CN110002513B - Preparation method of cobaltosic oxide - Google Patents
Preparation method of cobaltosic oxide Download PDFInfo
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- CN110002513B CN110002513B CN201910329430.0A CN201910329430A CN110002513B CN 110002513 B CN110002513 B CN 110002513B CN 201910329430 A CN201910329430 A CN 201910329430A CN 110002513 B CN110002513 B CN 110002513B
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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 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 51
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 48
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 48
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 40
- 239000010941 cobalt Substances 0.000 claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 230000032683 aging Effects 0.000 claims description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 27
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 19
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000005086 pumping Methods 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 230000007423 decrease Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 149
- 230000035484 reaction time Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 4
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
- C01P2006/11—Powder tap density
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- 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
- C01P2006/12—Surface area
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention discloses a preparation method of cobaltosic oxide, which increases or decreases the concentration gradient of a cobalt solution added into a reaction kettle along with the prolonging of synthesis time, and simultaneouslyRegulating the solid-liquid ratio of the slurry in the reaction kettle, and synthesizing compact cobalt hydroxide by a wet method; and after the synthesis is finished, washing, drying and calcining the synthesized product to obtain the cobaltosic oxide product. By utilizing the process, the laser granularity D can be prepared10At 12 to 15 μm, D50At 17-19 mu m, D90The tap density is ≧ 2.4g/cm at 22-25 μm3The specific surface area is 1.0-3.0 m2(g) large-particle-size cobaltosic oxide product or laser particle size D with spherical or spheroidal morphology10At 1 to 3 μm, D50At 3-5 mu m, D907 to 10 mu m, a tap density of ≧ 2.5g/cm3, and a specific surface area of 1.0 to 3.0m2(iii) a small particle size cobaltosic oxide product with spherical or spheroidal morphology.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of large-particle-size cobaltosic oxide for preparing high-voltage lithium cobaltate.
Background
The lithium ion battery prepared by using lithium cobaltate as the anode material has the characteristics of light weight, large capacity, high specific energy, high working voltage, stable discharge, suitability for large-current discharge, good cycle performance, long service life and the like, and is mainly applied to the field of 3C digital codes.
Lithium cobaltate is developing towards high voltage, high compaction and high cycle performance, the requirement on the raw material cobaltosic oxide is higher and higher, and Co3O4Is a functional material with special structure and performance, and is Co with conventional grain size (5-10 microns)3O4The market has faced the current situation of gradual shrinkage, large particle size Co3O4The market demand is gradually highlighted. It has become a hot spot to study how to prepare high-performance large-particle-size cobaltosic oxide.
Chinese patent CN201510881580.4 discloses a method for preparing spherical cobaltosic oxide with large particle size and high density, which comprises the steps of preparing cobalt carbonate through multiple circulation crystallization in the cobalt carbonate synthesis stage, locally decomposing the cobalt carbonate in the low-temperature pre-decomposition stage through sectional thermal decomposition to form a micropore channel, and densifying the particle surface in the high-temperature thermal decomposition stage, thereby obtaining the spherical cobaltosic oxide with large particle size and high density. The method needs repeated circulating crystallization in the cobalt carbonate synthesis stage, has a complex process, and is not beneficial to industrial production. Chinese patent CN201210401514.9 discloses a method and a device for preparing large-particle-size spherical cobaltosic oxide, which is characterized in that the particle size of cobaltosic oxide particles at a discharge port is tested when cobaltosic oxide with a preset particle size is prepared, if the particle size of cobaltosic oxide particles is smaller than the preset production particle size of cobaltosic oxide, suspension in the discharge port is introduced into a reaction device again for continuous reaction, and when the particle size of cobaltosic oxide at the discharge port of the reaction device is not smaller than the preset production particle size, the suspension is introduced into a filter press for filtering to obtain the spherical cobaltosic oxide.
Disclosure of Invention
The invention aims to provide a preparation method of cobaltosic oxide with large or small particle size, which has stable growth of cobalt hydroxide and simple and easily-controlled production process.
