CN111646519A - Preparation method of aluminum-doped cobaltosic oxide - Google Patents
Preparation method of aluminum-doped cobaltosic oxide Download PDFInfo
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- CN111646519A CN111646519A CN202010691844.0A CN202010691844A CN111646519A CN 111646519 A CN111646519 A CN 111646519A CN 202010691844 A CN202010691844 A CN 202010691844A CN 111646519 A CN111646519 A CN 111646519A
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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 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 63
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 63
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 52
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 52
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 50
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 38
- 239000010941 cobalt Substances 0.000 claims abstract description 38
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000004806 packaging method and process Methods 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 102
- 238000003756 stirring Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 25
- 238000005086 pumping Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 1
- -1 cobalt content Chemical compound 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention relates to the technical field of battery material preparation, in particular to a preparation method of aluminum-doped cobaltosic oxide, which comprises the following steps: step one, preparing a solution: preparing aluminum-doped cobalt solution and ammonium bicarbonate solution; step two, seed crystal synthesis; step three, growing cobalt carbonate; step four, washing and drying; step five, calcining; and step six, mixing and packaging. The preparation method of the aluminum-doped cobaltosic oxide has the advantages that the prepared aluminum-doped cobaltosic oxide has uniform particles and does not have compact massive particles and particle aggregates.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a preparation method of aluminum-doped cobaltosic oxide.
Background
With the updating of 3C products and the release of various high-end wearable devices, people have higher and higher requirements on lithium ion batteries, and positive electrode material manufacturers commonly mix particles with different sizes to improve the compaction density of a positive electrode, so that the energy density of the lithium ion batteries is improved. The cobaltosic oxide is used as an important precursor for preparing the lithium cobaltate serving as the lithium battery anode material, and various indexes of the cobaltosic oxide influence the performance of the lithium cobaltate anode material and a downstream lithium ion battery. Recently, lithium cobaltate positive electrode material manufacturers have made higher requirements for traditional indexes of cobaltosic oxide, such as cobalt content, tap density, specific surface, sphericity and the like, and also have made requirements for agglomerates in small-particle-size cobaltosic oxide products. The existence of the agglomerates has a certain influence on the uniformity of the whole product and the mixed material calcination of the downstream cathode material. In the preparation of cobaltosic oxide, along with the increase of the aluminum doping amount in the cobaltosic oxide, agglomeration is easier to occur. At present, some cobaltosic oxide manufacturers gradually pay attention to the agglomerates in the product, but a better solution is not provided for a while.
Disclosure of Invention
The present invention is directed to solving the above-mentioned problems, and an object of the present invention is to provide a method for preparing aluminum-doped cobaltosic oxide, which can reduce or even eliminate the formation of agglomerates during the production process of aluminum-doped cobaltosic oxide.
In order to achieve the purpose, the invention designs a preparation method of aluminum-doped cobaltosic oxide, which specifically comprises the following steps:
step one, preparing a solution: preparing aluminum-doped cobalt solution and ammonium bicarbonate solution;
step two, seed crystal synthesis: injecting pure water or low-concentration ammonium bicarbonate solution into the reaction kettle as base solution, pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution prepared in the step one into the reaction kettle in proportion while stirring the reaction kettle, and continuously stirring and dispersing after stopping feeding to obtain cobalt carbonate seed crystals; the median particle diameter is 1.4-3 μm.
Step three, cobalt carbonate growth: putting the crystal seeds obtained in the step two in a growth kettle, pumping the aluminum-doped cobalt liquid and the ammonium bicarbonate solution prepared in the step one into the growth kettle in proportion while stirring the growth kettle at a high speed until the material in the growth kettle reaches an upper limit, stopping stirring while stopping feeding, standing, removing supernatant after the material is settled, continuing to start stirring and feeding, and repeating the process for multiple times until the target particle size is reached to obtain aluminum-doped cobalt carbonate slurry;
step four, washing and drying: introducing the aluminum-doped cobalt carbonate slurry into a centrifuge after washing by adopting clean water, centrifugally dewatering to obtain an aluminum-doped cobalt carbonate wet material, and drying the aluminum-doped cobalt carbonate wet material;
step five, calcining: filtering the dried aluminum-doped cobalt carbonate by using a vibrating screen, then calcining the filtered aluminum-doped cobalt carbonate in a rotary kiln to obtain aluminum-doped cobaltosic oxide, and then transferring the aluminum-doped cobaltosic oxide to a mixing bin by using a furnace tail vibrating screen;
step six, mixing and packaging: and packaging the mixed material of the aluminum-doped cobaltosic oxide to obtain an agglomeration-free aluminum-doped cobaltosic oxide product.
