CN113636604B - Preparation method of high-aluminum-doped small-particle-size cobalt carbonate particles - Google Patents
Preparation method of high-aluminum-doped small-particle-size cobalt carbonate particles Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 121
- 229910021446 cobalt carbonate Inorganic materials 0.000 title claims abstract description 94
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 56
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 53
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 53
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000012010 growth Effects 0.000 claims abstract description 40
- 239000012266 salt solution Substances 0.000 claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 44
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 32
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 32
- 239000006228 supernatant Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229940044175 cobalt sulfate Drugs 0.000 claims description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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 abstract description 44
- 229910052782 aluminium Inorganic materials 0.000 abstract description 35
- 238000001354 calcination Methods 0.000 abstract description 16
- 238000009826 distribution Methods 0.000 abstract description 9
- MNHLPGIEDGLHBE-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Al+3].[Co+2] Chemical compound S(=O)(=O)([O-])[O-].[Al+3].[Co+2] MNHLPGIEDGLHBE-UHFFFAOYSA-L 0.000 abstract 1
- 230000006911 nucleation Effects 0.000 description 13
- 238000010899 nucleation Methods 0.000 description 13
- 239000002002 slurry Substances 0.000 description 13
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 10
- 238000005086 pumping Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000009646 cyclic growth Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- IWRAVVYDORMLAM-UHFFFAOYSA-L C([O-])([O-])=O.[Co+2].[Al+3] Chemical compound C([O-])([O-])=O.[Co+2].[Al+3] IWRAVVYDORMLAM-UHFFFAOYSA-L 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/06—Carbonates
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a preparation method of highly aluminum-doped small-particle-size cobalt carbonate particles, which mainly comprises the following steps: preparing a mixed salt solution of soluble cobalt salt and aluminum salt, wherein the mass ratio of aluminum element to cobalt element is 0.011-0.014; adding a mixed salt solution of cobalt aluminum sulfate and an ammonium bicarbonate solution into a diluted ammonium bicarbonate solution, and preparing a cobalt carbonate seed crystal with the D50 of 1.3-1.5 mu m by adopting a synthesis process with low temperature and low feeding rate; and then preparing the cobalt carbonate particles with small particle size through a subsequent synthetic growth process. The prepared cobalt carbonate has the characteristics of high aluminum doping amount and consistent overall crystallinity of particles, and the problems of uneven aluminum distribution and porous inside the particles of the cobalt tetraoxide obtained after calcination of the high aluminum doping cobalt carbonate are effectively solved.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a preparation method of cobalt carbonate serving as a precursor of a lithium battery anode material.
Background
Cobalt carbonate is a very important raw material in the lithium cobalt oxide cathode material industry. The cobalt carbonate is changed into cobaltosic oxide through calcination, so that the cobaltosic oxide can be further sintered with lithium carbonate to prepare lithium cobaltate.
Increasing the energy density of a battery by increasing the charge cutoff voltage and the compacted density of lithium cobaltate is a current and future technological development direction. This in turn has led to the development of tricobalt tetraoxide and cobalt carbonate in two directions: firstly, product particles develop towards the two ends of the large particle size and the small particle size so as to improve the compaction density of the positive electrode material by proportionally mixing the large particle size and the small particle size; secondly, by introducing aluminum doping elements, the stability of the crystal structure of the finally obtained lithium cobaltate is improved, more lithium ions participate in charge and discharge, and the specific capacity of the lithium cobaltate is effectively improved. Researches show that the aluminum doping amount in the cobaltosic oxide is increased to 0.8-1.0%, and the corresponding lithium cobaltate charge cut-off voltage can be increased to more than 4.48V.
However, in the field of small-particle cobalt carbonate and cobaltosic oxide, the research results of people mainly lie in improving the tap density of particles, but the aluminum doping content is still low (the aluminum doping amount in the cobaltosic oxide is less than 0.7wt%) and the requirement of developing lithium cobaltate with the voltage of 4.48V and higher cannot be met. For example, the cobalt carbonate particles prepared by the overflow method in Chinese patent application CN110407257A have less than 0.4wt% of aluminum oxide, and the particles have uneven particle size and larger diameter distance QD than 0.8; in Chinese patent application CN111056575A, sodium hexametaphosphate is used as a dispersing agent, and the aluminum doping amount of cobaltosic oxide corresponding to the small-particle cobalt carbonate prepared by adopting a batch method is less than 0.6wt%.
