CN101585559B - Preparation method of spherical cobaltosic oxide with high battery security - Google Patents
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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 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 230000005291 magnetic effect Effects 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- 241000220317 Rosa Species 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 16
- 239000010405 anode material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 3
- 230000005294 ferromagnetic effect Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 15
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 102220042174 rs141655687 Human genes 0.000 description 4
- 102220076495 rs200649587 Human genes 0.000 description 4
- 102220043159 rs587780996 Human genes 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 101100006982 Mus musculus Ppcdc gene Proteins 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation method of spherical cobaltosic oxide with high battery security. The point of the method lies in that the spherical cobaltosic oxide powder is obtained by directoxidization. This powder uses a deironing device to reduce the content of the magnetic foreign substance. The specific steps are as follows: preparing the cobalt salt into the solution with concentration of 1 to 2 mol/L; then adding quantitative complexing agent A; the hydroxide solution being the first and second mixed solutions; simultaneously leading the first and second mixed solutions to a reaction container by means of parallel flow; making the first and second mixed solutions react with each other by strong stirring; strictly controlling pH value, flow, stirring speed and reaction temperature during the reaction process; continuously leading the oxidizing agent with certain flow to the reaction system during the reaction process; after the reaction is finished, aging for 3 to 24 hours in a constant temperature; filter pressing the material by a filter press and the washing the material; then washing the material by the washing kettle and filter pressing, washing it; drying it;filtering the powder by a ferromagnetic filtering device to reduce the content of the magnetic foreign substance; the spherical cobaltosic oxide with high battery security belongs to the battery anodematerial.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of precursor of lithium ionic cell positive material---the preparation method of high battery security spherical cobaltic-cobaltous oxide.
Background technology
Along with the successful exploitation of lithium ion cell anode material lithium cobaltate and developing rapidly of industrialization thereof, and in the widespread use of every field such as mobile telephone, pick up camera, notebook computer, portable electronics, the accident of lithium cell blast also takes place again and again.Therefore, safety performance to lithium ion battery is had higher requirement, and battery grade spherical cobaltosic oxide particle is as the main raw material of lithium ion cell anode material lithium cobaltate, its physicals is (as density, granularity, specific surface area, size distribution, crystal morphology, magnetic foreign body content), chemical property, security and stability are directly determining the performance of cobalt acid lithium, thereby performance and security to battery play important effect, thus the quality of battery grade spherical cobaltosic oxide particle product performance particularly the control of magnetic foreign body be the key that solves lithium cell industrial safety problem.
The patent of invention 03148092.6 that Chinese patent literature discloses discloses " preparation method of high purity spherical cobaltic-cobaltous oxide "; Patent of invention 200510015002.9 discloses " preparation method of lithium ion cell cobaltic-cobaltous oxide negative pole material "; Patent of invention 200810162690.5 discloses the " wet preparation method of battery grade spherical cobaltosic oxide particle; The related technology of these three patents has certain enlightenment effect to relevant product.Co
3O
4Production method roughly can be divided into three major types, that is: vapor phase process, liquid phase method, solid phase method.Co
3O
4The synthetic general calcination or the thermal decomposition method of adopting of micro mist.The Co that the calcination method makes
3O
4Micro mist purity is low, granularity is bigger, the requirement that size-grade distribution is wide, sintering activity is poor, physicochemical property are difficult to reach electronic industry; Thermal decomposition method is generally selected CoAc
2, CoC
2O
4, Co (OH) 2, divalent cobalt such as CoCO3 thermolysis at a certain temperature obtain, and the problem of this method is that energy expenditure is big, the Co that obtains
3O
4Poor activity.
Famous scholar Huang Kelong etc. has utilized Hydrothermal Preparation mono-dispersed nano Co
3O
4The powder theory, the shortcoming point is to adapt to suitability for industrialized production.
Famous scholar Ni Haiyong etc. have prepared by conditions such as control precipitation agent consumption, dosage of surfactant and kinds that dispersing property is good, spheric Co
3O
4Powder, used precipitation agent are NH
4HCO
3, the application of high-molecular weight tensio-active agent causes certain difficulty to sedimentation and filtration.
The refined grade of famous scholar Zhong Wen is with Co (NO
3)
2, H
2O
2, NaOH is a raw material, the synthetic Co of direct oxidation from the aqueous solution
3O
4, but containing the oxyhydroxide and the hydrate thereof of part cobalt in the precipitation, product drying, calcining back are about the coacervate of the particle of 0.5 Ч m for particle diameter.Therefore, reunion how to eliminate particle is the subject matter that preparation tricobalt tetroxide particulate need solve.
