CN106882843A - A kind of preparation method of fine and close crystal formation cobaltosic oxide - Google Patents
A kind of preparation method of fine and close crystal formation cobaltosic oxide Download PDFInfo
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- CN106882843A CN106882843A CN201710043633.4A CN201710043633A CN106882843A CN 106882843 A CN106882843 A CN 106882843A CN 201710043633 A CN201710043633 A CN 201710043633A CN 106882843 A CN106882843 A CN 106882843A
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- cobaltosic oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/41—Particle morphology extending in three dimensions octahedron-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The present invention relates to a kind of preparation method of cobaltosic oxide, more particularly to a kind of preparation method of lithium ion battery cobaltosic oxide.A kind of preparation method of fine and close crystal formation cobaltosic oxide of the invention, by controlling cobalt carbonate particle diameter for certain value (2~5 μm), effectively controls the particle diameter of cobaltosic oxide；A certain amount of NH is remained by keeping cobalt carbonate4Cl (0.1~1%), makes cobalt carbonate each crystal face speed of growth in thermal decomposition process change, and fine and close crystal growth mode is easily formed, while NH4Cl decomposition discharges ammonia and chlorination Hydrogen Energy effectively controls particle agglomeration and adhesion；By high temperature fast decoupled, fine particle is set to be merged to form complete fine and close crystal formation.The cobaltosic oxide soilless sticking that is prepared by the inventive method, without adhesion, cobaltosic oxide pattern is in polyhedron or octahedron, and Electronic Speculum display particle soilless sticking and adhesion, Laser particle-size distribution are narrow.
Description
Technical field
The present invention relates to a kind of preparation method of cobaltosic oxide, more particularly to a kind of lithium ion battery cobaltosic oxide
Preparation method.
Background technology
Cobalt acid lithium is the first-selected positive electrode of 3C lithium ion batteries, and cobaltosic oxide is the important forerunner for producing cobalt acid lithium
Body.In recent years, large and small particle diameter cobaltosic oxide was pressed when cobalt acid lithium is prepared by the domestic positive electrode producer of South Korea's Samsung and part
Certain proportion is mixed, and big particle diameter cobaltosic oxide is spherical second particle, and D50 is 15~20 μm, the oxidation of small particle four three
The preferred densification crystal particle (non-secondary agglomeration body) of cobalt, D50 is 2~5 μm, and its effect is filling bulky grain gap, can significantly be carried
Cobalt acid lithium compacted density high, and performance to battery has improvement.Following cobaltosic oxide progressively develops to big particle diameter, big particle diameter four
The development of Co 3 O has driven the demand of fine and close crystal formation small particle cobaltosic oxide product.
The method for preparing fine and close crystal formation cobaltosic oxide has spray pyrolysis, precipitation-thermal decomposition method etc..Spray pyrolysis with
Cobalt chloride is raw material, by cobalt chloride solution atomization be droplet, directly thermally decompose at high temperature, generate cobaltosic oxide with
Hydrochloric acid.Spray pyrolysis process is simple, but equipment investment is very big, and gained octahedron cobaltosic oxide crystal is aggregate, and D50 reaches
More than 10 μm, also need to be ground by gas, obtain dispersed preferably small particle product.
Patent CN103964514A discloses a kind of preparation method of regular octahedron cobaltosic oxide, including step：1) will
Concentration of cobalt ions is that the cobalt salt solution of 1.0~2.0mol/L and complexing agent are hybridly prepared into mixed liquor；2) hydroxide is prepared
As the hydroxide solution that hydroxyl concentration is 5.0~10.0mol/L；3) by above-mentioned mixed liquor and hydroxide solution cocurrent
It is passed into reaction vessel and prepares the hydroxide suspension liquid of cobalt；4) the hydroxide suspension liquid of cobalt filtered, washed
And drying；5) hydroxide solids of the cobalt after drying are carried out in calcining furnace calcining prepared regular octahedron cobaltosic oxide.
The method needs to add complexing agent, and the impurity natrium washing of presoma cobalt hydroxide is more difficult.
Patent CN103964514A discloses precipitation-thermal decomposition method and prepares octahedra cobaltosic oxide, i.e., first carbonate synthesis
Cobalt, then calcines prepared cobaltosic oxide again, and the method products therefrom is octahedra irregular, and particle adhesion, size distribution is wide.Specially
Sharp CN1648054A also reports similar method, it is necessary to foreign ion chlorine root, sulfate radical and sodium ion are thoroughly washed extremely
Below 50ppm, finally also needs to crush to obtain bulk polyhedron and octahedron.
Prepare at present fine and close crystal formation cobaltosic oxide exist reunite, size distribution is wide, have the problems such as adhesion between particle.Cause
This, is badly in need of a kind of method of the fine and close crystal formation cobaltosic oxide of preparation simple and easy to control, to capture above-mentioned problem, meets market need
Ask, comply with future developing trend.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of crystal formation rule, crystal are fine and close, without powder
It is broken, without adhesion between particle, and the fine and close crystal formation cobaltosic oxide of narrow particle size distribution preparation method.
In order to achieve the above object, the preparation method of a kind of fine and close crystal formation cobaltosic oxide of the invention, it includes as follows
Step：
The first step：To first account in the pure water injection reactor of reactor effective volume 1/10-1/5 as bottom liquid, be warming up to
30~60 DEG C, cobalt chloride solution and ammonium bicarbonate soln are added in reactor simultaneously under agitation precipitation reaction occurs, plus
The pH value of reaction solution is controlled 6~8 by adjusting ammonium bicarbonate soln flow during material, when cobalt carbonate particle diameter is long to 2~5 μm
When stop charging；
Second step：The cobalt carbonate slurry that the first step is obtained carries out press filtration, drying, keeps remaining NH in cobalt carbonate4Cl's
Content is 0.1~1%；Dry cobalt carbonate is calcined, calcination process is in two steps：First step low temperature predecomposition, temperature is
200~300 DEG C, 0.5~2h, second step high temperature fast decoupled are incubated, temperature is 600~800 DEG C, is incubated 3~4h.
Preferably, the range of flow of cobalt chloride solution is 500~600L/h in the first step, ammonium bicarbonate soln
Initial range of flow is 1400~1800L/h.
Preferably, the concentration of cobalt chloride solution is 90~150g/L in the first step.
Preferably, the concentration of ammonium bicarbonate soln is 100~220g/L in the first step.
Preferably, in the second step, gained filter cake after cobalt carbonate slurry press filtration is carried out into drip washing with pure water, during drip washing
Between be no more than 10 minutes.
Key point of the invention：One is to control cobalt carbonate particle diameter for certain value (2~5 μm), and the particle diameter of control cobalt carbonate can
Effectively to control the particle diameter of cobaltosic oxide；Two is not exclusively to remove the NH in cobalt carbonate4Cl, but it is certain to remain cobalt carbonate
The NH of amount4Cl (0.1~1%), remains a certain amount of NH4Cl can make cobalt carbonate each crystal face speed of growth in thermal decomposition process
Change, fine and close crystal growth mode is easily formed, while NH4Cl decomposition discharges ammonia and chlorination Hydrogen Energy effectively controls particle
Reunite and adhesion；Three is high temperature fast decoupled, and high temperature fast decoupled can make fine particle be merged to form complete densification
Crystal formation.
The cobaltosic oxide soilless sticking that is prepared by the inventive method, without adhesion, cobaltosic oxide pattern is in polyhedron
Or it is octahedra, Electronic Speculum display particle soilless sticking and adhesion, Laser particle-size distribution are narrow.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the products obtained therefrom of the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the products obtained therefrom of the embodiment of the present invention 2.
Fig. 3 is the scanning electron microscope (SEM) photograph of the products obtained therefrom of the embodiment of the present invention 3.
Specific embodiment
Embodiment 1
1500L pure water is first injected into 10M3Reactor is warming up to 30 DEG C as bottom liquid, is under agitation 90g/L by concentration
There is precipitation reaction in cobalt chloride solution and 100g/L ammonium bicarbonate solns, cobalt chloride solution flow is in adding reactor simultaneously
550L/h, ammonium bicarbonate soln starting flow is 1600L/h, and the pH value control of reaction solution becomes 6 according to pH value during charging
Change appropriate fine setting ammonium bicarbonate soln flow, feed time is 4h, detect cobalt carbonate particle diameter for 2.2 μm, stop charging, stirring
10min；Cobalt carbonate slurry is carried out into press filtration, filter cake directly carries out expansion drying, to measure and remain NH in cobalt carbonate4The content of Cl is
0.991%, again through two-section calcining, first paragraph low temperature predecomposition, temperature is 200 DEG C to cobalt carbonate, is incubated 2h, and second segment high temperature is quick
Decompose, temperature is 600 DEG C, is incubated 4h, obtains fine and close crystal formation cobaltosic oxide.
After testing, its median particle diameter D50 is 2.1 μm to gained densification crystal formation cobaltosic oxide, and Electronic Speculum is shown in Fig. 1, particle dispersion
Property is good, soilless sticking, without adhesion.
Embodiment 2
1500L pure water is first injected into 10M3Reactor is warming up to 45 DEG C as bottom liquid, is under agitation 120g/L by concentration
There is precipitation reaction in cobalt chloride solution and 160g/L ammonium bicarbonate solns, cobalt chloride solution flow is in adding reactor simultaneously
500L/h, ammonium bicarbonate soln starting flow is 1400L/h, and the pH value control of solution changes 7 according to pH value during charging
Appropriate fine setting ammonium bicarbonate soln flow, feed time is 3h, detects cobalt carbonate particle diameter for 3.7 μm, stops charging, stirring
10min；Cobalt carbonate slurry is carried out into press filtration, then filter cake pure water drip washing 5 minutes carry out expansion drying, in measuring cobalt carbonate
Residual NH4The content of Cl is 0.453%, and again through two-section calcining, first paragraph low temperature predecomposition, temperature is 250 DEG C to cobalt carbonate, insulation
1.5h, second segment high temperature fast decoupled, temperature is 700 DEG C, is incubated 3.5h, obtains fine and close crystal formation cobaltosic oxide.
After testing, its median particle diameter D50 is 3.5 μm to gained densification crystal formation cobaltosic oxide, and Electronic Speculum is shown in Fig. 2, particle dispersion
Property is good, soilless sticking, without adhesion.
Embodiment 3
1500L pure water is first injected into 10M3Reactor is warming up to 60 DEG C as bottom liquid, is under agitation 150g/L by concentration
There is precipitation reaction in cobalt chloride solution and 220g/L ammonium bicarbonate solns, cobalt chloride solution flow is in adding reactor simultaneously
600L/h, ammonium bicarbonate soln starting flow is 1800L/h, and the pH value control of solution changes 8 according to pH value during charging
Appropriate fine setting ammonium bicarbonate soln flow, feed time is 2h, detects cobalt carbonate particle diameter for 4.4 μm, stops charging, stirring
10min；Cobalt carbonate slurry is carried out into press filtration, then filter cake pure water drip washing 10 minutes carry out expansion drying, in measuring cobalt carbonate
Residual NH4The content of Cl is 0.106%, and again through two-section calcining, first paragraph low temperature predecomposition, temperature is 300 DEG C to cobalt carbonate, insulation
0.5h, second segment high temperature fast decoupled, temperature is 800 DEG C, is incubated 3h, obtains fine and close crystal formation cobaltosic oxide.
After testing, its median particle diameter D50 is 4.5 μm to gained densification crystal formation cobaltosic oxide, and Electronic Speculum is shown in Fig. 3, particle dispersion
Property is good, soilless sticking, without adhesion.