One reason why highly aluminum-doped cobalt carbonate particles are difficult to prepare is that: as the amount of aluminum doped increases, it is difficult to control the uniformity of crystallinity of the cobalt carbonate particles, resulting in uneven distribution of aluminum and internal porosity in the cobaltosic oxide particles obtained by high-temperature calcination. In addition, as the aluminum doping amount is increased, the cobalt carbonate particles are easy to agglomerate, so that the particle size is uneven, and the compaction density of the subsequently obtained positive electrode material is affected. The above problems are to be solved.
Disclosure of Invention
The invention provides a preparation method of high-aluminum-doped small-particle-size cobalt carbonate particles, and aims to solve the problems of uneven aluminum distribution, porous inside particles and uneven particle size caused by agglomeration while increasing the aluminum doping amount.
According to the embodiment of the invention, a preparation method of highly-doped aluminum cobalt carbonate particles with small particle size is provided, and comprises the following steps:
(1) Preparing a solution: preparing a mixed salt solution of soluble cobalt salt and aluminum salt, wherein the mass ratio of aluminum element to cobalt element is 0.011-0.014, and preparing an ammonium bicarbonate solution;
(2) Seed crystal preparation: adding water and the ammonium bicarbonate solution as base solution into a reaction kettle, and adding the mixed salt solution and the ammonium bicarbonate solution in a parallel flow feeding mode, so that the feeding rate of cobalt ions relative to the volume of the reaction kettle is 0.048+/-0.012 mol/L/hour, controlling the reaction temperature to be 35+/-5 ℃ and basically constant, and reacting until cobalt carbonate seed crystals with the particle size D50 of 1.3-1.5 mu m are obtained; and
(3) And (3) synthesis and growth: and continuously adding the mixed salt solution and the ammonium bicarbonate solution in a parallel flow feeding mode, so that the cobalt carbonate particles grow to the final point granularity.
Preferably, in the step (2), during the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is kept to be 0.16-0.18.
Preferably, in the step (2), the concentration of ammonium bicarbonate in the base solution is 20+/-5 g/L, and the pH value is controlled to be more than or equal to 8.
Preferably, in the step (2), stirring is performed at a stirring speed at which the reaction time for controlling the particle diameter D50 of the cobalt carbonate particles to 1.3 to 1.5 μm is 6 to 8 hours.
Preferably, in step (3), the reaction temperature in step (2) is increased by 5-10 ℃ and kept substantially constant while controlling the feeding rate of cobalt ions relative to the volume of the reaction vessel to be 0.072+/-0.012 mol/L/hour.
Preferably, in the step (3), the pH value is controlled to be 7.6-7.8 by regulating and controlling the feeding mass ratio of cobalt ions and ammonium bicarbonate in the range of 0.18-0.26 in the parallel flow feeding process.
Preferably, in the step (3), the cobalt carbonate particles are grown for a plurality of times by a cycle mode of feeding, standing and extracting supernatant liquid, and the particle size D50 is 3-4 mu m.
Preferably, in the step (3), stirring is performed at a stirring speed that controls the total growth time of the synthetic growth stage to be not less than 33 hours.
Preferably, the concentration of cobalt ions in the mixed salt solution prepared in the step (1) is 120+/-10 g/L, and the concentration of the ammonium bicarbonate solution is 210+/-20 g/L.
The cobalt salt can comprise one or more of cobalt sulfate, cobalt chloride and cobalt nitrate.