Famous scholar's Li Yadong etc. has been reported with Na
2CO
3For precipitation agent prepares Co
3O
4, throw out is difficult to realize solid-liquid separation, and is adsorbed on the impurity Na on the micelle
+Being difficult to washing eliminates; With NH
4HCO
3Be precipitation agent, the gained precipitation is a cobaltous dihydroxycarbonate, though be easy to solid-liquid separation and washing, just can obtain Co through high-temperature heat treatment
3O
4, the big and granule-morphology of energy consumption is owed.What have utilizes NH
4HCO
3For precipitation agent prepares cobaltous dihydroxycarbonate or cobaltous carbonate, obtain Co through thermolysis again
3O
4, the problem of existence also has precipitation not exclusively to cause the metal flow vector bigger, and the waste water that contains the ammonia root in a large number needs to handle, and the environmental issue expectation that relates to solves.
Summary of the invention
For overcoming above-mentioned deficiency, the present invention seeks to provide a kind of preparation method of high battery security spherical cobaltic-cobaltous oxide to this area.Make its technical problem that can solve above-mentioned existence, prepared spherical cobaltic-cobaltous oxide powder size and density evenly, washing easily, magnetic foreign body content is low, technology is simple, easy to operate, realize suitability for industrialized production easily.The objective of the invention is to realize by the following technical solutions.
A kind of preparation method of high battery security spherical cobaltic-cobaltous oxide, the characteristics of this method are:
(1), direct oxidation obtains the spherical cobaltic-cobaltous oxide powder in solution;
(2), the spherical cobaltic-cobaltous oxide powder that makes is selected for use equipment for removing ferric ion reduce the content of magnetic foreign body (Fe+Ni+Zn+Cr).
The concrete steps of this method are:
1), cobalt salt is mixed with the solution that concentration is 1～2mol/L, adding quantitative complexing agent A then is first mixing solutions;
2), compound concentration is that the hydroxide solution of 8～10mol/L is second mixing solutions;
3), adopt and the method for stream feeds first mixing solutions, second mixing solutions in the reaction vessel simultaneously, under violent stirring, both are reacted, strict pH value, flow, stirring velocity and the temperature of reaction controlled of reaction process;
4), the continuous oxygenant of feeding certain flow in the reaction system in reaction process;
5), the reaction finish after, constant temperature ageing 3～24 hours;
6), material is earlier by pressure filter press filtration and washing, washs press filtration washing again after the still washing then;
7), dry oven dry;
8), powder is filtered reduction magnetic foreign body (Fe+Ni+Zn+Cr) content with strong magnetic filter.
Cobalt salt described in above-mentioned described preparation method's the step 1) is a kind of or this two kinds the mixing salt in rose vitriol, the cobalt chloride, and complexing agent A is Padil, disodium ethylene diamine tetraacetate.
Described preparation method's step 2) oxyhydroxide in is sodium hydroxide, potassium hydroxide.
The pH value span of control of described preparation method's step 3) is PH9～12; Temperature of reaction is 40～80 ℃; The feed liquid flow control is at 200～500L/h; Flux of alkaline liquor is controlled at 100～300L/h; The rotating speed of stirring velocity is controlled at 100～200 rev/mins.
Oxygenant in described preparation method's the step 4) is air, oxygen.
Dry bake out temperature described in described preparation method's the step 7) is controlled at 100 ℃～700 ℃, and the time is 2～10 hours.
But the present invention only adopt inexpensive relatively cobalt salt, caustic soda, air and a small amount of complexing agent just building-up reactions active high, density is high, even particle size distribution and powder easy to control, almost spherical, do not need directly from liquid phase, to have synthesized tricobalt tetroxide through the high-temperature calcination of cobalt salt secondary.Solve shortcomings such as conventional solid-state method purity is low, granularity is bigger, and size-grade distribution is wide, sintering activity is poor, energy expenditure is big, also solved the shortcoming that traditional method such as particle are easily reunited, inconvenience is washed.
But use the inventive method industrialization and produce the high battery security spherical cobaltic-cobaltous oxide, utilize cobalt compound oxidized characteristic of solution very under alkaline condition, directly oxidation obtains cobaltosic oxide powder from solution, easily washing, density height, energy consumption is low, magnetic foreign body content is low, technology is simple, easy to operate, be easy to realize suitability for industrialized production.Be to provide a kind of comparatively ideal cell positive material for mobile telephone, pick up camera, notebook computer, portable electronics.
Embodiment
Embodiment 1
On big examination experiment line, preparation 2mol/L cobalt sulfate solution, in feed liquid, add a certain amount of disodium ethylene diamine tetraacetate, with cobalt liquid and alkali lye simultaneously and stream be passed in the reactor, the pH value of control intermediate reaction is 11, temperature of reaction is 60 ℃, control feed liquid total amount is at 500 liters/hour, and the reactor mixing speed is 180 rev/mins, and reaction finishes the back and continues constant temperature ageing 10 hours, washing then, dry oven dry remove magnetic foreign body through strong magnetic vibration strainer.Other technologies are carried out on request, continuous production 10 days, the loose density 1.75g/cm of the cobalt that obtains acid lithium presoma spherical cobaltic-cobaltous oxide
3, tap density 2.53g/cm
3, granularity is: D10=2.23 micron, D50=4.15 micron, D90=6.56 micron, magnetic foreign body content 0.036PPM.