The invention is realized by the following technical scheme:
a preparation method of large-particle-size cobaltosic oxide specifically comprises the following steps:
step (a), liquid preparation:
preparing a cobalt solution with the cobalt concentration of 20-40 g/L as an A solution and a cobalt solution with the cobalt concentration of 140-160 g/L as a B solution by using cobalt salt as a raw material; the volume ratio of the solution A to the solution B is 1: 1.5;
preparing a solution C: preparing ammonia water with the concentration of 180g/L, adding 5-20 ml of hydrazine hydrate solution with the mass concentration of 80% into each liter of ammonia water, and then mixing the hydrazine hydrate solution with sodium hydroxide solution with the concentration of 200-300 g/L according to the volume ratio of 0.1-0.2: 1;
step (b), synthesis reaction:
adding the solution B into the solution A at a flow rate of 300L/h, adding the solution B and the solution C mixed with the solution B into a reaction kettle at a flow rate of 500L/h in parallel, controlling the pH value of the reaction to be 8.4-8.8, stirring to synthesize cobalt hydroxide, pumping slurry in the reaction kettle into a precision filter to concentrate when the volume of the added material reaches 80-85% of the volume of the reaction kettle, returning the concentrated slurry to the reaction kettle to continue synthesis, and keeping the liquid level in the kettle constant all the time;
step (c), aging:
after the reaction is finished, closing the precision filter, beginning to age, and after the aging is finished, filtering, washing and drying the synthesized product to obtain a large-particle-size cobalt hydroxide product;
step (d), calcination:
calcining the cobalt hydroxide with large particle size obtained in the step (c) to obtain a cobaltosic oxide product with large particle size.
For the synthesis reaction of the step (b) of the present invention described above: replacing the addition mode of A, B solution D, adjusting the raw material proportion and the process parameters, and finally preparing the small-granularity cobaltosic oxide product, which comprises the following steps:
step (a), liquid preparation:
preparing a cobalt solution with the cobalt concentration of 20-40 g/L as an A solution and a cobalt solution with the cobalt concentration of 140-160 g/L as a B solution by using cobalt salt as a raw material; the volume ratio of the solution A to the solution B is 1: 1;
preparing a solution C: preparing ammonia water with the concentration of 180g/L, adding 5-20 ml of hydrazine hydrate solution with the mass concentration of 80% into each liter of ammonia water, and then mixing the hydrazine hydrate solution with sodium hydroxide solution with the concentration of 200-300 g/L according to the volume ratio of 0.05-0.1: 1;
step (b), synthesis reaction:
adding the solution A into the solution B at a flow rate of 250L/h, adding the solution A and the solution C mixed with the solution A into a reaction kettle at a flow rate of 500L/h in parallel at the same time, controlling the pH value to be 8.8-9.0, stirring to synthesize cobalt hydroxide, pumping slurry in the reaction kettle into a precision filter to concentrate when the volume of the added material reaches 75-80% of the volume of the reaction kettle, returning the concentrated slurry into the reaction kettle to continue synthesis, and keeping the liquid level in the kettle constant all the time;
step (c), aging:
after the reaction is finished, closing the precision filter, beginning to age, and after the aging is finished, filtering, washing and drying the synthesized product to obtain a small-granularity cobalt hydroxide product;
step (d), calcination:
calcining the small-granularity cobalt hydroxide obtained in the step (c) to obtain a small-granularity cobaltosic oxide product.
When the cobaltosic oxide with large particle size or small particle size is prepared, in the step (a), the cobalt salt is any one of cobalt sulfate, cobalt nitrate or cobalt chloride.
When the small-granularity cobaltosic oxide product is prepared, in the step (b), the reaction temperature is strictly controlled to be 70-75 ℃ in the reaction process, and the stirring intensity is 300-320 revolutions per minute.
When the large-particle-size cobaltosic oxide product is prepared, in the step (b), the reaction temperature is strictly controlled to be 75-80 ℃ in the reaction process, and the stirring intensity is 200-250 revolutions per minute.
When the cobaltosic oxide with large particle size or small particle size is prepared, in the step (b), the amount of the materials added into the reaction kettle is controlled according to the amount of the mother liquor discharged by the precision filter, so that the liquid level in the kettle is kept unchanged.
In the step (c), the aging time is 1-2 h.
In the step (c), the washing is carried out by using deionized water at the temperature of 80-90 ℃ for centrifugal washing.
In the step (c), a flash evaporation machine is adopted for drying, and the drying temperature is 200-300 ℃.
In the step (d), the calcination is performed by adopting a rotary kiln, the calcination temperature is 700-750 ℃, and the calcination time is 4-6 h.
The large-particle-size cobaltosic oxide product obtained by the invention comprises the following components in parts by weight: the laser particle size D10 is 12-15 mu m, the D50 is 17-19 mu m, the D90 is 22-25 mu m, the tap density is not less than 2.4g/cm3, the specific surface area is 1.0-3.0 m2/g, and the morphology of the cobaltosic oxide with large particle size is spherical or sphere-like.
The small-granularity cobaltosic oxide product obtained by the invention comprises the following components in percentage by weight: laser particle size D10At 1 to 3 μm, D50At 3-5 mu m, D90The tap density is not less than 2.5g/cm at 7-10 μm3The specific surface area is 1.0-3.0 m2The shape is spherical or sphere-like.
Compared with the prior art, the invention has the following advantages:
1. when the large-particle-size cobaltosic oxide is prepared, the following steps are carried out: by respectively preparing cobalt solutions with high concentration (B solution) and low concentration (A solution) as cobalt sources, firstly adding the cobalt solution with high concentration into the cobalt solution with low concentration at a certain flow rate for mixing, adding the cobalt solution with high concentration and the cobalt solution with low concentration which are being mixed into a reaction kettle in parallel flow, leading the concentration of the cobalt solution which is in parallel flow with the C solution to be in a gradient gradually-increasing state along with the increase of the synthesis time, (leading the concentration of the cobalt of the mixed solution which is in parallel flow to be increased along with the increase of the synthesis time) so as to achieve that the cobalt source with low concentration is provided at the initial stage of synthesis, being beneficial to reducing the generation quantity of cobalt hydroxide crystal nuclei at the initial stage of the synthesis reaction, being beneficial to the growth of cobalt hydroxide, being beneficial to preparing cobalt hydroxide with compact crystals, being provided at the middle and later stages of synthesis as the cobalt sources with gradually-increasing cobalt concentrations, promoting the cobalt hydroxide crystal nuclei, the purpose of controlling the stable growth of cobalt hydroxide is achieved, and the cobalt hydroxide with large particle size of 18-20 mu m is synthesized by a wet method in a short time; after the synthesis is finished, aging, washing, drying and calcining under certain conditions to obtain a cobaltosic oxide product with large granularity; the synthesis reaction of step (b) of the present invention: when the synthesis reaction starts, the adding mode is replaced, the solution A is added into the solution B, the solution A and the solution C which are mixed with the solution A are added into the reaction kettle in parallel flow, and the concentration of the cobalt in the mixed solution which is in parallel flow is reduced gradually along with the extension of the synthesis time, so that the generation quantity of cobalt hydroxide crystal nuclei at the beginning stage of the synthesis reaction is increased, the growth of cobalt hydroxide is inhibited, and the preparation of cobalt hydroxide with compact crystals is facilitated.
2. Carry out the concentration through precision filter, dense thick liquids return and continue to synthesize in the reation kettle, and the mother liquor volume of discharging according to precision filter controls the material volume of adding in the reation kettle, makes the liquid level in the cauldron remain unchanged throughout, through the solid-to-liquid ratio of the interior thick liquids of adjustment synthesis reation kettle, has increased reation kettle's effective volume, has increased single cauldron productivity, has improved equipment utilization rate.
3. According to the invention, the sodium hydroxide solution is used as a precipitator, the ammonia water solution is used as a complexing agent, and the hydrazine hydrate solution is used as a reducing agent to prepare the solution C, so that the control of the flow rate during the parallel flow with the cobalt source is facilitated.
4. After the synthesis is carried out for a period of time, the synthesis slurry is concentrated and the concentrated slurry is returned to the reaction kettle for continuous synthesis, so that the laser granularity D can be synthesized10At 13-16 μm, D50At 18-20 mu m, D90Preparing a cobalt hydroxide product with the particle size of D from 23-26 mu m10At 12-15 μm, D50At 17-19 mu m and D90The tap density is more than or equal to 2.4g/cm at 22-25 mu m3The specific surface area is 1.0-3.0 m2A spherical or spheroidal cobaltosic oxide product per gram.