According to the embodiment of the invention, when the high-alumina cobalt carbonate particles with small particle diameters are prepared, a low-temperature and low-feeding rate mode is adopted in the seed crystal preparation process, so that the nucleation rate of cobalt carbonate in the initial synthesis stage is reduced, an amorphous structure formed by aluminum enrichment is avoided, the overall crystallinity of the small particles is consistent, and the problems of uneven aluminum distribution and porous inside the cobalt tetraoxide particles obtained after calcination of the high-alumina cobalt carbonate are effectively solved. In addition, the reduction of the nucleation rate of the cobalt carbonate is also beneficial to avoiding agglomeration caused by too fast nucleation and untimely dispersion, eliminating large agglomerate particles and further reducing the particle size distribution.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the accompanying drawings in which:
FIG. 1 is an SEM image (3000 times) of cobalt carbonate particles of example 1 of the invention;
FIG. 2 is an SEM image (3000 times) of a sliced tricobalt tetraoxide obtained by calcining the cobalt carbonate particles obtained in example 1 of the present invention;
FIG. 3 is an SEM image (3000 times) of cobalt carbonate particles of example 2 of the invention;
FIG. 4 is an SEM image (3000 times) of a sliced tricobalt tetraoxide obtained by calcining the cobalt carbonate particles obtained in example 2 of the present invention;
FIG. 5 is an SEM image (3000 times) of cobalt carbonate particles of example 3 of the invention;
FIG. 6 is an SEM image (3000 times) of a sliced tricobalt tetraoxide obtained by calcining the cobalt carbonate particles obtained in example 3 of the present invention;
FIG. 7 is an SEM image (2000 times) of the cobalt carbonate particles obtained in a comparative example;
fig. 8 is an SEM image (3000 times) of a cut piece of tricobalt tetraoxide obtained by calcining the cobalt carbonate particles obtained in the comparative example.
Detailed Description
The present application is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
The preparation method of the high aluminum-doped small-particle-size cobalt carbonate particles can be used for preparing small-particle-size cobalt carbonate particles which can obtain cobaltosic oxide with aluminum content of more than or equal to 0.8wt% after calcination. The term "small-sized cobalt carbonate particles" as used herein refers to cobalt carbonate particles having a particle size D50 of 10 μm or less. The preparation method of the high-aluminum-doped small-particle-size cobalt carbonate particles is particularly suitable for preparing the cobalt carbonate particles with the particle size D50 of 3-5 mu m, especially 3-4 mu m.
The inventors of the present invention found that: when preparing aluminum-doped cobalt carbonate particles, along with the improvement of aluminum doping amount, aluminum enrichment is easy to occur in the seed crystal preparation stage due to rapid nucleation, and the enrichment part is of an amorphous structure, so that the internal and external crystallinity of the cobalt carbonate particles are inconsistent, and aluminum in the cobaltosic oxide is finally distributed unevenly and the particles are porous due to the crystallinity difference after high-temperature calcination. The enrichment of aluminum that occurs as a result of rapid nucleation is also a significant cause of agglomeration because amorphous enriched aluminum tends to cause irregular growth of particles, thereby forming large agglomerate particles. In addition, the rapid nucleation also brings about untimely dispersion of crystal nucleus/crystal grain, and further aggravates the problem of agglomeration.
Based on the above findings, the preparation method of the highly aluminum-doped cobalt carbonate particles with small particle diameters is provided, and comprises the following steps:
(1) Preparing a solution: preparing a mixed salt solution of soluble cobalt salt and aluminum salt, wherein the mass ratio of aluminum element to cobalt element is 0.011-0.014, and preparing an ammonium bicarbonate solution;
(2) Seed crystal preparation: adding water and ammonium bicarbonate solution as base solution into a reaction kettle, and adding mixed salt solution and ammonium bicarbonate solution in a parallel flow feeding mode, so that the feeding rate of cobalt ions relative to the volume of the reaction kettle is 0.048+/-0.012 mol/L/hour, controlling the reaction temperature to be 35+/-5 ℃ and basically constant, and reacting until cobalt carbonate seed crystals with the particle size D50 of 1.3-1.5 mu m are obtained; and
(3) And (3) synthesis and growth: and continuously adding the mixed salt solution and the ammonium bicarbonate solution in a parallel flow feeding mode, so that the cobalt carbonate particles grow to the final particle size.
The mass ratio of aluminum to cobalt in the mixed salt solution prepared in the above step (1) is determined according to the desired amount of aluminum to be doped. In the invention, the desired amount of aluminum doped cobalt carbonate is such that the cobalt carbonate, upon calcination, yields a tricobalt tetraoxide having an aluminum doping of not less than 0.8 wt%. In some cases where the cobalt carbonate has a low water content or other impurity content, this means that the cobalt carbonate has an aluminum loading of greater than or equal to 0.5wt%.
Further, for example, the concentration of cobalt ions in the mixed salt solution prepared in step (1) may be 120.+ -.10 g/L, and the concentration of ammonium bicarbonate solution may be 210.+ -.20 g/L.
