WO2024060557A1 - Carbonate de cobalt dopé à l'aluminium et sa méthode de préparation - Google Patents

Carbonate de cobalt dopé à l'aluminium et sa méthode de préparation Download PDF

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WO2024060557A1
WO2024060557A1 PCT/CN2023/083440 CN2023083440W WO2024060557A1 WO 2024060557 A1 WO2024060557 A1 WO 2024060557A1 CN 2023083440 W CN2023083440 W CN 2023083440W WO 2024060557 A1 WO2024060557 A1 WO 2024060557A1
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aluminum
cobalt carbonate
doped cobalt
molten metal
liquid
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PCT/CN2023/083440
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English (en)
Chinese (zh)
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周思源
李长东
阮丁山
刘更好
卢星华
胡海涵
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024060557A1 publication Critical patent/WO2024060557A1/fr

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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
    • C01G51/06—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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

Definitions

  • the invention belongs to the technical field of battery materials, and particularly relates to aluminum-doped cobalt carbonate and a preparation method thereof.
  • Lithium cobalt oxide lithium-ion batteries can release higher capacity at high voltages and have unique advantages in energy density.
  • lithium cobalt oxide has the problem of unstable bulk structure under high voltage.
  • Doping with aluminum can stabilize the layered structure with oxygen as the skeleton and improve the structural stability.
  • Cobalt tetroxide is the precursor of lithium cobalt oxide, and its performance is largely determined by the performance of cobalt carbonate. With the increase of aluminum doping, how to achieve uniform distribution of aluminum in cobalt carbonate has become a challenge to be tackled.
  • the present invention aims to solve at least one of the technical problems existing in the prior art.
  • the present invention proposes an aluminum-doped cobalt carbonate and a preparation method thereof.
  • the aluminum-doped cobalt carbonate prepared by the preparation method has a uniform size, few small particles, and a uniform distribution of aluminum elements.
  • a preparation method of aluminum-doped cobalt carbonate including the following steps:
  • Liquid preparation Dissolve soluble cobalt salt, soluble aluminum salt and dispersant in water to obtain molten metal A. Dissolve soluble cobalt salt and soluble aluminum salt in water to obtain molten metal B. Prepare bicarbonate as the bottom liquid. , prepare carbonate as precipitating agent;
  • Reaction I Add the molten metal A and the precipitant into the bottom liquid in parallel flow and react to generate a mixed system containing aluminum-doped cobalt carbonate crystals;
  • Reaction II When the D50 of the aluminum-doped cobalt carbonate crystal generated in step (2) grows to 14-15 ⁇ m, stop adding the molten metal A to the mixed system, and simultaneously add the molten metal B and The precipitant is added to the mixed system in parallel flow and reacts. When the D50 of the generated aluminum-doped cobalt carbonate crystal grows to 18-20 ⁇ m, the solid and liquid are separated to obtain the aluminum-doped cobalt carbonate.
  • the dispersant is fulvic acid.
  • the molar ratio of fulvic acid to aluminum in the molten metal A is 0.01-0.5.
  • the molar ratio of fulvic acid to aluminum in the molten metal A is 0.05-0.3.
  • the mass ratio of aluminum ions to cobalt ions in the metal liquid A and the metal liquid B is 0.005-0.02.
  • the mass ratio of aluminum ions to cobalt ions in the molten metal A and the molten metal B is 0.008-0.0165.
  • the cobalt ion concentration in the metal liquid A and the metal liquid B is 0.3-4 mol/L.
  • the cobalt ion concentration in the metal liquid A and the metal liquid B is 0.5-3 mol/L.
  • the bicarbonate is ammonium bicarbonate.
  • the carbonate is ammonium bicarbonate and/or ammonium carbonate, and the concentration of the carbonate is 1-5 mol/L.
  • the concentration of the carbonate is 2-3 mol/L.
  • the soluble cobalt salt is at least one of cobalt chloride, cobalt sulfate and cobalt nitrate.
  • the soluble aluminum salt is aluminum sulfate octadecahydrate.
  • the reaction temperature in step (2) is 30-50°C.
  • reaction temperature in step (2) is 35-48°C.
  • the concentration of the bottom liquid is 0.2-5 mol/L.
  • the concentration of the bottom liquid is 0.5-3 mol/L.
  • the flow rate of the molten metal A is 5-40 L/h, and the flow rate of the precipitant is controlled so that the molar ratio of the precipitant to the cobalt salt in the molten metal A is 2-4.
