CN115321605B - Preparation method and application of crystal-transformed aluminum-doped cobalt carbonate - Google Patents
Preparation method and application of crystal-transformed aluminum-doped cobalt carbonate Download PDFInfo
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- 229910021446 cobalt carbonate Inorganic materials 0.000 title claims abstract description 109
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 149
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 149
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 149
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 149
- 229910052751 metal Inorganic materials 0.000 claims abstract description 92
- 239000002184 metal Substances 0.000 claims abstract description 92
- 239000013078 crystal Substances 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 239000007788 liquid Substances 0.000 claims abstract description 66
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001868 cobalt Chemical class 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 39
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims 1
- 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 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 211
- 229910052782 aluminium Inorganic materials 0.000 description 29
- 239000000047 product Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 19
- 230000012010 growth Effects 0.000 description 17
- 239000011164 primary particle Substances 0.000 description 17
- 230000009466 transformation Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- 238000007873 sieving Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000005204 segregation Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000010413 mother solution Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229940118662 aluminum carbonate Drugs 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- -1 hydroxide ions Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect 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
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010900 secondary nucleation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2006/12—Surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of crystal-transformed aluminum-doped cobalt carbonate, which comprises the following steps: (1) Preparing cobalt salt and aluminum salt into mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution; (2) The mixed metal solution and the second ammonium bicarbonate solution are added into the first ammonium bicarbonate solution in parallel flow for mixing reaction, and the reaction temperature is controlled to be 40-45 ℃ until the specific surface area is 0.3-0.6cm 2 A/g of a seed crystal of the crystal-transformed aluminum-doped cobalt carbonate; (3) And (3) adding a mixed metal solution and a third ammonium bicarbonate solution into the solution containing the crystal-doped aluminum cobalt carbonate crystal seeds obtained in the step (2) in parallel flow, mixing and reacting until the granularity of the crystal-doped aluminum cobalt carbonate crystal seeds grows to 16.0-19.0 mu m, carrying out solid-liquid separation, and washing and drying the obtained solid to obtain the crystal-doped aluminum cobalt carbonate. The crystal-converted aluminum-doped cobalt carbonate prepared by the preparation method has a good aluminum-doped effect.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a preparation method and application of crystal-transition aluminum-doped cobalt carbonate.
Background
The lithium cobaltate anode material is mainly applied to the 3C field due to the advantage of high energy density. The high voltage lithium cobaltate may have a higher capacity, but its structure is easily collapsed during the cycle, and in order to improve its cycle performance, a certain amount of aluminum element is typically doped into the tricobalt tetraoxide precursor.
In the preparation process of the aluminum-doped cobalt carbonate, the aluminum can exist in the form of amorphous aluminum carbonate, crystal aluminum hydroxide or crystal basic aluminum ammonium carbonate and other compounds. In order to ensure the uniformity of aluminum doping, the reaction conditions are generally controlled, aluminum is doped in the cobalt carbonate particles in the form of amorphous aluminum carbonate, but the substances are extremely unstable, hydrolysis and recrystallization are easy to occur in the washing and drying processes of the product, so that the aluminum doping effect is poor, the phenomenon of aluminum segregation occurs, and the recycling performance of the aluminum-doped cobalt carbonate is influenced.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a preparation method and application of the crystal-transformed aluminum-doped cobalt carbonate, and the crystal-transformed aluminum-doped cobalt carbonate prepared by the preparation method of the crystal-transformed aluminum-doped cobalt carbonate has a good aluminum-doped effect, so that the aluminum-doped cobalt carbonate is guaranteed to have good cycle performance.
The technical aim of the invention is realized by the following technical scheme:
the preparation method of the crystal-transformed aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing cobalt salt and aluminum salt into mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of the first ammonium bicarbonate solution is 0.8-1.6mol/L, the concentration of the second ammonium bicarbonate solution is 2.5-3.0mol/L, and the concentration of the third ammonium bicarbonate solution is 1.5-2.0mol/L;
(2) The mixed metal solution and the second ammonium bicarbonate solution are added into the first ammonium bicarbonate solution in parallel flow for mixing and reacting, and the reaction temperature is controlled to be 40-45 ℃ until the specific surface area is 0.3-0.6cm 2 A/g of a seed crystal of the crystal-transformed aluminum-doped cobalt carbonate;
(3) And (3) adding the mixed metal solution and the third ammonium bicarbonate solution into the solution containing the crystal-transformed aluminum-doped cobalt carbonate crystal seeds obtained in the step (2) in parallel flow, mixing and reacting until the particle size of the crystal-transformed aluminum-doped cobalt carbonate crystal seeds grows to 16.0-19.0 mu m, performing solid-liquid separation, and washing and drying the obtained solid to obtain the crystal-transformed aluminum-doped cobalt carbonate.
Preferably, in the step (1), the concentration of cobalt ions in the mixed metal solution is 1.5-2.5mol/L, and the molar ratio of aluminum element to cobalt element is 0.001-0.01.
Further preferably, in the step (1), the concentration of cobalt ions in the mixed metal solution is 1.5 to 2.2mol/L, and the molar ratio of aluminum element to cobalt element is 0.005 to 0.01.