4. In the process of preparing the cobalt hydroxide with large particle size, the cobalt hydroxide is contacted with air, so that the surface of the cobalt hydroxide is oxidized, the growth of the cobalt hydroxide is not facilitated, and the generated cobalt hydroxide is prevented from being oxidized by adding hydrazine hydrate serving as a reducing agent into a precipitator solution, so that the compact growth of cobalt hydroxide particles is ensured.
Drawings
FIG. 1 is an SEM photograph of a product of example 1;
FIG. 2 is an SEM photograph of a product of example 2;
FIG. 3 is an SEM photograph of a product prepared in example 3;
FIG. 4 is an SEM photograph of a product of example 4;
FIG. 5 is an SEM photograph of a product of example 5;
FIG. 6 is an SEM photograph of a product prepared in example 6.
Detailed Description
The present invention will be described in further detail with reference to specific examples;
example 1
A preparation method of large-particle-size cobaltosic oxide specifically comprises the following steps:
step (a), liquid preparation:
prepared solution A: is 10m3Cobalt nitrate solution with the cobalt concentration of 20 g/L;
preparing a solution B: is 15m3Cobalt nitrate solution with cobalt concentration of 160 g/L;
solution C prepared: taking ammonia water with the concentration of 180g/L, adding 5ml of hydrazine hydrate solution with the mass concentration of 80% into each liter of ammonia water solution, and then mixing the hydrazine hydrate solution with sodium hydroxide solution with the concentration of 200g/L according to the volume ratio of 0.1:1 mixing the components.
Step (b), synthesis reaction:
when the synthesis reaction starts, adding the solution B into the solution A at the flow rate of 300L/h, simultaneously adding A, B solution into a reaction kettle in parallel with the solution C at the flow rate of 500L/h while mixing, performing cobalt hydroxide synthesis under the stirring intensity of 200 r/min, starting a precision filter when the volume of slurry in the reaction kettle reaches 80% of the volume of the reaction kettle, pumping the slurry in the reaction kettle into the precision filter by a pump for concentration, returning the concentrated slurry into the reaction kettle for continuous synthesis, and controlling the liquid level of the added raw materials in the reaction kettle to be 80% by adjusting the amount of the discharged mother liquor. The pH value of the reaction is strictly controlled to be 8.4 in the reaction process, the reaction temperature is 75 ℃, the stirring intensity is 200 r/min, and the reaction time is 50 h.
Step (c), aging, filtering, washing and drying:
and after the A, B solution is completely added into the reaction kettle, closing the precision filter, starting aging, aging for 1h, filtering and washing the synthesized product by using a centrifugal machine, wherein the washing material adopts 80 ℃ deionized water, the drying material equipment is a flash evaporation machine, and the drying temperature is 200 ℃, so that the large-particle-size cobalt hydroxide product is obtained.
Step (d), calcination:
calcining the obtained cobalt hydroxide with large particle size on a rotary kiln at 700 ℃ for 6 h. The large-particle-size cobaltosic oxide product is obtained, part of physicochemical indexes of the product in example 1 are shown in the following table, and the micro-morphology indexes of the prepared product are shown in the figure 1.
TABLE 1 partial physicochemical indices of the product of example 1
Example 2
A preparation method of large-particle-size cobaltosic oxide specifically comprises the following steps:
step (a), liquid preparation:
prepared solution A: 10m3Cobalt sulfate solution with the cobalt concentration of 30 g/L;
preparing a solution B: 15m3Cobalt sulfate solution with cobalt concentration of 150 g/L;
preparing a solution C: taking ammonia water with the concentration of 180g/L, adding 15ml of hydrazine hydrate solution with the mass concentration of 80% into each liter of ammonia water solution, and then mixing the hydrazine hydrate solution with sodium hydroxide solution with the concentration of 250g/L according to the volume ratio of 0.15: 1 mixing the components.