Embodiment 2
On big examination experiment line, preparation 2mol/L cobalt chloride solution, in feed liquid, add a certain amount of disodium ethylene diamine tetraacetate, with cobalt liquid and alkali lye simultaneously and stream be passed in the reactor, the pH value of control intermediate reaction is 11, temperature of reaction is 60 ℃, control feed liquid total amount is at 350 liters/hour, and the reactor mixing speed is 180 rev/mins, and reaction finishes the back and continues constant temperature ageing 10 hours, washing then, dry oven dry remove magnetic foreign body through strong magnetic vibration strainer.Other technologies are carried out on request, continuous production 10 days, the loose density 1.68g/cm of the cobalt that obtains acid lithium presoma spherical cobaltic-cobaltous oxide
3, tap density 2.48g/cm
3, granularity is: D10=2.42 micron, D50=4.35 micron, D90=7.02 micron, magnetic foreign body content 0.028PPM.
Embodiment 3
On big examination experiment line, preparation 1.5mol/L cobalt chloride solution, in feed liquid, add a certain amount of Padil, with cobalt liquid and alkali lye simultaneously and stream be passed in the reactor, the pH value of control intermediate reaction is 11.5, temperature of reaction is 50 ℃, control feed liquid total amount is at 500 liters/hour, and the reactor mixing speed is 150 rev/mins, and reaction finishes the back and continues constant temperature ageing 10 hours, washing then, dry oven dry remove magnetic foreign body through strong magnetic vibration strainer.Other technologies are carried out on request, continuous production 10 days, the loose density 1.25g/cm of the cobalt that obtains acid lithium presoma spherical cobaltic-cobaltous oxide
3, tap density 2.52g/cm
3, granularity is: D10=2.47 micron, D50=4.15 micron, D90=6.81 micron, magnetic foreign body content 0.038PPM.
Embodiment 4
On big examination experiment line, preparation 1.5mol/L cobalt chloride solution, in feed liquid, add a certain amount of Padil, with cobalt liquid and alkali lye simultaneously and stream be passed in the reactor, the pH value of control intermediate reaction is 11.5, temperature of reaction is 50 ℃, control feed liquid total amount is at 350 liters/hour, and the reactor mixing speed is 150 rev/mins, and reaction finishes the back and continues constant temperature ageing 10 hours, washing then, dry oven dry remove magnetic foreign body through strong magnetic vibration strainer.Other technologies are carried out on request, continuous production 10 days, the loose density 1.21g/cm of the cobalt that obtains acid lithium presoma spherical cobaltic-cobaltous oxide
3, tap density 2.46g/cm
3, granularity is: D10=2.55 micron, D50=4.68 micron, D90=7.21 micron, magnetic foreign body content 0.029PPM.
Claims (5)
1. the preparation method of a high battery security spherical cobaltic-cobaltous oxide the method is characterized in that:
(1), direct oxidation obtains the spherical cobaltic-cobaltous oxide powder in solution;
(2), select for use equipment for removing ferric ion to reduce the content of magnetic foreign body Fe+Ni+Zn+Cr in the spherical cobaltic-cobaltous oxide powder that makes, described equipment for removing ferric ion is strong magnetic filter;
The concrete steps of this method are:
1), cobalt salt is mixed with the concentration that concentration is 1～2mol/L, adding quantitative complexing agent A then is first mixing solutions, and described complexing agent A is Padil or disodium ethylene diamine tetraacetate;
2), compound concentration is that the hydroxide solution of 8～10mol/L is second mixing solutions;
3), adopt and the method for stream feeds first mixing solutions, second mixing solutions in the reaction vessel simultaneously, under violent stirring, both are reacted, strict pH value, flow, stirring velocity and the temperature of reaction controlled of reaction process;
4), in reaction process the continuous oxygenant of feeding certain flow in the reaction system, described oxygenant is air, oxygen;
5), the reaction finish after, constant temperature ageing 3～24 hours;
6), material is earlier by pressure filter press filtration and washing, washs press filtration washing again after the still washing then;
7), dry oven dry;
8), powder is filtered with strong magnetic filter, reduce magnetic foreign body Fe+Ni+Zn+Cr content, obtain the high battery security spherical cobaltic-cobaltous oxide.
2. the preparation method of high battery security spherical cobaltic-cobaltous oxide as claimed in claim 1 is characterized in that the cobalt salt described in described preparation method's the step 1) is one or both the mixing salt in rose vitriol, the cobalt chloride.