Preferably, in the step (1), the cobalt salt is at least one of cobalt sulfate, cobalt nitrate or cobalt chloride.
Preferably, in step (1), the aluminum salt is at least one of aluminum sulfate, aluminum chloride or aluminum nitrate.
Preferably, the reactions in the step (2) and the step (3) are performed in a reaction kettle, in the step (2), the first ammonium bicarbonate solution is added into the reaction kettle as a base solution and heated, the mixed metal solution and the second ammonium bicarbonate solution are added in parallel flow through a liquid adding pipe in a stirring state for reaction, when the liquid level in the reaction kettle reaches a set value, concentration is started, and the specific surface area of the generated seed crystal is monitored until the specific surface area of the seed crystal reaches a target value.
Preferably, in the step (2), the base solution accounts for 20% -30% of the total volume of the reaction kettle, the flow rate of the mixed metal solution is 200-300L/h, the flow rate of the second ammonium bicarbonate solution is 100-150L/h, when the liquid level in the reaction kettle reaches 80% -85% of the total volume of the reaction kettle, the concentration is started, and the mixed metal solution and the second ammonium bicarbonate solution are continuously introduced to stabilize the liquid level in the kettle at 80% -85% of the total volume.
Preferably, the pH of the reaction in step (2) is controlled to 7.0-8.5.
It is further preferred that the pH of the reaction in step (2) is controlled to 7.0-7.5.
Preferably, in the step (3), the mixed metal solution and the third ammonium bicarbonate solution are added in parallel through a liquid adding pipe under the premise of starting concentration, the flow rate of the mixed metal solution is 100-200L/h, the pH value of the reaction is controlled to be 7.8-8.2 by continuously adding the third ammonium bicarbonate solution, the liquid level in the kettle is stabilized to be 80-85% of the total volume, and the sizes of the liquid adding pipes used by the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same. Preferably, in step (3), the reaction temperature is raised to 60-80℃at a rate of 10-30℃per hour.
It is further preferable that in the step (3), the reaction temperature is raised to 65 to 70℃at a temperature raising rate of 20 to 30℃per hour.
Preferably, the number of the liquid adding pipes of the mixed metal solution in the step (3) is greater than the number of the liquid adding pipes of the mixed metal solution in the step (2), and the number of the liquid adding pipes of the third ammonium bicarbonate solution in the step (3) is greater than the number of the liquid adding pipes of the second ammonium bicarbonate solution in the step (2).
Preferably, in the step (2), the number of the liquid adding pipes for mixing the metal solution and the second ammonium bicarbonate solution is one.
Preferably, the obtained material is screened and packaged after being dried in the step (3).
Preferably, the mesh number of the screen is 300-500 mesh, for example 400 mesh.
Preferably, the temperature of the water used for washing in the step (3) is 60-100 ℃ and the washing time is 20-100min.
It is further preferred that the temperature of the water used for the washing in step (3) is 80-100℃and the washing time is 30-60 minutes.
Preferably, the temperature of the drying in the step (3) is 100-150 ℃, and the moisture in the dried material is lower than 5%.
Further preferably, the temperature of the drying in the step (3) is 120-130 ℃, and the moisture in the dried material is lower than 1%.
The application of the crystal-transformed aluminum-doped cobalt carbonate prepared by the preparation method in the preparation of the lithium cobalt oxide anode material.
The beneficial effects of the invention are as follows:
(1) The invention keeps the lower temperature of 40-45 ℃ during the synthesis of the seed crystal, can slow down the precipitation speed of aluminumThe aluminum is doped in the cobalt carbonate in the form of amorphous aluminum carbonate, which is favorable for the uniform distribution of the aluminum; at the same time by preparing 0.3-0.6cm 2 The aluminum-doped cobalt carbonate particles with low specific surface area are used as crystal-transferred cobalt carbonate seed crystals, the surfaces of the aluminum-doped cobalt carbonate particles have rich surface defects, the mountain-shaped primary particles are more prominent, the gaps among the primary particles are larger, sufficient growth sites are provided for secondary nucleation of the flaky crystal-form cobalt carbonate, the flaky crystal-form firstly stably grows in the gaps and gradually covers the whole particle surfaces, and the purpose of cobalt carbonate crystal transfer is achieved; if the specific surface area of the seed crystal is larger, the defects on the surface of the particles are fewer, the mountain-shaped primary particles are densely arranged, gaps among the primary particles are smaller, the surface of the particles is smoother, the flaky crystal forms are difficult to stably grow, and newly generated cobalt carbonate crystal grains tend to grow on the original mountain-shaped primary particles, so that the aim of completely converting the cobalt carbonate crystal forms is difficult to achieve.
(2) According to the invention, a single metal liquid adding pipe and a single ammonium bicarbonate solution liquid adding pipe are used in the seed crystal preparation period, so that the supersaturation degree at the feeding moment can be increased, and more crystal nuclei can be generated; the quantity of the liquid adding pipes of the metal liquid and the ammonium bicarbonate solution is increased in the cobalt carbonate crystal form conversion and growth process, the supersaturation degree in the feeding moment can be reduced under the condition that the total quantity of the liquid is unchanged, the generation of small particles is avoided, and meanwhile, the decomposition of the ammonium bicarbonate solution can be accelerated.
