-19 | 2017-06-23 | 衢州华友钴新材料有限公司 | A kind of preparation method of fine and close crystal formation cobaltosic oxide |
| CN106882843B (en) * | 2017-01-19 | 2018-08-17 | 衢州华友钴新材料有限公司 | A kind of preparation method of densification crystal form cobaltosic oxide |
| CN108011101B (en) * | 2017-11-28 | 2020-04-03 | 衢州华友钴新材料有限公司 | Preparation method of large-particle-size uniformly-aluminum-doped cobaltosic oxide |
| CN108011101A (en) * | 2017-11-28 | 2018-05-08 | 衢州华友钴新材料有限公司 | A kind of big uniform particle sizes mix the preparation method of aluminium cobaltosic oxide |
| CN108190971A (en) * | 2017-12-25 | 2018-06-22 | 荆门市格林美新材料有限公司 | A kind of method and system for preparing cobalt carbonate |
| CN108609666A (en) * | 2018-04-25 | 2018-10-02 | 中南林业科技大学 | A kind of preparation method of the cobaltosic oxide of metallic element grade doping |
| CN108439489B (en) * | 2018-05-15 | 2020-08-04 | 厦门钨业股份有限公司 | Preparation method of high-tap-density battery-grade cobaltosic oxide |
| CN108439489A (en) * | 2018-05-15 | 2018-08-24 | 厦门钨业股份有限公司 | A kind of preparation method of high jolt ramming battery-grade cobaltosic oxide |
| CN109179516A (en) * | 2018-10-30 | 2019-01-11 | 中伟新材料有限公司 | Mix aluminium little particle spherical cobaltic-cobaltous oxide with and preparation method thereof |
| CN109179516B (en) * | 2018-10-30 | 2020-12-25 | 中伟新材料股份有限公司 | Aluminum-doped small-particle spherical cobaltosic oxide and preparation method thereof |
| CN109824094A (en) * | 2019-03-20 | 2019-05-31 | 兰州金川新材料科技股份有限公司 | A kind of production method of high voltage cobalt acid lithium bulky grain cobalt carbonate |
| CN110217831B (en) * | 2019-04-23 | 2021-08-27 | 金川集团股份有限公司 | Preparation method of large-particle spherical narrow-distribution cobaltosic oxide for high-voltage lithium cobaltate |
| 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 |
| CN110217831A (en) * | 2019-04-23 | 2019-09-10 | 金川集团股份有限公司 | A kind of preparation method of high voltage cobalt acid lithium large granular spherical narrow ditribution cobaltosic oxide |
| CN110217832B (en) * | 2019-04-23 | 2021-08-27 | 金川集团股份有限公司 | Preparation method of large-particle narrow-distribution aluminum-doped cobaltosic oxide |
| CN112479264B (en) * | 2019-09-12 | 2022-11-01 | 巴斯夫杉杉电池材料有限公司 | Doped large-particle cobalt carbonate and method for preparing same by using waste cobalt acid lithium battery |
| CN112479264A (en) * | 2019-09-12 | 2021-03-12 | 湖南杉杉能源科技股份有限公司 | Doped large-particle cobalt carbonate and method for preparing same by using waste cobalt acid lithium battery |
| CN112850801A (en) * | 2019-11-28 | 2021-05-28 | 荆门市格林美新材料有限公司 | Preparation method of large-particle cobaltosic oxide |
| CN112850801B (en) * | 2019-11-28 | 2023-10-31 | 荆门市格林美新材料有限公司 | Preparation method of large-particle cobaltosic oxide |
| CN111082007A (en) * | 2019-12-10 | 2020-04-28 | 衢州华友钴新材料有限公司 | Nano basic aluminum cobalt carbonate/cobalt carbonate composite spherical precursor |
| CN112897596A (en) * | 2021-04-22 | 2021-06-04 | 衢州华友钴新材料有限公司 | High-purity cobalt carbonate particles and preparation method thereof |
| CN112897596B (en) * | 2021-04-22 | 2023-03-10 | 衢州华友钴新材料有限公司 | High-purity cobalt carbonate particles and preparation method thereof |
| CN113277568A (en) * | 2021-05-14 | 2021-08-20 | 浙江中金格派锂电产业股份有限公司 | Preparation method of high-conductivity lithium cobalt oxide positive electrode material |
| CN114956197A (en) * | 2022-06-20 | 2022-08-30 | 江西佳纳能源科技有限公司 | Spherical cobalt carbonate, preparation method thereof and lithium ion battery cathode material |