Preferably, the aluminum-doped cobalt solution in the first step is one or a mixture of an aluminum-doped cobalt sulfate solution and an aluminum-doped cobalt chloride solution, the concentration of cobalt ions is 1.5-2.5 mol/L, and the mass ratio of aluminum to cobalt elements is 0.0014-0.014; the concentration of the ammonium bicarbonate solution is 2.5-2.9 mol/L.
And optimally, the volume of the bottom liquid in the second step is 6-20% of the rated capacity of the reaction kettle, namely, the liquid level just reaches the upper edge of the lower stirring blade. The concentration of ammonium bicarbonate in the base solution is less than or equal to 40g/L, and the pH value of the base solution is controlled to be 7.2-8.3; wherein the rotating speed of the reaction kettle is 320-500rpm when the aluminum-doped cobalt solution and the ammonium bicarbonate solution are pumped into the reaction kettle, the molar ratio of the aluminum-doped cobalt solution and the ammonium bicarbonate solution pumped into the reaction kettle is 0.2-0.25, the total volume of the pumped materials accounts for 16-50% of the rated capacity of the reaction kettle, and the pH value of the mixed solution of the aluminum-doped cobalt solution and the ammonium bicarbonate solution is controlled to be 7.8-8.2; the reaction temperature in the reaction kettle is controlled at 30-40 ℃; and (3) pumping the aluminum-doped cobalt solution and the ammonium bicarbonate into the reaction kettle for 1-3 hours, and continuously stirring for 1.5-2.5 hours for dispersing after the feeding is finished.
As optimization, the molar ratio of the aluminum-doped cobalt solution to the ammonium bicarbonate is pumped in the third step of 0.24-0.3, the pH value range is controlled to be 7.3-7.8, the stirring speed of the growth kettle is 300-400rpm during feeding, the rotation speed of the growth kettle is 200-350rpm during repeated feeding after subsequent clear liquid is pumped out, and the target particle size is set to be 3-8 mu m.
If the target particle size is not reached after the feeding is repeated for 8-12 times in the third step, transferring part of the materials in the growth kettle to other empty growth kettles, and repeating the process according to the third step until the materials reach the target particle size.
And as optimization, in the fourth step, the aluminum-doped cobalt carbonate wet material is washed for 10-20min by using clean water at the temperature of 70-80 ℃, and the moisture content of the aluminum-doped cobalt carbonate wet material after being dehydrated by a centrifugal machine is less than or equal to 25 percent. Drying the aluminum-doped cobalt carbonate wet material, wherein the drying can preferably adopt an oven or a flash evaporation dryer, and other drying equipment can be adopted. Wherein when the drying is carried out by adopting an oven, the drying temperature of the oven is controlled to be 90-105 ℃, and when the drying is carried out by adopting a flash evaporation dryer, the drying temperature is controlled to be 160-190 ℃.
And optimally, filtering the dried aluminum-doped cobalt carbonate in the step five by using a 300-mesh 400-mesh screen, then feeding the filtered aluminum-doped cobalt carbonate into a rotary kiln for calcination, filtering the calcined aluminum-doped cobaltosic oxide by using a 200-mesh 300-mesh furnace tail vibrating screen, then filtering the calcined aluminum-doped cobaltosic oxide by using a 400-mesh vibrating screen, and finally feeding the filtered aluminum-doped cobaltosic carbonate into a material mixing bin.
And optimally, mixing the aluminum-doped cobaltosic oxide in the sixth step for 1-15min, and packaging to obtain the aluminum-doped cobaltosic oxide, wherein D50 is 3-6 mu m, and the aluminum content is 0.1-1.0%.