(3) According to the invention, aluminum is doped in the cobalt carbonate in the form of amorphous aluminum carbonate during the synthesis of the seed crystal, and the higher synthesis temperature, the faster heating rate, the lower ammonium bicarbonate solution concentration and the plurality of ammonium bicarbonate solution charging pipes are used in the stage of the transformation and growth of the cobalt carbonate crystal form, so that ammonium bicarbonate is decomposed into more hydroxide ions, the concentration of the hydroxide ions in a reaction system is rapidly increased, the concentration of the carbonate ions is reduced, the concentration of each ion in the synthesis system is mutated, enough driving force is provided for crystal transformation, the newly generated aluminum-doped cobalt carbonate crystal form is transformed, and the transformed flaky crystal forms of basic cobalt aluminum carbonate are stacked and grown on the seed crystal with rich surface defects; if the temperature rising speed is slower and the temperature is not raised to a certain range or the cobalt carbonate crystal form is regulated and controlled during the transformationThe concentration of ammonium bicarbonate is higher, namely the concentration of carbonate ions in the system is higher, so that basic cobalt aluminum carbonate is difficult to generate, and obvious crystal form mutation can not occur; the components of the basic cobalt aluminum carbonate phase can be further increased by maintaining a higher reaction pH value, so that the purpose of complete crystal transformation of aluminum-doped cobalt carbonate is achieved, and the crystal transformation process is irreversible; from the chemical formula: 6CoCl 2 +Al 2 (SO 4 ) 3 +20H 2 O+18NH 4 HCO 3 ＝Co 6 Al 2 CO 3 (OH) 16 ·4H 2 O↓+3(NH 4 ) 2 SO 4 +12NH 4 Cl+17H 2 CO 3 The basic cobalt aluminum carbonate can be used for stably coprecipitating aluminum ions and cobalt ions, aluminum is more easily doped in crystal lattices of cobalt carbonate, uniformity of aluminum distribution can be improved, the crystallization product is more stable, subsequent lithium intercalation is facilitated, good cycle performance of a battery is guaranteed, meanwhile, the reaction rate can be accelerated through synthesis at a high temperature, the precipitation rate of cobalt is improved, the cobalt content in mother liquor is stabilized below 50ppm, and wastewater treatment cost is saved.
Drawings
FIG. 1 is an SEM image of a transcrystalline aluminum-doped cobalt carbonate seed crystal according to example 1 of the present invention;
FIG. 2 is an SEM image of a finished product of the transcrystalline aluminum-doped cobalt carbonate according to example 1 of the present invention;
FIG. 3 is an XRD pattern of a finished product of the transcrystalline aluminum-doped cobalt carbonate according to example 1 of the present invention;
FIG. 4 is an SEM image of a transcrystalline aluminum-doped cobalt carbonate seed crystal according to example 2 of the present invention;
FIG. 5 is an SEM image of a finished product of the transcrystalline aluminum-doped cobalt carbonate according to example 2 of the present invention;
FIG. 6 is an SEM image of a finished product of the transcrystalline aluminum-doped cobalt carbonate according to example 3 of the present invention;
FIG. 7 is an SEM image of the finished cobalt of the inventive comparative example 1 aluminum-doped carbonic acid;
FIG. 8 is an SEM image of a comparative example 2 of an aluminum-doped cobalt carbonate seed crystal according to the present invention;
FIG. 9 is an SEM image of a finished product of comparative example 2 of aluminum-doped cobalt carbonate;
FIG. 10 is an SEM image of a finished product of comparative example 3 of aluminum-doped cobalt carbonate;
fig. 11 is an SEM image of the finished product of comparative example 4 aluminum-doped cobalt carbonate of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1:
the preparation method of the crystal-transformed aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing a solution: preparing cobalt chloride and aluminum chloride into a mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of cobalt in the mixed metal solution is 2.0mol/L, the molar ratio of aluminum to cobalt is 0.01, the concentration of the first ammonium bicarbonate solution is 1.0mol/L, the concentration of the second ammonium bicarbonate solution is 3mol/L, and the concentration of the third ammonium bicarbonate solution is 2mol/L;
(2) Synthesizing crystal-transferred cobalt carbonate seed crystal: adding a first ammonium bicarbonate solution serving as a base solution into a reaction kettle, wherein the volume of the first ammonium bicarbonate solution accounts for 30% of the total volume of the reaction kettle, the pH value of the base solution is 8.3, heating to 45 ℃, and adding a mixed metal solution and a second ammonium bicarbonate solution in parallel under the condition of high-speed stirring; wherein the mixed metal solution and the second ammonium bicarbonate solution are both single liquid adding pipes and are fed simultaneously, the flow rate of the mixed metal solution is 300L/h, the flow rate of the second ammonium bicarbonate solution is 150L/h, when the pH value is reduced to 7.50, the flow rate of the second ammonium bicarbonate solution is regulated by a PLC control system to stabilize the pH value to be constant to 7.50, when the liquid level in the reaction kettle reaches 83% of the total volume, the concentration is started, the mixed metal solution and the second ammonium bicarbonate solution are continuously fed in the concentration period and keep the liquid level in the kettle stable to be 83% of the total volume, and when the BET measured by a seed crystal sample is 0.35cm 2 At the time of/g, completing synthesis of the crystal-transformed aluminum-doped cobalt carbonate crystal seeds, wherein an SEM image of the obtained crystal-transformed aluminum-doped cobalt carbonate crystal seeds is shown as a figure 1, D50 is measured to be 8.6 mu m, and meanwhile, according to the figure 1, primary particles are in a block shape and have no aluminum segregation;
(3) Cobalt carbonate crystal form transformation and growth: the reaction temperature is raised to 65 ℃, the heating speed of the reaction kettle is controlled at 20 ℃/h, the mixed metal solution and the third ammonium bicarbonate solution are added in parallel flow, and concentration is started, wherein the mixed metal solution and the third ammonium bicarbonate solution are all three liquid adding pipes for simultaneously feeding liquid, the sizes of the liquid adding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 200L/h, the third ammonium bicarbonate solution is regulated by a PLC control system, the pH value of the seed crystal growth stage is kept at 8.0, the mixed metal solution and the third ammonium bicarbonate solution are continuously fed in the kettle during concentration and keep the liquid level in the kettle at 83% of the total volume, the cobalt ion concentration in the mother solution is 40mg/L during the reaction, and the grain size is grown to 16.7 mu m, so as to obtain the crystal-doped aluminum cobalt carbonate slurry;
(4) Washing, drying and sieving the crystal-transformation aluminum-doped cobalt carbonate: filtering slurry in a reaction kettle by a centrifugal machine, washing for 40min by hot pure water at 85 ℃, taking a filter cake, drying at 110 ℃ until the water content is 0.1%, sieving by a 400-mesh vibrating screen, packaging to obtain a finished product of the crystal-doped aluminum cobalt carbonate, wherein an SEM (X-ray diffraction) diagram of the finished product of the crystal-doped aluminum cobalt carbonate is shown in figure 2, an XRD (X-ray diffraction) diagram of the finished product of the crystal-doped aluminum cobalt carbonate is shown in figure 3, D50 is 16.7 mu m, the content of aluminum element is 4820ppm, primary particles are flaky and have no aluminum segregation, and the finished product of the crystal-doped aluminum cobalt carbonate is a mixture of cobalt carbonate and basic cobalt aluminum carbonate as shown in figure 3.
Example 2:
the preparation method of the crystal-transformed aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing a solution: preparing cobalt sulfate and aluminum sulfate into a mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of cobalt in the mixed metal solution is 2.2mol/L, the molar ratio of aluminum to cobalt is 0.008, the concentration of the first ammonium bicarbonate solution is 0.8mol/L, the concentration of the second ammonium bicarbonate solution is 2.8mol/L, and the concentration of the third ammonium bicarbonate solution is 1.7mol/L;
(2) Synthesizing crystal-transferred cobalt carbonate seed crystal: adding a first ammonium bicarbonate solution serving as a base solution into a reaction kettle, wherein the volume of the first ammonium bicarbonate solution accounts for 40% of the total volume of the reaction kettle, the pH value of the base solution is 7.5, heating to 43 ℃, and adding a mixed metal solution and a second ammonium bicarbonate solution in parallel under the condition of high-speed stirring; wherein the metal solution is mixedThe second ammonium bicarbonate solution is a single liquid adding pipe and is fed simultaneously, the flow rate of the mixed metal solution is 250L/h, the flow rate of the second ammonium bicarbonate solution is 120L/h, when the pH value is reduced to 7.40, the flow rate of the second ammonium bicarbonate solution is regulated by a PLC control system to stabilize the pH value to 7.40, when the liquid level in the reaction kettle is opened and concentrated to 80% of the total volume, the mixed metal solution and the ammonium bicarbonate A solution are continuously fed in the concentration period and keep the liquid level in the kettle stable to 80% of the total volume, and when the BET measured by a seed crystal sample is 0.41cm 2 At/g, the synthesis of the crystal-transformed aluminum-doped cobalt carbonate seed crystal is completed, the SEM diagram of the obtained crystal-transformed aluminum-doped cobalt carbonate seed crystal is shown in figure 4, the measured D50 is 10.5 mu m, and as can be seen from figure 4, the primary particles are in a block shape and have no aluminum segregation;
(3) Cobalt carbonate crystal form transformation and growth: the reaction temperature is raised to 67 ℃, the heating speed of a reaction kettle is controlled at 24 ℃/h, a mixed metal solution and a third ammonium bicarbonate solution are added in parallel flow, and concentration is started, wherein the mixed metal solution and the third ammonium bicarbonate solution are respectively four liquid adding pipes for simultaneously feeding liquid, the sizes of the liquid adding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 250L/h, the flow rate of the third ammonium bicarbonate solution is regulated by a PLC control system, the pH value of a seed crystal in a growth stage is kept at 8.2, the mixed metal solution and the third ammonium bicarbonate solution are continuously fed in the kettle during concentration, the liquid level in the kettle is kept at 80% of the total volume, the cobalt ion concentration in a mother solution is 20mg/L during the reaction, and when the particle size grows to 18.8 mu m, the crystal-converted aluminum-doped cobalt carbonate slurry is obtained;
(4) Washing, drying and sieving the crystal-transformation aluminum-doped cobalt carbonate: filtering the slurry in the reaction kettle by a centrifugal machine, washing for 30min by hot pure water at 90 ℃, taking a filter cake, drying at 120 ℃ until the water content is 0.28%, sieving by a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein an SEM (scanning electron microscope) diagram of the obtained crystal-doped cobalt carbonate finished product is shown in figure 5, D50 is 18.8 mu m, the content of aluminum element is 3693ppm, and as can be seen from figure 5, primary particles are sheet-shaped and have no aluminum segregation.
Example 3:
the preparation method of the crystal-transformed aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing a solution: preparing cobalt nitrate and aluminum nitrate into a mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of cobalt in the mixed metal solution is 1.5mol/L, the molar ratio of aluminum to cobalt is 0.005, the concentration of the first ammonium bicarbonate solution is 1.6mol/L, the concentration of the second ammonium bicarbonate solution is 2.5mol/L, and the concentration of the third ammonium bicarbonate solution is 1.5mol/L;
(2) Synthesizing crystal-transferred cobalt carbonate seed crystal: adding a first ammonium bicarbonate solution serving as a base solution into a reaction kettle, wherein the volume of the first ammonium bicarbonate solution accounts for 35 percent of the total volume of the reaction kettle, the pH value of the base solution is 8.5, heating to 40 ℃, and adding a mixed metal solution and a second ammonium bicarbonate solution in parallel under the condition of high-speed stirring; wherein the mixed metal solution and the second ammonium bicarbonate solution are both single liquid adding pipes and are fed simultaneously, the flow rate of the mixed metal solution is 200L/h, the flow rate of the second ammonium bicarbonate solution is 100L/h, when the pH value is reduced to 7.60, the flow rate of the second ammonium bicarbonate solution is regulated by a PLC control system to stabilize the pH value to be constant to 7.60, when the liquid level in the reaction kettle is 85% of the total volume, the concentration is started, the mixed metal solution and the second ammonium bicarbonate solution are continuously fed in the concentration period and keep the liquid level in the kettle stable to be 85% of the total volume, and when the BET measured by a seed crystal sample is 0.56cm 2 At the time of/g, completing the synthesis of crystal-transition aluminum-doped cobalt carbonate crystal seeds, wherein D50 is 12.5 mu m, primary particles are in a block shape, and no aluminum segregation is generated;
(3) Cobalt carbonate crystal form transformation and growth: the reaction temperature is raised to 70 ℃, the heating speed of a reaction kettle is controlled to be 30 ℃/h, a mixed metal solution and a third ammonium bicarbonate solution are added in parallel flow, and concentration is started, wherein the mixed metal solution and the third ammonium bicarbonate solution are both two liquid adding pipes for simultaneously feeding liquid, the sizes of the liquid adding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 100L/h, the flow rate of the third ammonium bicarbonate solution is regulated by a PLC control system, the pH value of a seed crystal growing stage is made to be constant at 7.8, the mixed metal solution and the third ammonium bicarbonate solution are continuously fed in the concentration period, the liquid level in the kettle is kept to be constant at 85% of the total volume, the cobalt ion concentration in a mother solution is 50mg/L in the reaction process, and when the particle size grows to 17.5 mu m, the crystal-doped aluminum cobalt carbonate slurry is obtained;
(4) Washing, drying and sieving the crystal-transformation aluminum-doped cobalt carbonate: filtering the slurry in the reaction kettle by a centrifugal machine, washing for 600min by hot pure water at 95 ℃, taking a filter cake, drying at 110 ℃ until the water content is 0.82%, sieving by a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein an SEM (scanning electron microscope) diagram of the obtained crystal-doped aluminum-doped cobalt carbonate finished product is shown in figure 6, D50 is 17.5 mu m, the content of aluminum element is 2420ppm, and as can be seen from figure 6, primary particles are sheet-shaped and have no aluminum segregation.
Comparative example 1:
the preparation method of the aluminum-doped cobalt carbonate comprises the following steps:
(1) The same as in step (1) of example 1;
(2) Synthesizing aluminum-doped cobalt carbonate seed crystals: the same as in step (2) of example 1;
(3) Growth of aluminum-doped cobalt carbonate: the reaction temperature is controlled to be unchanged at 45 ℃, the same as the seed crystal temperature, a mixed metal solution and a third ammonium bicarbonate solution are added in parallel flow, and concentration is started, wherein the mixed metal solution and the third ammonium bicarbonate solution are all three liquid adding pipes for simultaneously feeding liquid, the sizes of the liquid adding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, wherein the flow rate of the mixed metal solution is 200L/h, the third ammonium bicarbonate solution is regulated by a PLC control system, the pH value of the seed crystal in the growth stage is kept to be 7.50, the pH value of the mixed metal solution is the same as the pH value of the seed crystal in the reaction control, the mixed metal solution and the third ammonium bicarbonate solution are continuously fed in the kettle during concentration, the liquid level in the kettle is kept to be 83% of the total volume, the cobalt ion concentration in the mother solution is 150mg/L in the reaction process, and when the particle size grows to 16.6 mu m, the aluminum-doped cobalt carbonate slurry is obtained;
(4) Washing, drying and sieving aluminum-doped cobalt carbonate: filtering the slurry in the reaction kettle by a centrifugal machine, washing for 40min by hot pure water at 85 ℃, taking a filter cake, drying at 110 ℃ until the water content is 0.21%, sieving by a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein an SEM (scanning electron microscope) diagram of the aluminum-doped cobalt carbonate finished product is shown as figure 7, D50 is 16.6 mu m, the content of aluminum element is 4758ppm, as can be seen from figure 7, primary particles are in a block shape, no crystal transformation occurs, and aluminum sheets are separated out on the surface.