| CN114956197B (en) * | 2022-06-20 | 2024-05-28 | 江西佳纳能源科技有限公司 | Spherical cobalt carbonate, preparation method thereof and lithium ion battery anode material |
| WO2024066183A1 (en) * | 2022-09-28 | 2024-04-04 | 广东邦普循环科技有限公司 | Aluminum-fluorine co-doped cobaltosic oxide, and preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105399148B (en) | 2017-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105399148A (en) | Preparation method of large-particle-size and high-density spherical cobalt oxide | |
| CN108011101B (en) | Preparation method of large-particle-size uniformly-aluminum-doped cobaltosic oxide | |
| US20200328406A1 (en) | Layered lithium-rich manganese-based cathode material with olivine structured limpo4 surface modification and preparation method thereof | |
| CN101420023B (en) | Electrochemical lithium ionic insertion/deinsertion electrode and production method thereof | |
| CN103762362B (en) | A kind of hydrothermal preparing process of nano lithium iron manganese phosphate anode material | |
| CN105742629B (en) | A kind of in-situ preparation method of lithium ion battery anode material lithium iron phosphate/graphene complex | |
| CN106602023B (en) | A kind of method of fabricated in situ graphite phase carbon nitride-oxidation carbon/carbon-copper composite material | |
| CN110255522A (en) | A kind of preparation method of multistage pore-creating formula LiFePO4 | |
| CN102185136B (en) | Preparation method of lithium ion battery cathode material nano lithium iron phosphate | |
| CN106981654A (en) | A kind of preparation method of high-voltage lithium-battery cathode material hollow ball shape nickel ion doped | |
| CN105655573A (en) | General preparing method for manganese-based lithium-ion battery electrode material of one-dimensional micro-nano structure with adjustable length-diameter ratio | |
| CN102800858A (en) | Preparation method and purpose for iron oxide-based anode material for lithium ion battery | |
| Xie et al. | Co 3 (PO 4) 2-coated LiV 3 O 8 as positive materials for rechargeable lithium batteries | |
| CN108511724A (en) | A kind of collosol and gel auxiliary supercritical CO2Drying prepares iron manganese phosphate for lithium method | |
| CN102544494A (en) | Preparation method of nano composite lithium iron phosphate cathode material | |
| CN103413918A (en) | Synthetic method for cathode material lithium cobaltous phosphate used for lithium ion batteries | |
| CN110534721A (en) | A kind of restorative procedure of the tertiary cathode material of performance degradation and the tertiary cathode material of acquisition | |
| CN104167541A (en) | Preparation process of positive electrode material for sodium ion battery | |
| CN103754856A (en) | Preparation method of cobalt lithium phosphate serving as positive material of lithium ion battery | |
| CN105226245A (en) | A kind of anode material for lithium-ion batteries and preparation method thereof | |
| CN102403500A (en) | Method for preparation of lithium iron phosphate material in static mixing tube type reactor | |
| CN104282887A (en) | Carbon coating method for electrode active material of lithium ion battery | |
| CN103296256B (en) | Method for preparing LiFePO4/C composite material by using sol-gel method | |
| CN102544488A (en) | Method for preparing LiFePO4 powder of cathode material of power battery | |
| CN102903915A (en) | Sol-gel method for preparing positive electrode material lithium iron phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |