CN106882843B - A kind of preparation method of densification crystal form cobaltosic oxide - Google Patents
A kind of preparation method of densification crystal form cobaltosic oxide Download PDFInfo
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- CN106882843B CN106882843B CN201710043633.4A CN201710043633A CN106882843B CN 106882843 B CN106882843 B CN 106882843B CN 201710043633 A CN201710043633 A CN 201710043633A CN 106882843 B CN106882843 B CN 106882843B
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- cobaltosic oxide
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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
- 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
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 form cobaltosic oxide of the present invention, is certain value (2~5 μm) by controlling cobalt carbonate grain size, effectively controls the grain size of cobaltosic oxide；By keeping cobalt carbonate to remain a certain amount of NH4Cl (0.1~1%) makes cobalt carbonate each crystal face speed of growth in thermal decomposition process change, and easily forms fine and close crystal growth mode, while NH4Cl decomposition releases ammonia and chlorination Hydrogen Energy effectively controls particle agglomeration and adhesion；By high temperature fast decoupled, fine particle is made to be merged to form complete fine and close crystal form.The cobaltosic oxide soilless sticking that is prepared by the method for the present invention, without adhesion, cobaltosic oxide pattern is in polyhedron or octahedron, and Electronic Speculum shows that 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 preferred 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 grain size cobaltosic oxide was pressed when preparing cobalt acid lithium by the domestic positive electrode producer of South Korea's Samsung and part
Certain proportion is mixed, and big grain size cobaltosic oxide is spherical second particle, and D50 is 15~20 μm, the oxidation of small particle four three
The preferably fine and close crystal particle (non-secondary agglomeration body) of cobalt, D50 is 2~5 μm, and effect is filling bulky grain gap, can significantly be carried
High cobalt acid lithium compacted density, and have improvement to the performance of battery.The following cobaltosic oxide gradually develops to big grain size, big grain size four
The development of Co 3 O has driven the demand of fine and close crystal form small particle cobaltosic oxide product.
The method for preparing fine and close crystal form 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, generation cobaltosic oxide with
Hydrochloric acid.Spray pyrolysis is simple for process, but equipment investment is very big, and gained octahedron cobaltosic oxide crystal is aggregate, and D50 reaches
It 10 μm or more, also needs to grind by gas, obtains dispersed preferable 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 of a concentration of 5.0~10.0mol/L of hydroxyl；3) by above-mentioned mixed liquor and hydroxide solution cocurrent
It is passed into the hydroxide suspension liquid that cobalt is prepared in reaction vessel；4) the hydroxide suspension liquid of cobalt is filtered, washed
And drying；5) hydroxide solids of the cobalt after drying are carried out calcining obtained regular octahedron cobaltosic oxide in calcining furnace.
This 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
Then cobalt calcines obtained cobaltosic oxide again, this method products therefrom is octahedra irregular, particle adhesion, and size distribution is wide.Specially
Sharp CN1648054A also reports similar method, needs thoroughly to wash foreign ion chlorine root, sulfate radical and sodium ion extremely
50ppm obtains bulk polyhedron and octahedron hereinafter, finally also needing to be crushed.
Prepare at present fine and close crystal form cobaltosic oxide exist reunite, size distribution is wide, has the problems such as adhesion between particle.Cause
This, a kind of method of the fine and close crystal form cobaltosic oxide of preparation simple and easy to control of urgent need meets market need to capture above-mentioned problem
It asks, complies with future developing trend.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of crystal form rule, crystal densifications, are not necessarily to powder
It is broken, without adhesion between particle, and the preparation method of the fine and close crystal form cobaltosic oxide of narrow particle size distribution.