Step (b), synthesis reaction:
when the synthesis reaction starts, adding the solution B into the solution A at the flow rate of 300L/h, simultaneously adding A, B solution into the reaction kettle in parallel with the solution C at the flow rate of 500L/h while mixing, carrying out cobalt hydroxide synthesis under the stirring of 220 r/min, when the volume of the slurry in the reaction kettle reaches 80% of the volume of the reaction kettle, starting a precision filter, pumping the slurry in the reaction kettle into the precision filter by a pump for concentration, returning the concentrated slurry into the reaction kettle for continuous synthesis, and controlling the liquid level of the added materials in the reaction kettle to be kept at 80% of the volume of the reaction kettle according to the amount of the drained mother liquor. The pH value of the reaction is strictly controlled to be 8.6 in the reaction process, the reaction temperature is 78 ℃, the stirring intensity is 220 r/min, and the reaction time is 50 h.
Step (c), aging, filtering, washing and drying:
when the A, B solution was added to the autoclave, the precision filter was closed and aging was initiated. And aging for 1.5h, filtering and washing the synthesized product by using a centrifugal machine, wherein deionized water with the temperature of 85 ℃ is adopted as a washing material, a flash evaporation machine is adopted as a material drying device, and the drying temperature is 250 ℃, so that a large-particle-size cobalt hydroxide product is obtained.
Step (d), calcination:
calcining the obtained cobalt hydroxide with large particle size on a rotary kiln at the temperature of 720 ℃ for 5 h. The large-particle-size cobaltosic oxide product is obtained, part of physicochemical indexes of the product in example 2 are shown in the following table, and the micro-morphology indexes of the prepared product are shown in the figure 2.
TABLE 2 partial physicochemical indices of the product of example 2
Example 3
A preparation method of large-particle-size cobaltosic oxide specifically comprises the following steps:
step (a), liquid preparation:
prepared solution A: is 10m3Cobalt chloride solution with the concentration of 40 g/L;
preparing a solution B: is 15m3Cobalt chloride solution with the cobalt concentration of 140 g/L;
preparing a solution C: taking ammonia water with the concentration of 180g/L, adding 20ml of hydrazine hydrate solution with the mass concentration of 80% into each liter of ammonia water solution, and then mixing the hydrazine hydrate solution with sodium hydroxide solution with the concentration of 300g/L according to the volume ratio of 0.2:1 mixing the components.
Step (b), synthesis reaction:
when the synthesis reaction starts, adding the solution B into the solution A at the flow rate of 300L/h, simultaneously adding A, B solution into the reaction kettle in parallel with the solution C at the flow rate of 500L/h while mixing, carrying out cobalt hydroxide synthesis under the stirring of 250 r/min, when the volume of the slurry in the reaction kettle reaches 85% of the volume of the reaction kettle, starting a precision filter, pumping the slurry in the reaction kettle into the precision filter by a pump for concentration, returning the concentrated slurry into the reaction kettle for continuous synthesis, and controlling the liquid level of the added materials in the reaction kettle to be kept at 85% of the volume of the reaction kettle according to the amount of the drained mother liquor. The pH value of the reaction is strictly controlled to be 8.8 in the reaction process, the reaction temperature is 80 ℃, the stirring intensity is 250 r/min, and the reaction time is 50 h.
Step (c), aging, filtering, washing and drying:
when the A, B solution was added to the autoclave, the precision filter was closed and aging was initiated. And aging for 2h, filtering and washing the synthesized product by using a centrifugal machine, wherein deionized water with the temperature of 90 ℃ is adopted as a washing material, a flash evaporation machine is adopted as a material drying device, and the drying temperature is 300 ℃ to obtain a large-particle-size cobalt hydroxide product.
Step (d), calcination:
calcining the obtained cobalt hydroxide with large particle size on a rotary kiln at the calcining temperature of 750 ℃ for 4 h. The large-particle-size cobaltosic oxide product is obtained, the physicochemical indexes of part of the product in example 3 are shown in the following table, and the microscopic morphology index of the prepared product is shown in figure 3.