It should be understood that the soluble cobalt salt may comprise one or more of cobalt sulfate, cobalt chloride, cobalt nitrate.
In the step (2), the method of low temperature (reaction temperature is 35+/-5 ℃) and low feeding rate (feeding rate is 0.048+/-0.012 mol/L/hour) is adopted in the preparation process of the seed crystal, so that the nucleation rate of cobalt carbonate in the initial stage of synthesis is reduced, the amorphous structure formed by aluminum enrichment is avoided, and the overall crystallinity of small particles is consistent. Correspondingly, after the finally obtained cobalt carbonate particles are calcined into the cobalt tetraoxide particles, the interior of the cobalt tetraoxide particles is more uniform and compact, and the pores are less. In addition, under the environment that nucleation and crystal nucleus growth compete mutually, the inhibition of cobalt carbonate nucleation can promote the crystal nucleus growth to be seed crystals with the required particle size, and the production efficiency is improved. In addition, the reduction of the nucleation rate of the cobalt carbonate is also beneficial to avoiding agglomeration caused by too fast nucleation and untimely dispersion, and further reducing the particle size distribution. This results in the preparation of cobalt carbonate particles having a uniform particle size and a narrower particle size distribution, and in some advantageous embodiments of the invention, a particle diameter distance qd= (d90—d10)/d50 +.0.7 can be achieved.
Preferably, in the step (2), in the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is kept to be 0.16-0.18. On the one hand, the feeding mass ratio can provide a material basis for effectively forming crystal nuclei and promoting crystal nucleus growth, and on the other hand, since the feeding rate of cobalt ions is controlled to be lower, the feeding rate of ammonium bicarbonate is also controlled to be lower, which is beneficial to reducing the nucleation speed of cobalt carbonate.
Preferably, in the step (2), the concentration of ammonium bicarbonate in the base solution is 20+/-5 g/L, and the pH value is controlled to be more than or equal to 8. Here, it is advantageous to suppress agglomeration by controlling the very low concentration of ammonium bicarbonate in the base liquid
The particle growth rate can be slowed down by high-strength stirring, the dispersing effect is enhanced, the agglomeration caused by too fast grain growth and insufficient dispersion is avoided, and the formation of larger agglomerate particles is avoided. It should be understood that since the effect of stirring dispersion is affected not only by the stirring speed but also by conditions such as the size and shape of the reaction vessel and the specific structure of the stirring apparatus (e.g., the size of the stirring paddles, the number of blades), the appropriate stirring conditions need to be selected according to the specific situation, and in particular, the stirring speed and the like cannot be uniquely and absolutely determined. In the step (2), the stirring speed is preferably controlled so that the reaction time for the particle diameter D50 of the cobalt carbonate particles to reach 1.3-1.5 μm is 6-8 hours, which is favorable for reducing the nucleation speed, slowing down the grain growth and simultaneously being favorable for improving the production efficiency.
The above-described step (3) may not be limited to the specific cobalt carbonate grain synthesis growth stage process. In the synthetic growth stage of the step (3), a higher reaction temperature and a larger feeding rate can be adopted to meet the requirement of grain growth and promote the occurrence of crystal form precipitation. Preferably, in step (3), the reaction temperature in step (2) is increased by 5-10 ℃ and kept substantially constant while controlling the feeding rate of cobalt ions relative to the volume of the reaction vessel to be 0.072+/-0.012 mol/L/hour.
The inventors of the present invention found that: in the synthetic growth stage, if the pH value of the reaction system is lower, aluminum sheets (an aluminum compound) on the surface of the synthesized cobalt carbonate can be larger, and meanwhile, the aluminum sheets possibly float on the surface of the cobalt carbonate or have longer growing parts, which indicates that the bulk doping is not uniform enough and does not meet the related requirements of cobalt carbonate particle products; if the pH value is too high, the cobalt content in the tail liquid is usually high, which is unfavorable for the subsequent tail liquid treatment. Thus, preferably, in step (3), the pH is controlled to 7.6-7.8, and preferably the above control of the pH is achieved by controlling the feed mass ratio of cobalt ions to ammonium bicarbonate in the range of 0.18-0.26 during co-current feed.