Comparative example 2:
the preparation method of the aluminum-doped cobalt carbonate comprises the following steps:
(1) The same as in step (1) of example 1;
(2) Synthesizing aluminum-doped cobalt carbonate seed crystals: adding a first ammonium bicarbonate solution serving as a base solution into a reaction kettle, wherein the volume of the first ammonium bicarbonate solution accounts for 30% of the total volume of the reaction kettle, the pH value of the base solution is 8.3, heating to 43 ℃, and adding a mixed metal solution and a second ammonium bicarbonate solution in parallel under the condition of high-speed stirring; wherein the mixed metal solution and the second ammonium bicarbonate solution are both single liquid adding pipes and are fed simultaneously, the flow rate of the mixed metal solution is 300L/h, the flow rate of the second ammonium bicarbonate solution is 150L/h, when the pH value is reduced to 7.50, the flow rate of the second ammonium bicarbonate solution is regulated by a PLC control system to stabilize the pH value to be constant to 7.50, when the liquid level in the reaction kettle reaches 83% of the total volume, the concentration is started, the mixed metal solution and the second ammonium bicarbonate solution are continuously fed in the concentration period and keep the liquid level in the kettle stable to be 83% of the total volume, and when the BET measured by a seed crystal sample is 5.2cm 2 At/g, completing synthesis of aluminum-doped cobalt carbonate seed crystal, wherein an SEM image of the obtained aluminum-doped cobalt carbonate seed crystal is shown in FIG. 8, and D50 is 6.2 μm, and as can be seen from FIG. 8, primary particles are small blocks and have no obvious aluminum segregation;
(3) Growth of aluminum-doped cobalt carbonate: the same as in step (3) of example 1;
(4) Washing, drying and sieving aluminum-doped cobalt carbonate: filtering the slurry in the reaction kettle by a centrifugal machine, washing for 40min by hot pure water at 85 ℃, taking a filter cake, drying at 110 ℃ until the water content is 0.15%, sieving by a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein an SEM (scanning electron microscope) diagram of the aluminum-doped cobalt carbonate finished product is shown as figure 9, D50 is 16.5 mu m, the aluminum element content is 4810ppm, and as can be seen from figure 9, primary particles are large blocks and have obvious aluminum segregation.
Comparative example 3:
the preparation method of the aluminum-doped cobalt carbonate comprises the following steps:
(1) The same as in step (1) of example 1;
(2) The same as in step (2) of example 1;
(3) Growth of aluminum-doped cobalt carbonate: the reaction temperature is increased to 50 ℃, the heating speed is controlled to be 5 ℃/h, the mixed metal solution and the third ammonium bicarbonate solution are added in parallel flow, and concentration is started, wherein the mixed metal solution and the third ammonium bicarbonate solution are all three liquid adding pipes for simultaneously feeding liquid, the sizes of the liquid adding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 200L/h, the third ammonium bicarbonate solution is regulated by a PLC control system, the pH value of the seed crystal growth stage is kept to be 8.0, the mixed metal solution and the third ammonium bicarbonate solution are continuously fed in and kept in the kettle to keep the liquid level in the kettle to be 83% of the total volume during concentration, the cobalt ion concentration in the mother solution is 150mg/L during the reaction, and when the granularity grows to 16.7 mu m, the aluminum-doped cobalt carbonate slurry is obtained;
(4) Washing, drying and sieving aluminum-doped cobalt carbonate: filtering the slurry in the reaction kettle by a centrifugal machine, washing for 40min by hot pure water at 85 ℃, taking a filter cake, drying at 120 ℃ until the water content is 0.28%, sieving by a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein an SEM (scanning electron microscope) diagram of the aluminum-doped cobalt carbonate finished product is shown as figure 10, D50 is 16.9 mu m, the aluminum element content is 4729ppm, and as can be seen from figure 10, primary particles are in a mixed crystal form of a block shape and a sheet shape, and obvious aluminum segregation is cut on the surfaces of the particles.