  • step (2) the flow rate of the molten metal A is 7-35L/h, and the flow rate of the precipitant is controlled at a molar ratio of the precipitant to the cobalt salt in the molten metal A of 2.2- 3.
  • the reaction in step (2) is carried out under stirring, and the stirring frequency is 10-30 Hz.
  • step (2) is carried out under stirring, and the stirring frequency is 12-28 Hz.
  • the reaction in step (3) is carried out under stirring, and the stirring frequency is lower than that in step (3).
  • step (3) is carried out under stirring, and the stirring frequency is reduced by 1-3 Hz compared with step (2).
  • the flow rate of the molten metal B is 5-40L/h.
  • step (3) the flow rate of the molten metal B is 7-35L/h.
  • step (3) the solid after solid-liquid separation is also washed and dried to obtain the aluminum-doped cobalt carbonate.
  • the washing method is centrifugal washing, and the temperature of the water used for washing is 40-80°C.
  • the temperature of water used for washing is 50-70°C.
  • the drying temperature is 70-150°C.
  • the drying temperature is 90-120°C.
  • both reaction I and reaction II are carried out in a reaction kettle, and the bottom liquid volume is 0.3-0.6 times the total volume of the reaction kettle.
  • the D50 of the aluminum-doped cobalt carbonate crystal generated in reaction I is half of the length of the kettle when it reaches 9-10 ⁇ m.
  • dividing half of the kettle means dividing half of the materials in the reaction kettle into another reaction kettle to continue the reaction.
  • the pot is divided into half.
  • Aluminum-doped cobalt carbonate is prepared by the preparation method as described above.
  • the present invention in order to increase production capacity, is designed to use a larger cobalt salt flow rate to participate in the reaction.
  • the size of the aluminum-doped cobalt carbonate particles is small and has a large specific surface area.
  • the reaction conditions of large cobalt salt flow rate will bring about the problem of particle agglomeration.
  • the present invention A dispersant is added to the metal liquid. The dispersant can effectively change the surface state of the particles and form a polymer film on the surface of the particles to prevent the particles from contacting each other and effectively alleviate particle agglomeration.
  • reaction metal liquid is replaced in the later stage of the reaction, and the molten metal A is Switching to the metal liquid B can increase the surface energy of the cobalt carbonate particles, which is conducive to the particle surface capturing metal ions in the reaction system for secondary growth and avoiding the generation of new nuclei.
  • the dispersant used is fulvic acid.
  • Fulvic acid is a substance extracted from humus. It is safe, non-toxic, and environmentally friendly.
  • the fulvic acid structure contains a large number of phenolic hydroxyl groups. , carbonyl and other groups, it can be used as a chelating agent to combine with metal ions, which is beneficial to the uniform distribution of aluminum elements, and can also be used as a dispersant to inhibit particle agglomeration.
  • Figure 1 is an SEM image of aluminum-doped cobalt carbonate prepared in Example 1 of the present invention.
  • Figure 2 is a cross-sectional SEM image and EDS spectrum of aluminum-doped cobalt carbonate prepared in Example 2 of the present invention
  • Figure 3 is an SEM image of aluminum-doped cobalt carbonate prepared in Comparative Example 1 of the present invention.
  • Figure 4 is an SEM image and a cross-sectional SEM image of aluminum-doped cobalt carbonate prepared in Comparative Example 2 of the present invention
  • Figure 5 is an SEM image of aluminum-doped cobalt carbonate prepared in Comparative Example 3 of the present invention.
  • a preparation method of aluminum-doped cobalt carbonate including the following steps:
  • Liquid preparation Add cobalt chloride, aluminum sulfate octahydrate, fulvic acid and water to metal liquid preparation tank A to obtain metal liquid A.
  • concentration of cobalt ions in metal liquid A is 0.5mol/L, and the concentration of aluminum ions is 0.5mol/L.
  • the mass ratio to cobalt ions is 0.008, and the molar ratio of fulvic acid to aluminum ions is 0.05; add cobalt chloride, aluminum sulfate octahydrate and water to metal liquid tank B to obtain metal liquid B.
  • Cobalt in metal liquid B The concentration of ions is 0.5mol/L, and the mass ratio of aluminum ions to cobalt ions is 0.008; add precipitant to the precipitant preparation tank.