TABLE 3 partial materialization index of the product of example 3
Example 4
A preparation method of small-particle-size cobaltosic oxide specifically comprises the following steps:
step (a), liquid preparation:
the prepared solution A is 10m3Cobalt nitrate solution with the cobalt concentration of 20 g/L; the prepared solution B is 10m3Cobalt nitrate solution with cobalt concentration of 160 g/L; the prepared solution C is a mixed solution of a sodium hydroxide solution and an ammonia water solution. Wherein the concentration of the sodium hydroxide solution is 200g/L, the concentration of the ammonia water solution is 180g/L, 10ml of hydrazine hydrate solution with the mass concentration of 80% is added into each liter of the ammonia water solution, and the volume ratio of the ammonia water solution in the solution C to the sodium hydroxide solution is 0.05.
Step (b), synthesis reaction:
when the synthesis reaction starts, adding the solution A into the solution B at the flow rate of 250L/h, simultaneously adding A, B solution into a reaction kettle in parallel with the solution C at the flow rate of 500L/h while mixing, carrying out cobalt hydroxide synthesis under the stirring of 300 r/min, when the volume of the slurry in the reaction kettle reaches 75% of the volume of the reaction kettle, starting a precision filter, pumping the slurry in the reaction kettle into the precision filter by a pump for concentration, returning the concentrated slurry into the reaction kettle for continuous synthesis, and keeping the liquid level of the reaction kettle at 75% of the volume of the reaction kettle by adjusting the amount of the discharged mother liquor. The pH value of the reaction is strictly controlled to be 8.8 in the reaction process, the reaction temperature is 70 ℃, the stirring intensity is 300 r/min, and the reaction time is 40 h.
Step (c), aging, filtering, washing and drying:
when the A, B solution was added to the autoclave, the precision filter was closed and aging was initiated. And aging for 1h, filtering and washing the synthesized product by using a centrifugal machine, wherein the washing material adopts 80 ℃ deionized water, the material drying equipment is a flash evaporation machine, and the drying temperature is 200 ℃ to obtain a small-granularity cobalt hydroxide product.
Step (d), calcination:
calcining the obtained small-particle-size cobalt hydroxide on a rotary kiln at the temperature of 700 ℃ for 6 h. Obtaining the small-granularity cobaltosic oxide product.
TABLE 4 partial materialization index of example 4
The micro-morphology index of the prepared product is shown in figure 4.
Example 5
A preparation method of small-particle-size cobaltosic oxide specifically comprises the following steps:
step (a), liquid preparation:
the prepared solution A is 10m3The cobalt concentration is 30g/L cobalt sulfate solution, and the prepared B solution is 10m3Cobalt sulfate solution with cobalt concentration of 150 g/L. The prepared solution C is a mixed solution of a sodium hydroxide solution and an ammonia water solution, wherein the concentration of the sodium hydroxide solution is 250g/L, the concentration of the ammonia water solution is 180g/L, 15ml of hydrazine hydrate solution with the mass concentration of 80% is added into each liter of the ammonia water solution, and the volume ratio of the ammonia water solution to the sodium hydroxide solution in the solution C is 0.08.
Step (b), synthesis reaction:
when the synthesis reaction starts, adding the solution A into the solution B at the flow rate of 250L/h, simultaneously adding A, B solution into a reaction kettle in parallel with the solution C at the flow rate of 500L/h while mixing, carrying out cobalt hydroxide synthesis under the stirring of 310 r/min, when the volume of the slurry in the reaction kettle reaches 78% of the volume of the reaction kettle, starting a precision filter, pumping the slurry in the reaction kettle into the precision filter by a pump for concentration, returning the concentrated slurry into the reaction kettle for continuous synthesis, and keeping the liquid level of the reaction kettle at 78% of the volume of the reaction kettle by adjusting the amount of the discharged mother liquor. The pH value of the reaction is strictly controlled to be 8.9 in the reaction process, the reaction temperature is 72 ℃, the stirring intensity is 310 r/min, and the reaction time is 40 h.
Step (c), aging, filtering, washing and drying: when the A, B solution was added to the autoclave, the precision filter was closed and aging was initiated. Aging for 1.5h, filtering and washing the synthesized product by a centrifugal machine, wherein deionized water with the temperature of 85 ℃ is adopted as washing materials, a flash evaporation machine is adopted as equipment for drying the materials, and the drying temperature is 250 ℃, so that a small-granularity cobalt hydroxide product is obtained.