The preparation method of the aluminum-doped cobaltosic oxide has the advantages that the prepared aluminum-doped cobaltosic oxide has uniform particles and does not have compact massive particles and particle aggregates.
The preparation method of the aluminum-doped cobaltosic oxide has the following characteristics:
1. the low-temperature reaction in the seed crystal synthesis step greatly reduces the crystallization rate of the cobalt carbonate, so that the cobalt carbonate has enough time to be dispersed under high-speed stirring to form crystal nuclei independently, thereby avoiding the agglomeration of the crystal nuclei. And stirring and dispersing are carried out after the feeding in the seed crystal stage is finished, so that the amorphous cobalt carbonate which is not crystallized is prevented from being adhered, agglomerated and crystallized into larger particles.
2. In the seed crystal synthesis step, the volume of the base solution is just equal to that of the lower layer, and the lower layer is stirred, so that the strong heat and mass transfer capacity can be provided for the seed crystal stage at a certain stirring speed.
3. The cobalt carbonate dried in the step five passes through a vibrating screen, and 1) large blocky caking wall materials appearing on a reaction kettle, a stirring shaft and blades in the synthesis process can be removed; 2) can disperse part of slightly agglomerated cobalt carbonate, and avoid the formation of compact agglomerates when calcined and decomposed by a rotary kiln.
4. In the step five, the vibrating screen with larger diameter of the tail of the furnace can 1) remove larger conglutination agglomerates and other foreign matters in the calcining process; 2) can remove part of the large agglomerates in advance, and avoid the influence on the productivity caused by material blockage caused by a vibrating screen with a smaller aperture in the follow-up process.
5. The aggregates with a size of more than 20 μm are further removed by a vibrating screen with a high mesh number and a low pore diameter.
Drawings
FIG. 1 is an SEM photograph (1000 times) of a product obtained in example 1 of the present invention.
FIG. 2 is an SEM photograph (1000 times) of a product obtained in example 2 of the present invention.
FIG. 3 is an SEM photograph (1000 times) of a product obtained in example 3 of the present invention.
FIG. 4 is an SEM photograph (1000 times) of a product obtained in example 4 of the present invention.
Detailed Description
The invention is further described by way of example with reference to the accompanying drawings.
Example 1:
the preparation method of aluminum-doped cobaltosic oxide described in this embodiment includes the following specific steps:
step one, preparing a solution: the concentration of the aluminum-doped cobalt sulfate solution is 2.4 mol/L, the mass ratio of aluminum elements to cobalt elements is 0.014, and the concentration of the ammonium bicarbonate solution is 2.8 mol/L.
Step two, seed crystal synthesis: and (3) injecting pure water into the reaction kettle, adding the low-concentration ammonium bicarbonate solution obtained by mixing and diluting the ammonium bicarbonate solution in the step one as a base solution, wherein the volume of the base solution is 6%, the concentration of the ammonium bicarbonate in the base solution is 40g/L, and the pH value of the base solution is controlled to be 8.3. And (2) simultaneously pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution prepared in the step one into a reaction kettle according to a certain proportion at a high stirring speed of 500rpm, wherein the feeding molar ratio of cobalt salt to ammonium bicarbonate is 0.20, the total volume of the pumped materials accounts for 16% of the rated capacity of the reaction kettle, the pH value range is controlled to be 8.2, and the synthesis temperature is controlled to be 40 ℃. Feeding for 3h, stopping pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution, continuously stirring at a high speed for 1.5h for dispersing, and preparing the cobalt carbonate seed crystal with the median particle size of 1.4 mu m.
Step three, cobalt carbonate growth: and (3) putting the seed crystal in the step two into a growth kettle, and simultaneously pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution into the growth kettle according to a certain proportion at a high stirring speed of 400rpm, wherein the feeding molar ratio is 0.24, and the pH value range is controlled to be 7.8. Stopping feeding and stirring after the materials in the growth kettle reach the upper limit, settling the materials, removing supernatant, and continuing to start stirring and feeding. The stirring speed was reduced to 350rpm and repeated 9 times to reach the set target particle size of 3.8. mu.m.