  • the precipitant is ammonium bicarbonate with a concentration of 2mol/L, and the prepared concentration is 0.5mol/L. Ammonium bicarbonate is used as the base liquid;
  • Reaction I Add a bottom liquid into the reactor, the volume of the bottom liquid is 0.3 times the total volume of the reactor, add the metal liquid A and the precipitant into the reactor in parallel, wherein the flow rate of the metal liquid A is 7 L/h, the flow rate of the precipitant is controlled so that the molar ratio of the precipitant to the cobalt salt is 2.2, the temperature is raised to 35°C, the stirring speed is 12 Hz, and the reactor is left to stand and evacuate when it is full.
  • the D50 of the cobalt aluminate-doped carbonate crystals grows to 9 ⁇ m, half of the reactor is divided, and then the parallel flow reaction is continued;
  • Reaction II When the kettle is full, let it stand and drain. When the D50 of the aluminum-doped cobalt carbonate crystal grows to 14 ⁇ m, divide the kettle into half, switch the molten metal A to the molten metal B, and continue to add the molten metal B into the reaction kettle in parallel flow. and precipitant, lower the stirring speed by 1 Hz, and control the reaction temperature and flow rate the same as Reaction I. When the kettle is full, let it stand and drain, until the D50 of the aluminum-doped cobalt carbonate crystal grows to 18 ⁇ m, the reaction ends, and the solid-liquid separation is performed to obtain a solid;
  • the SEM image of the aluminum-doped cobalt carbonate prepared in Example 1 is shown in Figure 1. It can be seen from the figure that the size of the aluminum-doped cobalt carbonate particles is uniform, there are almost no small particles, and there is no aluminum segregation on the surface.
  • a method for preparing aluminum-doped cobalt carbonate comprises the following steps:
  • Liquid preparation Add cobalt sulfate, aluminum sulfate octahydrate, fulvic acid and water to the metal liquid preparation tank A to obtain metal liquid A.
  • concentration of cobalt ions in metal liquid A is 3mol/L.
  • Aluminum ions and cobalt The mass ratio of ions is 0.0165, and the molar ratio of fulvic acid to aluminum ions is 0.3; add cobalt sulfate, aluminum sulfate octahydrate and water to metal liquid preparation tank B to obtain metal liquid B.
  • the concentration of cobalt ions in metal liquid B The mass ratio of aluminum ions to cobalt ions is 0.0165; add precipitant to the precipitant liquid tank.
  • the precipitant is ammonium carbonate with a concentration of 3mol/L.
  • Reaction I Pour the bottom liquid into the reaction kettle. The volume of the bottom liquid is 0.6 times the total volume of the reaction kettle. Add molten metal A and the precipitant into the reaction kettle in parallel flow. The flow rate of molten metal A is 35L/h. , the flow rate of the precipitant is controlled so that the molar ratio of the precipitant to the cobalt salt is 3, the temperature rises to 48°C, the stirring speed is 28Hz, and the kettle is left to stand and drained when it is full, until the D50 of the aluminum-doped cobalt carbonate crystal grows to 10 ⁇ m. Half, then continue the parallel flow reaction;
  • Reaction II When the kettle is full, let it stand and pump out the water until the D50 of the cobalt aluminate-doped carbonate crystals grows to 15 ⁇ m. Half of the kettle is divided, and the metal liquid A is switched to the metal liquid B. The metal liquid B and the precipitant are added to the reactor in parallel. The stirring speed is lowered by 3 Hz. The reaction temperature and flow rate are controlled in the same way as in Reaction I. When the kettle is full, let it stand and pump out the water until the D50 of the cobalt aluminate-doped carbonate crystals grows to 20 ⁇ m. The reaction is terminated and the solid-liquid separation is performed to obtain a solid.
  • the SEM image of the aluminum-doped cobalt carbonate prepared in Example 2 is shown in Figure 2. It can be seen from the figure that the interior of the bulk phase of the aluminum-doped cobalt carbonate is smooth and there is no aluminum aggregation, indicating that the aluminum element is evenly distributed in the bulk phase, and at the same time, cross section
  • the EDS surface scan obtained the EDS energy spectrum as shown in Figure 2. The test results show that there are metal elements cobalt and aluminum in the cross section, indicating that aluminum has been doped inside the cobalt carbonate.
  • a preparation method of aluminum-doped cobalt carbonate including the following steps:
  • Liquid preparation Add cobalt nitrate, aluminum sulfate octahydrate, fulvic acid and water to the metal liquid preparation tank A to obtain metal liquid A.