Step (d), calcination:
calcining the obtained small-particle-size cobalt hydroxide on a rotary kiln at the temperature of 720 ℃ for 5 h. Obtaining the small-granularity cobaltosic oxide product.
TABLE 5 partial materialization index of example 5
The micro-morphology index of the prepared product is shown in figure 5.
Example 6
A preparation method of small-particle-size cobaltosic oxide specifically comprises the following steps:
step (a), liquid preparation:
the prepared solution A is 10m3Cobalt chloride solution with the concentration of 40 g/L; the prepared solution B is 10m3Cobalt chloride solution with the cobalt concentration of 140 g/L; the prepared solution C is a mixed solution of a sodium hydroxide solution and an ammonia water solution. Wherein the concentration of the sodium hydroxide solution is 300g/L, the concentration of the ammonia water solution is 180g/L, 20ml of hydrazine hydrate solution with the mass concentration of 80 percent is added into each liter of the ammonia water solution, and the ammonia water solution in the solution C and the hydrogen hydroxide solutionThe volume ratio of the sodium solution was 0.1.
Step (b), synthesis reaction:
when the synthesis reaction starts, adding the solution A into the solution B at the flow rate of 250L/h, simultaneously adding A, B solution into a reaction kettle in parallel with the solution C at the flow rate of 500L/h while mixing, carrying out cobalt hydroxide synthesis under the stirring of 320 r/min, when the volume of the slurry in the reaction kettle reaches 80% of the volume of the reaction kettle, starting a precision filter, pumping the slurry in the reaction kettle into the precision filter by a pump for concentration, returning the concentrated slurry into the reaction kettle for continuous synthesis, and keeping the liquid level of the reaction kettle at 80% of the volume of the reaction kettle by adjusting the amount of the discharged mother liquor. The pH value of the reaction is strictly controlled to be 9.0 in the reaction process, the reaction temperature is 75 ℃, the stirring intensity is 320 r/min, and the reaction time is 40 h.
Step (c), aging, filtering, washing and drying:
when the A, B solution was added to the autoclave, the precision filter was closed and aging was initiated. And aging for 2h, filtering and washing the synthesized product by using a centrifugal machine, wherein deionized water with the temperature of 90 ℃ is adopted as a washing material, a flash evaporation machine is adopted as a material drying device, and the drying temperature is 300 ℃ to obtain a small-granularity cobalt hydroxide product.
Step (d), calcination:
calcining the obtained small-particle-size cobalt hydroxide on a rotary kiln at the calcining temperature of 750 ℃ for 4 h. Obtaining the small-granularity cobaltosic oxide product.
TABLE 6 product part materialization index of example 6
The micro-morphology index of the prepared product is shown in figure 6.
Claims (10)
1. A preparation method of cobaltosic oxide is characterized by comprising the following steps: the method specifically comprises the following steps:
step (a), liquid preparation:
preparing a cobalt solution with the cobalt concentration of 20-40 g/L as an A solution and a cobalt solution with the cobalt concentration of 140-160 g/L as a B solution by using cobalt salt as a raw material; the volume ratio of the solution A to the solution B is 1: 1.5;
preparing a solution C: preparing ammonia water with the concentration of 180g/L, adding 5-20 ml of hydrazine hydrate solution with the mass concentration of 80% into each liter of ammonia water, and then mixing the hydrazine hydrate solution with sodium hydroxide solution with the concentration of 200-300 g/L according to the volume ratio of 0.1-0.2: 1;
step (b), synthesis reaction:
adding the solution B into the solution A at a flow rate of 300L/h, adding the solution B and the solution C mixed with the solution B into a reaction kettle at a flow rate of 500L/h in parallel, controlling the pH value of the reaction to be 8.4-8.8, stirring to synthesize cobalt hydroxide, pumping slurry in the reaction kettle into a precision filter to concentrate when the volume of the added material reaches 80-85% of the volume of the reaction kettle, returning the concentrated slurry to the reaction kettle to continue synthesis, and keeping the liquid level in the kettle constant all the time;
step (c), aging:
after the reaction is finished, closing the precision filter, beginning to age, and after the aging is finished, filtering, washing and drying the synthesized product to obtain a large-particle-size cobalt hydroxide product;
step (d), calcination:
calcining the cobalt hydroxide with large particle size obtained in the step (c) to obtain a cobaltosic oxide product with large particle size.