Preferably, in step (3), the cobalt carbonate particles may be grown a plurality of times by a cyclic manner of feeding, standing and extracting the supernatant to grow to, for example, a particle diameter D50 of 3 to 4 μm.
Similar to that discussed above for the stirring conditions in step (2), in step (3), it is preferable to continue to slow down the particle growth rate by high intensity stirring, enhance the dispersing effect, avoid the formation of agglomerates due to too fast and slow grain growth, and avoid the formation of larger agglomerate particles. In the step (3), stirring is preferably performed at a stirring speed that controls the total growth time of the synthetic growth stage to be greater than or equal to 33 hours, which is advantageous in slowing down grain growth, avoiding agglomeration, and improving production efficiency.
According to the preparation method of the high-alumina small-particle-size cobalt carbonate particles, after the cobalt carbonate particles are grown, the slurry containing the cobalt carbonate particles can be transferred into a centrifuge for dehydration and centrifugal washing, and then transferred into a drying device for drying, so that the cobalt carbonate powder is prepared. However, the invention is not limited in this regard.
The following describes examples and comparative examples of the present invention. It should be understood that the present invention is not limited to any of the following embodiments.
Example 1 ]
Preparing a solution: preparing a cobalt sulfate solution with the cobalt content of 115g/L, and doping aluminum salt to obtain a mixed salt solution, wherein the mass ratio of aluminum element to cobalt element in the mixed salt solution is 0.0113. Preparing ammonium bicarbonate solution.
Seed crystal preparation: preparing 10L of diluted ammonium bicarbonate solution with the concentration of 15g/L as base solution in a reaction kettle with the volume of 50L, and adjusting the pH value of the base solution to be more than or equal to 8 through heating, stirring and induced draft. And (3) under the condition of constant-temperature water bath at 30 ℃, the mixed salt solution and the ammonium bicarbonate solution are pumped into the reaction kettle in parallel, so that the pumping flow rate of the mixed salt solution is 16mL/min (the feeding rate of cobalt ions relative to the volume of the reaction kettle is about 0.036 mol/L/hour). In the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is kept to be 0.18. The particle diameter D50 of the prepared cobalt carbonate seed crystal is 1.32 mu m by adopting a propelling stirring paddle (three layers and three leaves) and carrying out reaction for 6 hours under the strong stirring condition of stirring rotation speed of 310 rpm. And standing and settling the slurry of the prepared cobalt carbonate seed crystal for 2-3 hours, and pumping out supernatant.
And (3) synthesis and growth: in a reaction kettle with the volume of 50L, the temperature of a reaction system in the reaction kettle is raised to 40 ℃ through a constant-temperature water bath, and the mixed salt solution and the ammonium bicarbonate solution are continuously and parallelly pumped into the reaction kettle, so that the pumping flow rate of the mixed salt solution is 26mL/min (the feeding rate of cobalt ions relative to the volume of the reaction kettle is about 0.06 mol/L/hour). In the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is adjusted to be 0.18-0.26, and the pH value is controlled to be 7.6-7.8. The reaction was continued for 3 hours with a frame stirrer under strong stirring at a stirring speed of 260rpm, and then the slurry was allowed to stand still for 2 hours, and the supernatant was removed. And (3) carrying out the cyclic growth of feeding, standing and extracting the supernatant according to the growth conditions and the feeding mode, wherein the total growth time in the synthetic growth stage is 42 hours, and the final particle size of the obtained cobalt carbonate particles is d50=3.27 μm and the diameter distance QD=0.675.
The reaction end point slurry is transferred into a centrifuge, and the high aluminum-doped cobalt carbonate powder is prepared through the procedures of mother liquor removal, centrifugal washing, dehydration, drying and the like, wherein the morphology of cobalt carbonate particles is shown in figure 1. And calcining the cobalt carbonate into cobaltosic oxide, and detecting to obtain the aluminum doped amount of 0.81% in the cobaltosic oxide. Fig. 2 is a slice electron microscope image of the tricobalt tetraoxide.
Example 2 ]
Preparing a solution: preparing a cobalt sulfate solution with the cobalt content of 120g/L, and doping aluminum salt to obtain a mixed salt solution, wherein the mass ratio of aluminum element to cobalt element in the mixed salt solution is 0.0126. Preparing ammonium bicarbonate solution.