Comparative example 4:
the preparation method of the aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing a solution: preparing cobalt chloride and aluminum chloride into a mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of cobalt in the mixed metal solution is 2.0mol/L, the molar ratio of aluminum to cobalt is 0.01, the concentration of the first ammonium bicarbonate solution is 1.0mol/L, and the concentrations of the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are 3mol/L;
(2) Synthesizing crystal-transferred cobalt carbonate seed crystal: adding a first ammonium bicarbonate solution as a base solution into a reaction kettle, wherein the volume of the first ammonium bicarbonate solution is 30 percent of the total volume of the reaction kettle, the pH value of the base solution is 8.3, heating to 45 ℃, and adding a mixed metal solution and the mixed metal solution in parallel under the condition of high-speed stirringA second ammonium bicarbonate solution; wherein the mixed metal solution and the second ammonium bicarbonate solution are both single liquid adding pipes and are fed simultaneously, the flow rate of the mixed metal solution is 300L/h, the flow rate of the second ammonium bicarbonate solution is 150L/h, when the pH value is reduced to 7.50, the flow rate of the second ammonium bicarbonate solution is regulated by a PLC control system to stabilize the pH value to be constant to 7.50, when the liquid level in the reaction kettle reaches 83% of the total volume, the concentration is started, the mixed metal solution and the second ammonium bicarbonate solution are continuously fed in the concentration period and keep the liquid level in the kettle stable to be 83% of the total volume, and when the BET measured by a seed crystal sample is 0.30cm 2 And/g, completing synthesis of crystal-transformed aluminum-doped cobalt carbonate crystal seeds;
(3) Cobalt carbonate crystal form transformation and growth: the reaction temperature is raised to 65 ℃, the heating speed of the reaction kettle is controlled at 20 ℃/h, the mixed metal solution and the third ammonium bicarbonate solution are added in parallel flow, and concentration is started, wherein the mixed metal solution and the third ammonium bicarbonate solution are fed into a single feeding pipe at the same time, the sizes of the feeding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, wherein the flow rate of the mixed metal solution is 200L/h, the third ammonium bicarbonate solution is regulated by a PLC control system, the pH value of the seed crystal growth stage is kept at 8.0, the mixed metal solution and the third ammonium bicarbonate solution are continuously fed into the kettle during concentration, the liquid level in the kettle is kept at 83% of the total volume, the cobalt ion concentration in the mother solution is 40mg/L during the reaction, and when the granularity grows to 16.7 mu m, the aluminum-doped cobalt carbonate slurry is obtained;
(4) Washing, drying and sieving the crystal-transformation aluminum-doped cobalt carbonate: filtering the slurry in the reaction kettle by a centrifugal machine, washing for 40min by hot pure water at 85 ℃, taking a filter cake, drying at 110 ℃ until the water content is 0.5%, sieving by a 400-mesh vibrating screen, and packaging to obtain a crystal-doped aluminum-doped cobalt carbonate finished product, wherein an SEM (scanning electron microscope) diagram of the obtained aluminum-doped cobalt carbonate finished product is shown as figure 11, D50 is 16.7 mu m, the content of aluminum element is 4810ppm, and as can be seen from figure 11, primary particles are in a block shape, crystal transformation does not occur, and aluminum segregation is cut on the surfaces of the particles.
It can be obtained from comparative examples 1 and 1 that the basic cobalt aluminum carbonate with flaky morphology formed after crystal transformation not only ensures the uniformity of aluminum distribution in the synthesis process, but also avoids precipitation of aluminum sheets in the post-treatment process of finished products due to the structural stability; as can be seen from comparative examples 1 and 2, the seed crystals having a large specific surface area cannot undergo seeding under the growth conditions of high temperature and high pH, and the primary particles still inherit the bulk morphology of the seed crystals and become coarse as the particles grow; as can be seen from comparative examples 1 and 3, in the phase of transformation and growth of cobalt carbonate crystal form, the slower heating rate and lower temperature lead to incomplete grain transformation, coarse and flaky attachment of primary grains and poor consistency of the surface of the grains; as can be seen from comparative examples 1 and 4, the same ammonium bicarbonate concentration and single feed line feed during the transformation and growth phase of the aluminum-doped cobalt carbonate crystals as during the seed crystal preparation phase still maintained the carbonate ion concentration in the mother liquor at a higher value and no grain transformation occurred.