  • concentration of cobalt ions in metal liquid A is 2.5 mol/L, and the aluminum ions and The mass ratio of cobalt ions is 0.0137, and the molar ratio of fulvic acid to aluminum ions is 0.2; add cobalt nitrate, aluminum sulfate octahydrate and water to metal liquid preparation tank B to obtain metal liquid B.
  • the cobalt ions in metal liquid B are The concentration is 2.5mol/L, and the mass ratio of aluminum ions to cobalt ions is 0.0137; add precipitant to the precipitant preparation tank.
  • the precipitant is ammonium carbonate with a concentration of 2.5mol/L, and prepare hydrogen carbonate with a concentration of 1mol/L. Ammonium serves as base liquid;
  • Reaction I Pour the bottom liquid into the reaction kettle.
  • the volume of the bottom liquid is 0.5 times the total volume of the reaction kettle.
  • the kettle is full, it is left to stand and drained until the D50 of the aluminum-doped cobalt carbonate crystal grows to 9.5 ⁇ m. Divide the kettle into half, and then continue the parallel flow reaction;
  • Reaction II When the kettle is full, let it stand and drain until the D50 of the aluminum-doped cobalt carbonate crystal grows to 14.5 ⁇ m. Divide the kettle into half, switch the molten metal A to the molten metal B, and continue to add the molten metal into the reaction kettle in parallel flow. B and precipitant, lower the stirring speed by 2 Hz, and control the reaction temperature and flow rate the same as reaction I. When the kettle is full, let it stand and drain out. The reaction ends when the D50 of the aluminum-doped cobalt carbonate crystal grows to 18.5 ⁇ m. The solid-liquid separation is obtained to obtain a solid. thing;
  • Washing and drying Use a centrifuge to centrifuge and wash the solid matter, select pure water at 60°C as the washing water, and then dry it in an oven at 110°C to obtain aluminum-doped cobalt carbonate.
  • Comparative Example 1 (The difference from Example 1 is that Comparative Example 1 also added a dispersant to the bottom liquid)
  • a method for preparing aluminum-doped cobalt carbonate comprises the following steps:
  • Liquid preparation Add cobalt chloride, aluminum sulfate octahydrate, fulvic acid and water to metal liquid preparation tank A to obtain metal liquid A.
  • concentration of cobalt ions in metal liquid A is 0.5mol/L
  • concentration of aluminum ions is 0.5mol/L.
  • the mass ratio to cobalt ions is 0.008, and the molar ratio of fulvic acid to aluminum ions is 0.05; add cobalt chloride, aluminum sulfate octahydrate and water to metal liquid tank B to obtain metal liquid B.
  • Cobalt in metal liquid B The concentration of ions is 0.5mol/L, and the mass ratio of aluminum ions to cobalt ions is 0.008; add precipitant to the precipitant preparation tank.
  • the precipitant is ammonium bicarbonate with a concentration of 2mol/L, and the prepared concentration is 0.5mol/L.
  • Ammonium bicarbonate was used as the base liquid, and the base liquid was added with Fulvic acid, and the concentration of fulvic acid in the bottom solution is 5g/L;
  • Reaction I Pour the bottom liquid into the reaction kettle. The volume of the bottom liquid is 0.3 times the total volume of the reaction kettle. Add molten metal A and the precipitant into the reaction kettle in parallel flow. The flow rate of molten metal A is 7L/h. , the flow rate of the precipitant is controlled so that the molar ratio of the precipitant to the cobalt salt is 2.2, the temperature rises to 35°C, the stirring speed is 12Hz, and the kettle is left to stand and drained when full, until the D50 of the aluminum-doped cobalt carbonate crystal grows to 9 ⁇ m. The kettle is half full, and then continue the parallel flow reaction;
  • Reaction II When the kettle is full, let it stand and drain. When the D50 of the aluminum-doped cobalt carbonate crystal grows to 14 ⁇ m, divide the kettle into half, switch the molten metal A to the molten metal B, and continue to add the molten metal B into the reaction kettle in parallel flow. and precipitant, lower the stirring speed by 1 Hz, and control the reaction temperature and flow rate the same as Reaction I. When the kettle is full, let it stand and drain, until the D50 of the aluminum-doped cobalt carbonate crystal grows to 18 ⁇ m, the reaction ends, and the solid-liquid separation is performed to obtain a solid;
  • Comparative Example 2 (The difference from Example 1 is that no dispersant is added to the molten metal A in Comparative Example 2)
  • a preparation method of aluminum-doped cobalt carbonate including the following steps:
  • Liquid preparation Add cobalt chloride, aluminum sulfate octahydrate and water to the metal liquid preparation tank A to obtain metal liquid A.