Seed crystal preparation: preparing 10L of diluted ammonium bicarbonate solution with the concentration of 20g/L as base solution in a reaction kettle with the volume of 50L, and adjusting the pH value of the base solution to be more than or equal to 8 through heating, stirring and induced draft. And (3) under the condition of constant-temperature water bath at 35 ℃, the mixed salt solution and the ammonium bicarbonate solution are pumped into the reaction kettle in parallel, so that the pumping flow rate of the mixed salt solution is 20mL/min (the feeding rate of cobalt ions relative to the volume of the reaction kettle is about 0.048 mol/L/hour). In the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is kept to be 0.17. The particle diameter D50 of the prepared cobalt carbonate seed crystal is 1.41 mu m by adopting a propelling stirring paddle (three layers and three leaves) and carrying out reaction for 7 hours under the strong stirring condition of stirring rotation speed of 330 rpm. And standing and settling the slurry of the prepared cobalt carbonate seed crystal for 2-3 hours, and pumping out supernatant.
And (3) synthesis and growth: in a reaction kettle with the volume of 50L, the temperature of a reaction system in the kettle is increased to 45 ℃ through a constant-temperature water bath; the mixed salt solution and the ammonium bicarbonate solution were continuously and concurrently pumped into the reaction vessel at a pumping flow rate of 30mL/min (about the feeding rate of cobalt ions relative to the volume of the reaction vessel was 0.072 mol/L/hour). In the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is adjusted to be 0.18-0.26, and the pH value is controlled to be 7.6-7.8. The reaction was continued for 3 hours with a frame stirrer under strong stirring at a stirring speed of 280rpm, and then the slurry was allowed to stand still for 2 hours, and the supernatant was removed. The cyclic growth of the supernatant liquid is carried out according to the growth conditions and the feeding mode, the total growth time of the synthetic growth stage is 36 hours, and the final particle size of the obtained cobalt carbonate particles is d50=3.66 μm and the diameter distance QD=0.686.
Transferring the reaction end slurry into a centrifuge, and performing the procedures of mother liquor removal, centrifugal washing, dehydration, drying and the like to obtain aluminum-doped cobalt carbonate powder, wherein the morphology of cobalt carbonate particles is shown in figure 3. And calcining the cobalt carbonate into cobaltosic oxide, and detecting to obtain the aluminum doped amount of 0.90% in the cobaltosic oxide. Fig. 4 is a slice electron microscope image of the tricobalt tetraoxide.
Example 3 ]
Preparing a solution: preparing a cobalt sulfate solution with the cobalt content of 125g/L, and doping aluminum salt to obtain a mixed salt solution, wherein the mass ratio of aluminum element to cobalt element in the mixed salt solution is 0.0138. Preparing ammonium bicarbonate solution.
Seed crystal preparation: preparing 10L of diluted ammonium bicarbonate solution with the concentration of 25g/L as base solution in a reaction kettle with the volume of 50L, and adjusting the pH value of the base solution to be more than or equal to 8 through heating, stirring and induced air. And (3) under the condition of constant-temperature water bath at 40 ℃, the mixed salt solution and the ammonium bicarbonate solution are pumped into the reaction kettle in parallel, so that the pumping flow rate of the mixed salt solution is 24mL/min (the feeding rate of cobalt ions relative to the volume of the reaction kettle is about 0.06 mol/L/hour). In the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is kept to be 0.16. The particle diameter D50 of the prepared cobalt carbonate seed crystal is 1.47 mu m by adopting a propelling stirring paddle (three layers and three leaves) and carrying out reaction for 8 hours under the strong stirring condition of stirring rotation speed of 350 rpm. The slurry of the prepared cobalt carbonate seed crystals was allowed to stand still for 2 hours, and the supernatant was removed.
And (3) synthesis and growth: in a reaction kettle with the volume of 50L, the temperature of a reaction system in the kettle is increased to 50 ℃ through a constant-temperature water bath; the mixed salt solution and the ammonium bicarbonate solution were continuously and concurrently pumped into the reaction vessel at a pumping flow rate of 33mL/min (about the feeding rate of cobalt ions to the volume of the reaction vessel was 0.084 mol/L/hour). In the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is adjusted to be 0.18-0.26, and the pH value is controlled to be 7.6-7.8. The reaction was continued for 3 hours with a frame stirrer under strong stirring at a stirring speed of 300rpm, and then the slurry was allowed to stand still for 2 hours, and the supernatant was removed. The cyclic growth of the supernatant liquid is carried out according to the growth conditions and the feeding mode, the total growth time of the synthetic growth stage is 33 hours, the final particle size is d50=3.98 μm, and the diameter distance qd=0.698.