In order to achieve the above object, the preparation method of a kind of fine and close crystal form cobaltosic oxide of the invention, it includes as follows
Step：
The first step：To first it be used as bottom liquid in the pure water injection reaction kettle that reaction kettle effective volume 1/10-1/5 accounted for, is warming up to
30~60 DEG C, cobalt chloride solution and ammonium bicarbonate soln is added in reaction kettle simultaneously precipitation reaction occurs under stiring, added
By adjusting the pH value of ammonium bicarbonate soln flow control reaction solution 6~8 during material, when cobalt carbonate grain size is grown 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 are
200~300 DEG C, 0.5~2h, second step high temperature fast decoupled are kept the temperature, temperature is 600~800 DEG C, keeps the temperature 3~4h.
Preferably, the range of flow of cobalt chloride solution is 500~600L/h in the first step, ammonium bicarbonate soln
Starting range of flow is 1400~1800L/h.
Preferably, in the first step cobalt chloride solution a concentration of 90~150g/L.
Preferably, in the first step ammonium bicarbonate soln a concentration of 100~220g/L.
Preferably, in the second step, gained filter cake after cobalt carbonate slurry press filtration is eluted with pure water, when elution
Between be no more than 10 minutes.
The key point of the present invention：First, control cobalt carbonate grain size is certain value (2~5 μm), the grain size for controlling cobalt carbonate can
Effectively to control the grain size of cobaltosic oxide；Second is that the NH not exclusively in removal cobalt carbonate4Cl, but keep cobalt carbonate residual certain
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
It changes, easily forms fine and close crystal growth mode, while NH4Cl decomposition releases ammonia and chlorination Hydrogen Energy effectively controls particle
Reunion and adhesion；Third, high temperature fast decoupled, high temperature fast decoupled can make fine particle be merged to form complete densification
Crystal form.
The cobaltosic oxide soilless sticking that is prepared by the method for the present invention, without adhesion, cobaltosic oxide pattern is in polyhedron
Or it is octahedra, Electronic Speculum shows that particle soilless sticking and adhesion, Laser particle-size distribution are narrow.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of 1 products obtained therefrom of the embodiment of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of 2 products obtained therefrom of the embodiment of the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph of 3 products obtained therefrom of the embodiment of the present invention.
Specific implementation mode
Embodiment 1
1500L pure water is first injected into 10M3Reaction kettle is warming up to 30 DEG C as bottom liquid, under stiring by a concentration of 90g/L
Cobalt chloride solution and 100g/L ammonium bicarbonate solns are added in reaction kettle simultaneously occurs precipitation reaction, and cobalt chloride solution flow is
550L/h, it is 1600L/h that ammonium bicarbonate soln, which originates flow, and the pH value of reaction solution is controlled 6 during charging, is become according to pH value
Change appropriate fine tuning ammonium bicarbonate soln flow, feed time 4h detects that cobalt carbonate grain size is 2.2 μm, stops charging, stirring
10min；Cobalt carbonate slurry is subjected to press filtration, filter cake directly carries out expansion drying, measures and remain NH in cobalt carbonate4The content of Cl is
0.991%, cobalt carbonate is again through two-section calcining, and first segment low temperature predecomposition, temperature is 200 DEG C, keeps the temperature 2h, second segment high temperature is quick
It decomposes, temperature is 600 DEG C, keeps the temperature 4h, obtains fine and close crystal form cobaltosic oxide.
After testing, median particle diameter D50 is 2.1 μm to gained densification crystal form 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 10M3Reaction kettle is warming up to 45 DEG C as bottom liquid, under stiring by a concentration of 120g/L
Cobalt chloride solution and 160g/L ammonium bicarbonate solns are added in reaction kettle simultaneously occurs precipitation reaction, and cobalt chloride solution flow is
500L/h, it is 1400L/h that ammonium bicarbonate soln, which originates flow, and the pH value of solution is controlled 7 during charging, is changed according to pH value
Appropriate fine tuning ammonium bicarbonate soln flow, feed time 3h detect that cobalt carbonate grain size is 3.7 μm, stop charging, stirring
10min；Cobalt carbonate slurry is subjected to press filtration, filter cake is eluted 5 minutes with pure water, then carries out expansion drying, measure in cobalt carbonate
Remain NH4The content of Cl is 0.453%, and cobalt carbonate is again through two-section calcining, and first segment low temperature predecomposition, temperature is 250 DEG C, heat preservation
1.5h, second segment high temperature fast decoupled, temperature are 700 DEG C, keep the temperature 3.5h, obtain fine and close crystal form cobaltosic oxide.