Claims (5)
1. a kind of preparation method of fine and close crystal formation cobaltosic oxide, it is characterised in that：Comprise the following steps：
The first step：To first account in the pure water injection reactor of reactor effective volume 1/10-1/5 as bottom liquid, it is warming up to 30~
60 DEG C, cobalt chloride solution and ammonium bicarbonate soln are added in reactor simultaneously under agitation precipitation reaction occurs, fed
Control the pH value of reaction solution 6~8 by adjusting ammonium bicarbonate soln flow in journey, when cobalt carbonate particle diameter it is long to 2~5 μm when stop
Only feed；
Second step：The cobalt carbonate slurry that the first step is obtained carries out press filtration, drying, keeps remaining NH in cobalt carbonate4The content of Cl is
0.1~1%；Dry cobalt carbonate is calcined, calcination process is in two steps：First step low temperature predecomposition, temperature be 200~
300 DEG C, 0.5~2h, second step high temperature fast decoupled are incubated, temperature is 600~800 DEG C, is incubated 3~4h.
2. the preparation method of a kind of fine and close crystal formation cobaltosic oxide according to claim 1, it is characterised in that：Described first
The range of flow of cobalt chloride solution is 500~600L/h in step, the initial range of flow of ammonium bicarbonate soln for 1400~
1800L/h。
3. the preparation method of a kind of fine and close crystal formation cobaltosic oxide according to claim 1, it is characterised in that：Described first
The concentration of cobalt chloride solution is 90~150g/L in step.
4. the preparation method of a kind of fine and close crystal formation cobaltosic oxide according to claim 1, it is characterised in that：Described first
The concentration of ammonium bicarbonate soln is 100~220g/L in step.
5. the preparation method of a kind of fine and close crystal formation cobaltosic oxide according to claim 1, it is characterised in that：Described second
In step, gained filter cake after cobalt carbonate slurry press filtration is carried out into drip washing with pure water, the drip washing time is no more than 10 minutes.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645393A (en) * | 2020-12-21 | 2021-04-13 | 格林美（江苏）钴业股份有限公司 | Preparation method of cobaltosic oxide |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
| CN113292106A (en) * | 2020-02-24 | 2021-08-24 | 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 |
| CN113617346A (en) * | 2021-08-18 | 2021-11-09 | 珠海市科立鑫金属材料有限公司 | Preparation method of small-particle cobaltosic oxide |
| CN113716618A (en) * | 2021-09-01 | 2021-11-30 | 荆门市格林美新材料有限公司 | Preparation method of cobaltosic oxide with octahedral morphology |
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| CN101293677A (en) * | 2007-04-28 | 2008-10-29 | 北京有色金属研究总院 | Method for preparing cobaltic-cobaltous oxide powder with octahedron shape |
| CN101913659A (en) * | 2010-08-10 | 2010-12-15 | 江苏东新能源科技有限公司 | Battery-grade cobaltosic oxide preparation method |
| CN105399148A (en) * | 2015-12-07 | 2016-03-16 | 衢州华友钴新材料有限公司 | Preparation method of large-particle-size and high-density spherical cobalt oxide |
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2017
- 2017-01-19 CN CN201710043633.4A patent/CN106882843B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101293677A (en) * | 2007-04-28 | 2008-10-29 | 北京有色金属研究总院 | Method for preparing cobaltic-cobaltous oxide powder with octahedron shape |
| CN101913659A (en) * | 2010-08-10 | 2010-12-15 | 江苏东新能源科技有限公司 | Battery-grade cobaltosic oxide preparation method |
| CN105399148A (en) * | 2015-12-07 | 2016-03-16 | 衢州华友钴新材料有限公司 | Preparation method of large-particle-size and high-density spherical cobalt oxide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292106A (en) * | 2020-02-24 | 2021-08-24 | 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 |
| CN112645393A (en) * | 2020-12-21 | 2021-04-13 | 格林美（江苏）钴业股份有限公司 | Preparation method of cobaltosic oxide |
| CN113233516A (en) * | 2021-05-28 | 2021-08-10 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
| CN113617346A (en) * | 2021-08-18 | 2021-11-09 | 珠海市科立鑫金属材料有限公司 | Preparation method of small-particle cobaltosic oxide |
| CN113716618A (en) * | 2021-09-01 | 2021-11-30 | 荆门市格林美新材料有限公司 | Preparation method of cobaltosic oxide with octahedral morphology |
| CN113716618B (en) * | 2021-09-01 | 2023-08-01 | 荆门市格林美新材料有限公司 | Preparation method of cobaltosic oxide with octahedral morphology |
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