The reaction end point slurry is transferred into a centrifuge, and the aluminum-doped cobalt carbonate powder is prepared after the procedures of dehydration, centrifugal washing, dehydration drying, drying and the like, wherein the morphology of cobalt carbonate particles is shown in figure 5. And calcining the cobalt carbonate into cobaltosic oxide, and detecting to obtain the aluminum doped amount of 1.01% in the cobaltosic oxide. Fig. 6 is a tricobalt tetraoxide slice electron microscope image.
Comparative example 1 ]
Preparing a solution: preparing a cobalt sulfate solution with the cobalt content of 120g/L, and doping aluminum salt to obtain a mixed salt solution, wherein the mass ratio of aluminum element to cobalt element in the mixed salt solution is 0.0113. Preparing ammonium bicarbonate solution.
Seed crystal preparation: 10L of ammonium bicarbonate solution with the concentration of 25g/L is added into a reaction kettle with the volume of 50L, and the pH value of the ammonium bicarbonate in the kettle is adjusted to be more than or equal to 8 through heating, stirring and induced air. And (3) under the condition of constant-temperature water bath at 45 ℃, the mixed salt solution and the ammonium bicarbonate solution are pumped into the reaction kettle in parallel, so that the pumping flow rate of the mixed salt solution is 30mL/min (the feeding rate of cobalt ions relative to the volume of the reaction kettle is about 0.072 mol/L/hour). In the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is kept to be 0.16. The particle diameter D50 of the prepared cobalt carbonate seed crystal is 1.62 mu m by adopting a propelling stirring paddle (three layers and three leaves) and carrying out reaction for 7 hours under the strong stirring condition of stirring rotation speed of 350 rpm. The slurry of the prepared cobalt carbonate seed crystals was allowed to stand still for 2 hours, and the supernatant was removed.
And (3) synthesis and growth: in a reaction kettle with the volume of 50L, keeping the temperature of a reaction system in the kettle at 50 ℃; the mixed salt solution and the ammonium bicarbonate solution were continuously and concurrently pumped into the reaction vessel at a pumping flow rate of 25mL/min (about the feeding rate of cobalt ions relative to the volume of the reaction vessel was 0.06 mol/L/hour). In the parallel flow feeding process, the feeding mass ratio of cobalt ions to ammonium bicarbonate is adjusted to be 0.18-0.26, and the pH value is controlled to be 7.6-7.8. The reaction was continued for 3 hours with a frame stirrer under strong stirring at a stirring speed of 300rpm, and then the slurry was allowed to stand still for 2 hours, and the supernatant was removed. The cyclic growth of the supernatant liquid is carried out according to the growth conditions and the feeding mode, the total growth time of the synthetic growth stage is 27h, the final particle size is d50=3.98 μm, and the diameter distance qd=0.752.
The reaction end point slurry is transferred into a centrifuge, and the aluminum-doped cobalt carbonate powder is prepared after the procedures of dehydration, centrifugal washing, dehydration drying, drying and the like, wherein the morphology of cobalt carbonate particles is shown in figure 7. And calcining the cobalt carbonate into cobaltosic oxide, and detecting to obtain the aluminum doped amount of 0.99% in the cobaltosic oxide. Fig. 8 is a slice electron microscope image of the tricobalt tetraoxide.
Comparing the SEM images of the cobaltosic oxide slices obtained by calcining the cobalt carbonate particles obtained by the preparation method according to the embodiment of the present invention shown in fig. 2, 4 and 6 with the SEM images of the cobaltosic oxide slices obtained by calcining the cobalt carbonate particles obtained by the preparation method according to the comparative example shown in fig. 8, it can be seen that the preparation method of the present invention can well eliminate/alleviate the problems of uneven distribution of aluminum inside the cobaltosic oxide particles and porous inside the particles obtained by calcining the highly aluminum-doped cobalt carbonate. In addition, comparing the morphology of the cobalt carbonate particles obtained by the preparation method according to the embodiment of the present invention shown in fig. 1, 3 and 5 with the morphology of the cobalt carbonate particles obtained by the preparation method according to the comparative example shown in fig. 8, it can be seen that the preparation method of the present invention can obtain cobalt carbonate particles having a uniform particle size/a narrow particle size distribution, and well avoid the formation and appearance of large agglomerate particles.