3. the preparation method of high battery security spherical cobaltic-cobaltous oxide as claimed in claim 1 is characterized in that described preparation method's step 2) in oxyhydroxide be sodium hydroxide, potassium hydroxide.
4. the preparation method of high battery security spherical cobaltic-cobaltous oxide as claimed in claim 1 is characterized in that the pH value span of control in described preparation method's the step 3) is pH9～12; Temperature of reaction is 40 ℃～80 ℃; The flow control of first mixing solutions is at 200～500L/h; The second mixing solutions flow control is at 100～300L/h; The rotating speed of stirring velocity is controlled at 100～200 rev/mins.
5. the preparation method of high battery security spherical cobaltic-cobaltous oxide as claimed in claim 1 is characterized in that dry bake out temperature is controlled at 100 ℃～700 ℃ described in described preparation method's the step 7), and the time is 2～10 hours.
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| JP5961004B2 (en) * | 2012-02-21 | 2016-08-02 | 日本化学工業株式会社 | Method for producing cobalt hydroxide, method for producing cobalt oxide, and method for producing lithium cobaltate |
| CN102689933A (en) * | 2012-03-15 | 2012-09-26 | 湖南红太阳电源新材料股份有限公司 | Method for producing hydroxy cobalt oxide |
| CN103771539B (en) * | 2012-10-19 | 2015-11-18 | 宁波金和锂电材料有限公司 | A kind of method and device preparing Large stone spherical cobaltic-cobaltous oxide |
| CN103833088A (en) * | 2012-11-23 | 2014-06-04 | 宁波科博特钴镍有限公司 | Method for preparing doped spherical cobaltosic oxide |
| CN103964514A (en) * | 2013-01-29 | 2014-08-06 | 宁波科博特钴镍有限公司 | Preparation method of regular octahedron-type cobaltosic oxide |
| CN104058468A (en) * | 2013-03-19 | 2014-09-24 | 南通瑞翔新材料有限公司 | Compact spherical cobalt oxide and preparation method thereof |
| CN103172125A (en) * | 2013-04-18 | 2013-06-26 | 宁波科博特钴镍有限公司 | Production method of cobaltosic oxide |
| CN103318976B (en) * | 2013-07-04 | 2015-12-09 | 中南大学 | A kind of technique being prepared tricobalt tetroxide by cobalt-carrying solution |
| CN103754959B (en) * | 2013-12-31 | 2016-05-04 | 常州博杰新能源材料有限公司 | A kind of preparation method of large granular spherical cobaltosic oxide |
| CN104986807A (en) * | 2015-04-23 | 2015-10-21 | 金川集团股份有限公司 | Spherical tricobalt tetraoxide preparation method |
| CN106340643A (en) * | 2015-07-10 | 2017-01-18 | 北京当升材料科技股份有限公司 | Method for preparing large-grain spherical cobaltosic oxide |
| CN106517360B (en) * | 2016-11-17 | 2018-11-02 | 合肥学院 | Particle self-assembly cobaltosic oxide micron spherical powder and preparation method thereof |
| CN106784800B (en) * | 2017-01-12 | 2020-04-28 | 格林美（江苏）钴业股份有限公司 | High-activity spherical cobaltosic oxide for power lithium ion battery and preparation method thereof |
| CN115636444A (en) * | 2022-11-18 | 2023-01-24 | 金川集团股份有限公司 | Preparation method of small-particle-size low-sodium-sulfur cobaltosic oxide for high-rate lithium cobaltate |
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| CN101434416A (en) * | 2008-11-28 | 2009-05-20 | 宁波金和新材料有限公司 | Hydroxy spherical cobaltosic oxide and preparation thereof |
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| CN1470460A (en) * | 2003-07-08 | 2004-01-28 | 中信国安盟固利电源技术有限公司 | High-purity spherical cobalto-cobaltic oxide, and its preparing method and use |
| CN101066781A (en) * | 2007-06-04 | 2007-11-07 | 仙桃市中星电子材料有限公司 | Process of preparing cobalto-cobaltic oxide for lithium ion cell |
| CN101434416A (en) * | 2008-11-28 | 2009-05-20 | 宁波金和新材料有限公司 | Hydroxy spherical cobaltosic oxide and preparation thereof |
| CN101434415A (en) * | 2008-11-28 | 2009-05-20 | 宁波金和新材料有限公司 | Battery grade spherical cobaltosic oxide particle size control method |
| CN101434417A (en) * | 2008-11-28 | 2009-05-20 | 宁波金和新材料有限公司 | Dry preparation of battery grade spherical cobaltosic oxide particle |
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| CN105668650A (en) * | 2016-03-23 | 2016-06-15 | 荆门市格林美新材料有限公司 | Method for preparing low-sodium cobaltosic oxide |
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