  • concentration of cobalt ions in metal liquid A is 0.5mol/L.
  • Aluminum ions and cobalt ions The mass ratio is 0.008; add cobalt chloride, aluminum sulfate octahydrate and water to the metal liquid preparation tank B to obtain metal liquid B.
  • the concentration of cobalt ions in metal liquid B is 0.5mol/L.
  • Aluminum ions and cobalt ions The mass ratio is 0.008; add precipitant to the precipitant liquid tank, the precipitant is ammonium bicarbonate with a concentration of 2mol/L, and ammonium bicarbonate with a concentration of 0.5mol/L is prepared as the bottom liquid;
  • Reaction I Pour the bottom liquid into the reaction kettle. The volume of the bottom liquid is 0.3 times the total volume of the reaction kettle. Add molten metal A and the precipitant into the reaction kettle in parallel flow. The flow rate of molten metal A is 7L/h. , the flow rate of the precipitant is controlled so that the molar ratio of the precipitant to the cobalt salt is 2.2, the temperature rises to 35°C, the stirring speed is 12Hz, and the kettle is left standing until the D50 of the aluminum-doped cobalt carbonate crystal reaches 9 ⁇ m. Divide the kettle into half, and then continue the parallel flow reaction;
  • Reaction II When the kettle is full, let it stand and drain. When the D50 of the aluminum-doped cobalt carbonate crystal grows to 14 ⁇ m, divide the kettle into half, switch the molten metal A to the molten metal B, and continue to add the molten metal B into the reaction kettle in parallel flow. He Shen Precipitation agent, the stirring speed is reduced by 1 Hz, the reaction temperature and flow control are the same as Reaction I, the kettle is left to stand and drained when full, and the reaction is completed when the D50 of the aluminum-doped cobalt carbonate crystal grows to 18 ⁇ m, and the solid-liquid is separated to obtain a solid;
  • Comparative Example 3 (The difference from Example 1 is that Comparative Example 3 uses molten metal A throughout the reaction)
  • a preparation method of aluminum-doped cobalt carbonate including the following steps:
  • Liquid preparation cobalt chloride, aluminum sulfate 18hydrate, fulvic acid and water are added to a metal liquid preparation tank A to obtain a metal liquid A, wherein the concentration of cobalt ions in the metal liquid A is 0.5 mol/L, the mass ratio of aluminum ions to cobalt ions is 0.008, and the molar ratio of fulvic acid to aluminum ions is 0.05; a precipitant is added to a precipitant preparation tank, wherein the precipitant is ammonium bicarbonate with a concentration of 2 mol/L, and ammonium bicarbonate with a concentration of 0.5 mol/L is prepared as a base liquid;
  • Reaction I Pour the bottom liquid into the reaction kettle. The volume of the bottom liquid is 0.3 times the total volume of the reaction kettle. Add molten metal A and the precipitant into the reaction kettle in parallel flow. The flow rate of molten metal A is 7L/h. , the flow rate of the precipitant is controlled so that the molar ratio of the precipitant to the cobalt salt is 2.2, the temperature rises to 35°C, the stirring speed is 12Hz, and the kettle is left standing until the D50 of the aluminum-doped cobalt carbonate crystal grows to 9 ⁇ m. Half, then continue the parallel flow reaction;
  • Reaction II When the kettle is full, let it stand and drain. When the D50 of the aluminum-doped cobalt carbonate crystal grows to 14 ⁇ m, divide the kettle into half. The molten metal A continues to flow into the reaction kettle together with the precipitant. The stirring speed is reduced by 1 Hz. The reaction The temperature and flow control are the same as in Reaction I. When the kettle is full, let it stand and drain. The reaction ends when the D50 of the aluminum-doped cobalt carbonate crystal grows to 18 ⁇ m. The solid and liquid are separated to obtain a solid;
  • the SEM image of the aluminum-doped cobalt carbonate prepared in Comparative Example 3 is shown in Figure 5. It can be seen from the figure that there are small particles of different sizes in the sample, indicating that the nucleation speed of the particles in the later stage of the reaction is greater than the growth rate. As the particle size continues to grow, the participation of dispersants makes the electrostatic repulsion and solvation film on the particle surface more obvious, making it more difficult for metal ions to attach to the particle surface and nucleate alone.