2. A preparation method of cobaltosic oxide is characterized by comprising the following steps: the method specifically comprises the following steps:
step (a), liquid preparation:
preparing a cobalt solution with the cobalt concentration of 20-40 g/L as an A solution and a cobalt solution with the cobalt concentration of 140-160 g/L as a B solution by using cobalt salt as a raw material; the volume ratio of the solution A to the solution B is 1: 1;
preparing a solution C: preparing ammonia water with the concentration of 180g/L, adding 5-20 ml of hydrazine hydrate solution with the mass concentration of 80% into each liter of ammonia water, and then mixing the hydrazine hydrate solution with sodium hydroxide solution with the concentration of 200-300 g/L according to the volume ratio of 0.05-0.1: 1;
step (b), synthesis reaction:
adding the solution A into the solution B at a flow rate of 250L/h, adding the solution A and the solution C mixed with the solution A into a reaction kettle at a flow rate of 500L/h in parallel at the same time, controlling the pH value to be 8.8-9.0, stirring to synthesize cobalt hydroxide, pumping slurry in the reaction kettle into a precision filter to concentrate when the volume of the added material reaches 75-80% of the volume of the reaction kettle, returning the concentrated slurry into the reaction kettle to continue synthesis, and keeping the liquid level in the kettle constant all the time;
step (c), aging:
after the reaction is finished, closing the precision filter, beginning to age, and after the aging is finished, filtering, washing and drying the synthesized product to obtain a small-granularity cobalt hydroxide product;
step (d), calcination:
calcining the small-granularity cobalt hydroxide obtained in the step (c) to obtain a small-granularity cobaltosic oxide product.
3. The method for preparing cobaltosic oxide according to claim 1 or 2, wherein: in the step (a), the cobalt salt is any one of cobalt sulfate, cobalt nitrate or cobalt chloride.
4. The method for preparing cobaltosic oxide according to claim 2, wherein: in the step (b), the reaction temperature is strictly controlled to be 70-75 ℃ in the reaction process, and the stirring intensity is 300-320 revolutions per minute.
5. The method for preparing cobaltosic oxide according to claim 1, wherein: in the step (b), the reaction temperature is strictly controlled to be 75-80 ℃ in the reaction process, and the stirring intensity is 200-250 revolutions per minute.
6. The method for preparing cobaltosic oxide according to claim 4 or 5, wherein: in the step (b), the amount of the materials added into the reaction kettle is controlled according to the amount of the mother liquor discharged by the precision filter, so that the liquid level in the kettle is kept unchanged.
7. The method for preparing cobaltosic oxide according to claim 6, wherein: in the step (c), the aging time is 1-2 h.
8. The method for preparing cobaltosic oxide according to claim 1, 2, 4, 5 or 7, wherein: in the step (c), the washing is carried out by using deionized water at the temperature of 80-90 ℃ for centrifugal washing.
9. The method for preparing cobaltosic oxide according to claim 8, wherein: in the step (c), a flash evaporation machine is adopted for drying, and the drying temperature is 200-300 ℃.
10. The method for preparing cobaltosic oxide according to claim 1 or 9, wherein: in the step (d), the calcination is performed by adopting a rotary kiln, the calcination temperature is 700-750 ℃, and the calcination time is 4-6 h.
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Effective date of registration: 20240204 Address after: 737100 No. 2 Lanzhou Road, Beijing Road Street, Jinchuan District, Jinchang City, Gansu Province Patentee after: Jinchuan Group Nickel Cobalt Co.,Ltd. Country or region after: China Patentee after: LANZHOU JINCHUAN ADVANGCED MATERIALS TECHNOLOGY Co.,Ltd. Address before: 737103 No. 98, Jinchuan Road, Jinchang, Gansu Patentee before: JINCHUAN GROUP Co.,Ltd. Country or region before: China Patentee before: LANZHOU JINCHUAN ADVANGCED MATERIALS TECHNOLOGY Co.,Ltd. |