Step four, washing and drying: and (3) introducing the aluminum-doped cobalt carbonate slurry into a centrifuge, washing for 20min by using water at the temperature of 70-80 ℃, and centrifugally dewatering to obtain an aluminum-doped cobalt carbonate wet material with the water content of 22%. And transferring the wet cobalt carbonate material into a flash evaporation dryer for drying, and setting the temperature to be 185 ℃ to obtain the dried aluminum-doped cobalt carbonate.
Step five, calcining: after the large aggregates of the dried aluminum-doped cobalt carbonate are removed by a 400-mesh screen, the dried aluminum-doped cobalt carbonate is sucked into a rotary kiln for calcination through a bucket elevator or a vacuum feeder, the calcined aluminum-doped cobaltosic oxide is obtained in a low-temperature zone 320 and a high-temperature zone 840 ℃, and then large agglomerated particles are removed through a 300-mesh furnace tail vibrating screen. And then the mixture is transferred into a mixing bin after passing through a vibrating screen with 600 meshes.
Step six, mixing and packaging: mixing the aluminum-doped cobaltosic oxide for 15min, packaging by a packaging machine to obtain the agglomeration-free aluminum-doped cobaltosic oxide product shown in figure 1, wherein the particle size is 3.7 mu m, the aluminum content is 1.0 percent,
example 2:
the preparation method of aluminum-doped cobaltosic oxide described in this embodiment includes the following specific steps:
step one, preparing a solution: the concentration of the aluminum-doped cobalt chloride solution is 2.2 mol/L, the mass ratio of aluminum elements to cobalt elements is 0.00972, and the concentration of the ammonium bicarbonate solution is 2.7 mol/L.
Step two, seed crystal synthesis: and (3) injecting pure water into the reaction kettle, adding the low-concentration ammonium bicarbonate solution obtained by mixing and diluting the ammonium bicarbonate solution in the step one as a base solution, wherein the volume of the base solution is 10%, the concentration of the ammonium bicarbonate in the base solution is 30 g/L, and the pH value of the base solution is controlled to be 8.0. And (2) simultaneously pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution prepared in the step one into a reaction kettle according to a certain proportion at a high stirring speed of 400rpm, wherein the feeding molar ratio of cobalt salt to ammonium bicarbonate is 0.22, the total volume of the pumped materials accounts for 30 percent of the rated capacity of the reaction kettle, the pH value range is controlled to be 8.0, and the synthesis temperature is controlled to be 38 ℃. And feeding for 2 hours, stopping pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution, continuously stirring at a high speed for 2.0 hours for dispersing, and preparing the cobalt carbonate seed crystal with the median particle size of 2.2 mu m.
Step three, cobalt carbonate growth: and (3) putting the seed crystal in the step two into a growth kettle, and simultaneously pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution into the growth kettle according to a certain proportion at a high stirring speed of 350rpm, wherein the feeding molar ratio is 0.30, and the pH value range is controlled to be 7.5. Stopping feeding and stirring after the materials in the growth kettle reach the upper limit, settling the materials, removing supernatant, and continuing to start stirring and feeding. The stirring speed was reduced to 300 rpm, and the target particle size of 6.4 μm was reached after 10 repetitions.
Step four, washing and drying: and (3) introducing the aluminum-doped cobalt carbonate slurry into a centrifuge, washing for 20min by using water at the temperature of 75 ℃, and centrifugally dewatering to obtain an aluminum-doped cobalt carbonate wet material with the water content of 18%. And (3) transferring the wet cobalt carbonate material into a flash evaporation dryer for drying, and setting the temperature at 180 ℃ to obtain the dried aluminum-doped cobalt carbonate.
Step five, calcining: after the large aggregates of the dried aluminum-doped cobalt carbonate are removed by a 400-mesh screen, the dried aluminum-doped cobalt carbonate is sucked into a rotary kiln for calcination through a bucket elevator or a vacuum feeder, the low-temperature area of the rotary kiln is 500 ℃, the high-temperature area is 740 ℃, the aluminum-doped cobaltosic oxide obtained after calcination is subjected to a 200-mesh furnace tail vibrating screen, and large agglomerated particles are removed. And then the mixture is transferred into a mixing bin after passing through a vibrating screen of 500 meshes.