The cobalt carbonate precursors prepared in examples 1 to 3 and comparative examples 1 to 4 were calcined in a box furnace at 700 ℃ for 4 hours, and then prepared into batteries according to the same conditions for electrochemical testing, in the following general method: the lithium cobaltate material prepared by mixing and sintering the precursor and lithium carbonate according to a certain proportion is used as an anode, graphite is used as a cathode, lithium hexafluorophosphate is used as electrolyte to prepare a button cell, the electrochemical test voltage is 4.55V, 1C high-temperature cycle test is carried out, the temperature is 45 ℃, and the test results are shown in the following table 1:
table 1: battery cycle performance test:
| project | Cycle retention of 50 weeks | 80-week cycle retention rate |
| Example 1 | 92.5％ | 83.1％ |
| Example 2 | 91.8％ | 82.7％ |
| Example 3 | 90.6％ | 81.5％ |
| Comparative example 1 | 85.1％ | 72.5％ |
| Comparative example 2 | 82.5％ | 73.6％ |
| Comparative example 3 | 82.4％ | 70.8％ |
| Comparative example 4 | 84.6％ | 71.3％ |
As can be seen from the data in table 1, the aluminum-doped precursor after crystal transformation prepared in each example is more favorable for lithium intercalation after preparing lithium cobaltate, has excellent cycle performance, the 50-cycle retention rate can reach more than 90.6%, the 80-cycle retention rate can reach more than 81.5%, and the aluminum-doped precursor without crystal transformation prepared in the comparative example has poor high-temperature cycle performance of lithium cobaltate material due to non-uniform aluminum distribution.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. A preparation method of crystal-transformed aluminum-doped cobalt carbonate is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing cobalt salt and aluminum salt into mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of the first ammonium bicarbonate solution is 0.8-1.6mol/L, the concentration of the second ammonium bicarbonate solution is 2.5-3.0mol/L, and the concentration of the third ammonium bicarbonate solution is 1.5-2.0mol/L;
(2) The mixed metal solution and the second ammonium bicarbonate solution are added into the first ammonium bicarbonate solution in parallel flow for mixing and reacting, and the reaction temperature is controlled to be 40-45 ℃ until the crystal-transformation aluminum-doped cobalt carbonate seed crystal with the specific surface area of 0.3-0.6cm < 2 >/g is generated;
(3) Adding the mixed metal solution and the third ammonium bicarbonate solution into the solution containing the crystal-transformed aluminum-doped cobalt carbonate seed crystal obtained in the step (2) in parallel flow, mixing and reacting until the granularity of the crystal-transformed aluminum-doped cobalt carbonate seed crystal grows to 16.0-19.0 mu m, performing solid-liquid separation, and washing and drying the obtained solid to obtain the crystal-transformed aluminum-doped cobalt carbonate; in the step (1), the concentration of cobalt ions in the mixed metal solution is 1.5-2.5mol/L, and the molar ratio of aluminum element to cobalt element is 0.001-0.01; the reaction of the step (2) and the step (3) is carried out in a reaction kettle, in the step (2), the first ammonium bicarbonate solution is firstly added into the reaction kettle as base solution and heated, the mixed metal solution and the second ammonium bicarbonate solution are added in parallel flow through a liquid adding pipe under a stirring state for reaction, when the liquid level in the reaction kettle reaches a set value, concentration is started, and the specific surface area of the generated seed crystal is monitored until the specific surface area of the seed crystal reaches a target value; in the step (3), the reaction temperature is raised to 60-80 ℃ at a heating rate of 10-30 ℃/h, the number of the liquid adding pipes of the mixed metal solution in the step (3) is more than that of the mixed metal solution in the step (2), and the number of the liquid adding pipes of the third ammonium bicarbonate solution in the step (3) is more than that of the second ammonium bicarbonate solution in the step (2).
2. The method for preparing the crystal-converted aluminum-doped cobalt carbonate according to claim 1, which is characterized in that: in the step (2), the bottom solution accounts for 20% -30% of the total volume of the reaction kettle, the flow rate of the mixed metal solution is 200-300L/h, the flow rate of the second ammonium bicarbonate solution is 100-150L/h, when the liquid level in the reaction kettle reaches 80% -85% of the total volume of the reaction kettle, the concentration is started, and the mixed metal solution and the second ammonium bicarbonate solution are continuously introduced to enable the liquid level in the kettle to be stabilized at 80% -85% of the total volume.
3. The method for preparing the crystal-converted aluminum-doped cobalt carbonate according to claim 1, which is characterized in that: the pH of the reaction in the step (2) is controlled to 7.0-8.5.
4. The method for preparing the crystal-converted aluminum-doped cobalt carbonate according to claim 1, which is characterized in that: in the step (3), on the premise of starting concentration, the mixed metal solution and the third ammonium bicarbonate solution are added in parallel through a liquid adding pipe, the flow rate of the mixed metal solution is 100-200L/h, the pH value of the reaction is controlled to be 7.8-8.2 by continuously adding the third ammonium bicarbonate solution, the liquid level in the kettle is stabilized to be 80-85% of the total volume, and the sizes of the liquid adding pipes used by the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same.
5. The method for preparing the crystal-converted aluminum-doped cobalt carbonate according to claim 1, which is characterized in that: in the step (2), the number of the liquid adding pipes for the mixed metal solution and the second ammonium bicarbonate solution is one.
6. Use of the transcrystalline aluminum-doped cobalt carbonate prepared by the preparation method according to any one of claims 1 to 5 for preparing lithium cobaltate cathode materials.
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| CN113636604A (en) * | 2021-08-30 | 2021-11-12 | 衢州华友钴新材料有限公司 | Preparation method of high-aluminum-doped small-particle-size cobalt carbonate particles |
| CN113816435A (en) * | 2021-08-27 | 2021-12-21 | 广东邦普循环科技有限公司 | Crystal transition precursor and preparation method thereof |
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- 2023-06-29 FR FR2306846A patent/FR3138913A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113830839A (en) * | 2021-08-18 | 2021-12-24 | 广东邦普循环科技有限公司 | Preparation method and application of flaky aluminum-doped cobalt carbonate |
| CN113816435A (en) * | 2021-08-27 | 2021-12-21 | 广东邦普循环科技有限公司 | Crystal transition precursor and preparation method thereof |
| CN113636604A (en) * | 2021-08-30 | 2021-11-12 | 衢州华友钴新材料有限公司 | Preparation method of high-aluminum-doped small-particle-size cobalt carbonate particles |
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| WO2024040901A1 (en) | 2024-02-29 |
| CN115321605A (en) | 2022-11-11 |
| FR3138913A1 (en) | 2024-02-23 |
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