The physicochemical index lookup tables for the products of each stage in examples 1-3 and comparative examples are shown in the following tables.
The foregoing description is only of the preferred embodiments of the present application and is presented as a description of the principles of the technology being utilized. It will be appreciated by persons skilled in the art that the scope of the invention referred to in this application is not limited to the specific combinations of features described above, but it is intended to cover other embodiments in which any combination of features described above or equivalents thereof is possible without departing from the spirit of the invention. Such as the above-described features and technical features having similar functions (but not limited to) disclosed in the present application are replaced with each other.
Claims (8)
1. A method for preparing highly aluminum-doped small-particle-size cobalt carbonate particles, wherein the particle size of the cobalt carbonate particles is 3-5 mu m, and the method comprises the following steps:
(1) Preparing a solution: preparing a mixed salt solution of soluble cobalt salt and aluminum salt, wherein the mass ratio of aluminum element to cobalt element is 0.011-0.014, and preparing an ammonium bicarbonate solution;
(2) Seed crystal preparation: adding water and the ammonium bicarbonate solution into a reaction kettle as base solution, and adding the mixed salt solution and the ammonium bicarbonate solution in a parallel flow feeding mode, so that the feeding rate of cobalt ions relative to the volume of the reaction kettle is 0.048+/-0.012 mol/L/hour, controlling the reaction temperature to be 35+/-5 ℃ and constant, and reacting until cobalt carbonate seed crystals with the particle size D50 of 1.3-1.5 mu m are obtained; and
(3) And (3) synthesis and growth: continuously adopting a parallel flow feeding mode to add the mixed salt solution and the ammonium bicarbonate solution, so that the cobalt carbonate particles grow to the final point granularity,
wherein in the step (2), in the process of parallel flow feeding, the feeding mass ratio of cobalt ions to ammonium bicarbonate is kept to be 0.16-0.18, and stirring is carried out at a stirring speed of controlling the particle diameter D50 of the cobalt carbonate particles to reach 1.3-1.5 mu m and the reaction time to be 6-8 hours; and in the step (3), the pH value is controlled to be 7.6-7.8.
2. The process according to claim 1, wherein the concentration of ammonium bicarbonate in the base solution in the step (2) is 20.+ -.5 g/L, and the pH is controlled to be not less than 8.
3. The production process according to claim 1 or 2, wherein in the step (3), the reaction temperature in the step (2) is increased by 5 to 10 ℃ and kept constant while controlling the feeding rate of cobalt ions to the volume of the reaction vessel to 0.072.+ -. 0.012mol/L/hour.
4. The preparation method of claim 1, wherein in the step (3), the control of the pH value to 7.6-7.8 is achieved by controlling the feeding mass ratio of cobalt ions and ammonium bicarbonate in the range of 0.18-0.26 in the parallel flow feeding process.
5. The process according to claim 4, wherein in the step (3), the cobalt carbonate particles are grown to a particle diameter D50 of 3 to 4. Mu.m, by a cycle of charging, standing and collecting the supernatant.
6. The process according to claim 5, wherein in the step (3), stirring is performed at a stirring rate at which the total growth time in the synthetic growth stage is not less than 33 hours.
7. The production method according to claim 1 or 2, wherein the concentration of cobalt ions in the mixed salt solution prepared in step (1) is 120±10g/L, and the concentration of the ammonium bicarbonate solution is 210±20g/L.
8. The preparation method of claim 1 or 2, wherein the cobalt salt comprises one or more of cobalt sulfate, cobalt chloride and cobalt nitrate.
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| CN111646519A (en) * | 2020-07-17 | 2020-09-11 | 衢州华友钴新材料有限公司 | Preparation method of aluminum-doped cobaltosic oxide |
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| CN111422915A (en) * | 2020-03-26 | 2020-07-17 | 衢州华友钴新材料有限公司 | Preparation method of low-sulfur compact crystal cobalt carbonate |
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