After testing, median particle diameter D50 is 3.5 μm to gained densification crystal form 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 10M3Reaction kettle is warming up to 60 DEG C as bottom liquid, under stiring by a concentration of 150g/L
Cobalt chloride solution and 220g/L ammonium bicarbonate solns are added in reaction kettle simultaneously occurs precipitation reaction, and cobalt chloride solution flow is
600L/h, it is 1800L/h that ammonium bicarbonate soln, which originates flow, and the pH value of solution is controlled 8 during charging, is changed according to pH value
Appropriate fine tuning ammonium bicarbonate soln flow, feed time 2h detect that cobalt carbonate grain size is 4.4 μm, stop charging, stirring
10min；Cobalt carbonate slurry is subjected to press filtration, filter cake is eluted 10 minutes with pure water, then carries out expansion drying, measure in cobalt carbonate
Remain NH4The content of Cl is 0.106%, and cobalt carbonate is again through two-section calcining, and first segment low temperature predecomposition, temperature is 300 DEG C, heat preservation
0.5h, second segment high temperature fast decoupled, temperature are 800 DEG C, keep the temperature 3h, obtain fine and close crystal form cobaltosic oxide.
After testing, median particle diameter D50 is 4.5 μm to gained densification crystal form cobaltosic oxide, and Electronic Speculum is shown in Fig. 3, particle dispersion
Property is good, soilless sticking, without adhesion.
Claims (4)
1. a kind of preparation method of densification crystal form cobaltosic oxide, it is characterised in that：Include the following steps：
The first step：It will first account in the pure water injection reaction kettle of reaction kettle effective volume 1/10-1/5 and be used as bottom liquid, it is warming up to 30~
60 DEG C, cobalt chloride solution and ammonium bicarbonate soln is added in reaction kettle simultaneously precipitation reaction occurs under stiring, fed
Stop when cobalt carbonate grain size is grown to 2~5 μm 6~8 by adjusting the pH value of ammonium bicarbonate soln flow control reaction solution in journey
Only feed；
Second step：Cobalt carbonate slurry that the first step obtains is subjected to press filtration, filter cake is directly dried, keep remaining in cobalt carbonate
NH4The content of Cl is 0.1~1% or the cobalt carbonate slurry press filtration that obtains the first step, and filter cake is eluted with pure water, is eluted
Time is no more than 10 minutes, is then dried, and keeps remaining NH in cobalt carbonate4The content of Cl is 0.1~1%；It will be dry
Cobalt carbonate is calcined, and calcination process is in two steps：First step low temperature predecomposition, temperature are 200~300 DEG C, keep the temperature 0.5~2h,
Second step high temperature fast decoupled, temperature are 600~800 DEG C, keep the temperature 3~4h.
2. a kind of preparation method of fine and close crystal form 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 starting range of flow of ammonium bicarbonate soln is 1400~
1800L/h。
3. a kind of preparation method of fine and close crystal form cobaltosic oxide according to claim 1, it is characterised in that：Described first
A concentration of 90~150g/L of cobalt chloride solution in step.
4. a kind of preparation method of fine and close crystal form cobaltosic oxide according to claim 1, it is characterised in that：Described first
A concentration of 100~220g/L of ammonium bicarbonate soln in step.
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| CN106882843B true CN106882843B (en) | 2018-08-17 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113292106B (en) * | 2020-02-24 | 2023-07-25 | 荆门市格林美新材料有限公司 | Three-time calcination preparation method of large-particle-size aluminum-doped cobaltosic oxide |
| 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 |
| CN113233516B (en) * | 2021-05-28 | 2023-01-06 | 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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- 2017-01-19 CN CN201710043633.4A patent/CN106882843B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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