Step five, mixing and packaging: after mixing the aluminum-doped cobaltosic oxide for 1min, packaging by a packaging machine to obtain an agglomeration-free aluminum-doped cobaltosic oxide product as shown in figure 2, wherein the particle size is 5.9 mu m, and the aluminum content is 0.7%.
Example 3:
the preparation method of aluminum-doped cobaltosic oxide described in this embodiment includes the following specific steps:
step one, preparing a solution: the concentration of the aluminum-doped cobalt sulfate solution is 1.5 mol/L, the mass ratio of aluminum elements to cobalt elements is 0.0083, and the concentration of the ammonium bicarbonate solution is 2.5 mol/L.
Step two, seed crystal synthesis: and (3) injecting pure water into the reaction kettle, adding the low-concentration ammonium bicarbonate solution obtained by mixing and diluting the ammonium bicarbonate solution in the step one as a base solution, wherein the volume of the base solution is 20%, the concentration of the ammonium bicarbonate in the base solution is 20 g/L, and the pH value of the base solution is controlled to be 7.8. And (2) simultaneously pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution prepared in the step one into a reaction kettle according to a certain proportion at a high stirring speed of 320 rpm, wherein the feeding molar ratio of cobalt salt to ammonium bicarbonate is 0.20, the total volume of the pumped materials accounts for 50% of the rated capacity of the reaction kettle, the pH value range is controlled to be 8.2, and the synthesis temperature is controlled to be 30 ℃. And after feeding for 3 hours, stopping pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution, continuously stirring at a high speed for 2.5 hours for dispersing to obtain the cobalt carbonate seed crystal with the median particle size of 3 microns.
Step three, cobalt carbonate growth: and (3) putting the seed crystal in the step two into a growth kettle, and simultaneously pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution into the reaction kettle according to a certain proportion at a high stirring speed of 300 rpm, wherein the feeding molar ratio is 0.24, and the pH value range is controlled to be 7.3. And stopping feeding and closing stirring after the materials in the reaction kettle reach the upper limit, settling the materials, removing supernatant, and continuing to start stirring and feeding. The stirring speed is reduced to 200rpm, after 8 times of repetition, the 1/2 material in the kettle is transferred to other empty kettles and the synthesis is continued according to the process. And separating the reactors and synthesizing for 2 times to grow the particles to the target particle size of 6 mu m to obtain the aluminum-doped cobalt carbonate slurry.
Step four, washing and drying: and (3) introducing the aluminum-doped cobalt carbonate slurry into a centrifuge, washing for 10min by using water at the temperature of 80 ℃, and centrifugally dewatering to obtain an aluminum-doped cobalt carbonate wet material with the water content of 20%. And transferring the wet cobalt carbonate material into an oven for drying at 105 ℃ to obtain the dried aluminum-doped cobalt carbonate.
Step five, calcining: after the large aggregates of the dried aluminum-doped cobalt carbonate are removed by a 300-mesh screen, the dried aluminum-doped cobalt carbonate is sucked into a rotary kiln for calcination through a bucket elevator or a vacuum feeder, the low-temperature zone of the rotary kiln is 285 ℃, the high-temperature zone of the rotary kiln is 720 ℃, the aluminum-doped cobaltosic oxide obtained after calcination is subjected to a 200-mesh furnace tail vibrating screen, and large agglomerated particles are removed. And then the mixture is transferred into a mixing bin after passing through a vibrating screen with 400 meshes.
Step five, mixing and packaging: after 10min, the mixture of aluminum-doped cobaltosic oxide was packed by a packer to obtain an agglomerate-free product of aluminum-doped cobaltosic oxide as shown in FIG. 3, with a particle size of 5.2 μm and an aluminum content of 0.7%.
Example 4:
the preparation method of aluminum-doped cobaltosic oxide described in this embodiment includes the following specific steps:
step one, preparing a solution: the concentration of the aluminum-doped cobalt chloride solution is 2.2 mol/L, the mass ratio of aluminum elements to cobalt elements is 0.0014, and the concentration of the ammonium bicarbonate solution is 2.9 mol/L.
Step two, seed crystal synthesis: pure water was injected into the reactor as a base solution, the volume of which was 6%. And (2) simultaneously pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution prepared in the step one into a reaction kettle according to a certain proportion at a high stirring speed of 500rpm, wherein the feeding molar ratio of cobalt salt to ammonium bicarbonate is 0.20, the total volume of the pumped materials accounts for 25% of the rated capacity of the reaction kettle, the pH value range is controlled to be 8.2, and the synthesis temperature is controlled to be 30 ℃. Feeding for 2 h, stopping pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution, continuously stirring at a high speed for 2.5h for dispersing, and preparing the cobalt carbonate seed crystal with the median particle size of 2.8 mu m.
Step three, cobalt carbonate growth: and (3) putting the seed crystal in the step two into a growth kettle, and simultaneously pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution into the growth kettle according to a certain proportion at a high stirring speed of 300 rpm, wherein the feeding molar ratio is 0.30, and the pH value range is controlled to be 7.3. And stopping feeding and stirring after the materials in the reaction kettle reach the upper limit, settling the materials, removing the supernatant, and continuing to start stirring and feeding. The stirring speed is reduced to 200rpm, after 12 times of repetition, the 1/2 material in the kettle is transferred to other empty kettles, and after 10 times of synthesis is continued according to the process, the materials grow in the kettle for 4 times again until the end point granularity is 6.5 mu m.
Step four, washing and drying: and (3) introducing the aluminum-doped cobalt carbonate slurry into a centrifuge, washing for 10min by using water at 72 ℃, and centrifugally dewatering to obtain an aluminum-doped cobalt carbonate wet material with the water content of 20%. And transferring the wet cobalt carbonate material to an oven for drying at the temperature of 95 ℃ to obtain the dried aluminum-doped cobalt carbonate.
Step five, calcining: after the large aggregates of the dried aluminum-doped cobalt carbonate are removed by a 300-mesh screen, the dried aluminum-doped cobalt carbonate is sucked into a rotary kiln for calcination through a bucket elevator or a vacuum feeder, the low-temperature zone of the rotary kiln is 280 ℃, the high-temperature zone is 760 ℃, the aluminum-doped cobaltosic oxide obtained after calcination is subjected to a 200-mesh furnace tail vibrating screen, and large agglomerated particles are removed. And then the mixture is transferred into a mixing bin after passing through a vibrating screen with 400 meshes.
Step five, mixing and packaging: after mixing the aluminum-doped cobaltosic oxide for 12min, packaging by a packaging machine to obtain an agglomeration-free aluminum-doped cobaltosic oxide product as shown in figure 4, wherein the particle size is 5.7 mu m, and the aluminum content is 0.1%.
Claims (8)
1. A preparation method of aluminum-doped cobaltosic oxide is characterized by comprising the following steps: the method specifically comprises the following steps:
step one, preparing a solution: preparing aluminum-doped cobalt solution and ammonium bicarbonate solution;
step two, seed crystal synthesis: injecting pure water or low-concentration ammonium bicarbonate solution into the reaction kettle as base solution, pumping the aluminum-doped cobalt solution and the ammonium bicarbonate solution prepared in the step one into the reaction kettle in proportion while stirring the reaction kettle, and continuously stirring and dispersing after stopping feeding to obtain cobalt carbonate seed crystals;
step three, cobalt carbonate growth: putting the crystal seeds obtained in the step two in a growth kettle, pumping the aluminum-doped cobalt liquid and the ammonium bicarbonate solution prepared in the step one into the growth kettle in proportion while stirring the growth kettle at a high speed until the material in the growth kettle reaches an upper limit, stopping stirring while stopping feeding, standing, removing supernatant after the material is settled, continuing to start stirring and feeding, and repeating the process for multiple times until the target particle size is reached to obtain aluminum-doped cobalt carbonate slurry;
step four, washing and drying: introducing the aluminum-doped cobalt carbonate slurry into a centrifuge after washing by adopting clean water, centrifugally dewatering to obtain an aluminum-doped cobalt carbonate wet material, and drying the aluminum-doped cobalt carbonate wet material;
step five, calcining: filtering the dried aluminum-doped cobalt carbonate by using a vibrating screen, then calcining the filtered aluminum-doped cobalt carbonate in a rotary kiln to obtain aluminum-doped cobaltosic oxide, and then transferring the aluminum-doped cobaltosic oxide to a mixing bin by using a furnace tail vibrating screen;
step six, mixing and packaging: and packaging the mixed material of the aluminum-doped cobaltosic oxide to obtain an agglomeration-free aluminum-doped cobaltosic oxide product.
2. The method for preparing the aluminum-doped cobaltosic oxide as claimed in claim 1, wherein the method comprises the following steps: the aluminum-doped cobalt solution in the first step is one or a mixture of an aluminum-doped cobalt sulfate solution and an aluminum-doped cobalt chloride solution, the concentration of cobalt ions is 1.5-2.5 mol/L, and the mass ratio of aluminum to cobalt elements is 0.0014-0.014; the concentration of the ammonium bicarbonate solution is 2.5-2.9 mol/L.
3. The method for preparing the aluminum-doped cobaltosic oxide as claimed in claim 2, wherein the method comprises the following steps: in the second step, the volume of the base solution is 6-20% of the rated capacity of the reaction kettle, the concentration of ammonium bicarbonate in the base solution is less than or equal to 40g/L, and the pH value of the base solution is controlled to be 7.2-8.3; wherein the rotating speed of the reaction kettle is 320-500rpm when the aluminum-doped cobalt solution and the ammonium bicarbonate solution are pumped into the reaction kettle, the molar ratio of the aluminum-doped cobalt solution and the ammonium bicarbonate solution pumped into the reaction kettle is 0.2-0.25, the total volume of the pumped materials accounts for 16-50% of the rated capacity of the reaction kettle, and the pH value of the mixed solution of the aluminum-doped cobalt solution and the ammonium bicarbonate solution is controlled to be 7.8-8.2; the reaction temperature in the reaction kettle is controlled at 30-40 ℃; and (3) pumping the aluminum-doped cobalt solution and the ammonium bicarbonate into the reaction kettle for 1-3 hours, and continuously stirring for 1.5-2.5 hours for dispersing after the feeding is finished.
4. The method for preparing the aluminum-doped cobaltosic oxide as claimed in claim 2, wherein the method comprises the following steps: the third step is that the mol ratio of the aluminum-doped cobalt solution and the ammonium bicarbonate is pumped in the third step is 0.24-0.3, the PH value range is controlled in the range of 7.3-7.8, the stirring speed of the growth kettle is 400rpm during feeding, the rotation speed of the growth kettle is 200rpm and 350rpm during repeated feeding after subsequent clear liquid is pumped out, and the target grain diameter is set to be 3-8 mu m.
5. The method for preparing the aluminum-doped cobaltosic oxide as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: in the fourth step, clean water at 70-80 ℃ is used for washing for 10-20min, and the moisture content of the aluminum-doped cobalt carbonate wet material after the dehydration of a centrifugal machine is less than or equal to 25 percent.
6. The method for preparing the aluminum-doped cobaltosic oxide as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: filtering the dried aluminum-doped cobalt carbonate in the step five by using a 300-mesh 400-mesh screen, then feeding the filtered aluminum-doped cobalt carbonate into a rotary kiln for calcination, filtering the calcined aluminum-doped cobaltosic oxide by using a 200-mesh 300-mesh furnace tail vibrating screen, then filtering the calcined aluminum-doped cobaltosic oxide by using a 400-mesh vibrating screen, and finally feeding the filtered aluminum-doped cobaltosic carbonate into a material mixing bin.
7. The method for preparing the aluminum-doped cobaltosic oxide as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: and sixthly, mixing the aluminum-doped cobaltosic oxide for 1-15min, and packaging to obtain the aluminum-doped cobaltosic oxide, wherein D50 is 3-6 mu m, and the aluminum content is 0.1-1.0%.
8. The method for preparing the aluminum-doped cobaltosic oxide as claimed in claim 4, wherein the method comprises the following steps: if the target particle size is not reached after the feeding is repeated for 8-12 times in the third step, transferring part of the materials in the growth kettle to other empty growth kettles, and repeating the process according to the third step until the materials reach the target particle size.
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