  • Comparative Example 4 (The difference from Example 1 is that fulvic acid is replaced by citric acid in the metal liquid A of Comparative Example 4)
  • a preparation method of aluminum-doped cobalt carbonate including the following steps:
  • Liquid preparation Add cobalt chloride, aluminum sulfate octahydrate, citric acid and water to metal liquid preparation tank A to obtain metal liquid A.
  • concentration of cobalt ions in metal liquid A is 0.5mol/L, and the concentration of aluminum ions is 0.5mol/L.
  • the mass ratio to cobalt ions is 0.008, and the molar ratio of citric acid to aluminum is 0.05; add cobalt chloride, aluminum sulfate octahydrate and water to metal liquid preparation tank B to obtain metal liquid B.
  • Cobalt ions in metal liquid B are The concentration is 0.5mol/L, and the mass ratio of aluminum ions to cobalt ions is 0.008; add precipitant to the precipitant preparation tank.
  • the precipitant is ammonium bicarbonate with a concentration of 2mol/L, and the prepared concentration is 0.5mol/L. Ammonium bicarbonate is used as the base liquid;
  • Reaction I Pour the bottom liquid into the reaction kettle. The volume of the bottom liquid is 0.3 times the total volume of the reaction kettle. Add molten metal A and the precipitant into the reaction kettle in parallel flow. The flow rate of molten metal A is 7L/h. , the flow rate of the precipitant is controlled at a molar ratio of precipitant to cobalt salt of 2.2, the temperature rises to 35°C, the stirring speed is 12Hz, and the kettle is left to stand and drained when it is full. When the D50 of the aluminum-doped cobalt carbonate crystal grows to 9 ⁇ m, the kettle is half filled. , and then continue the parallel flow reaction;
  • Reaction II When the kettle is full, let it stand and drain. When the D50 of the aluminum-doped cobalt carbonate crystal grows to 14 ⁇ m, divide the kettle into half, switch the molten metal A to the molten metal B, and continue to add the molten metal B into the reaction kettle in parallel flow. and precipitant, lower the stirring speed by 1 Hz, and control the reaction temperature and flow rate the same as Reaction I. When the kettle is full, let it stand and drain, until the D50 of the aluminum-doped cobalt carbonate crystal grows to 18 ⁇ m, the reaction ends, and the solid-liquid separation is performed to obtain a solid;
  • Example 1 The aluminum-doped cobalt carbonate prepared in Example 1, Comparative Example 2 and Comparative Example 4 were respectively calcined at 700°C for 3 hours to obtain tricobalt tetroxide. Then the obtained tricobalt tetroxide was evenly mixed with lithium carbonate according to the Li:Co molar ratio of 1.05, and placed in a push plate kiln for solid phase sintering at 950°C for 12 hours to obtain lithium cobalt oxide cathode material, and each of the obtained cobalt oxides was Lithium cathode materials are tested for electrochemical performance.

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  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne une méthode de préparation de carbonate de cobalt dopé à l'aluminium. La méthode de préparation comprend les étapes suivantes : (1) préparation d'un liquide : dissolution d'un sel de cobalt soluble, d'un sel d'aluminium soluble et d'un agent de dispersion dans de l'eau pour obtenir un métal fondu A, dissolution d'un sel de cobalt soluble et d'un sel d'aluminium soluble dans de l'eau pour obtenir un métal fondu B, préparation de bicarbonate en tant que solution de base, et préparation de carbonate en tant que précipitant ; (2) réaction I : ajout du métal fondu A et du précipitant dans la solution de base en parallèle, et réaction pour générer un système mixte contenant un cristal de carbonate de cobalt dopé à l'aluminium ; et (3) réaction II : arrêt de l'ajout du métal fondu A dans le système mixte lorsque le D50 du cristal de carbonate de cobalt dopé à l'aluminium généré à l'étape (2) atteint jusqu'à 14-15 µm, ajout simultanément du métal fondu B et du précipitant dans le système mixte en parallèle, réaction, et réalisation d'une séparation solide-liquide lorsque le D50 du cristal de carbonate de cobalt dopé à l'aluminium généré atteint jusqu'à 18-20 µm pour obtenir du carbonate de cobalt dopé à l'aluminium. Le carbonate de cobalt dopé à l'aluminium préparé par la méthode de préparation présente une taille uniforme, aucune petite particule et une distribution uniforme d'élément d'aluminium.
PCT/CN2023/083440 2022-09-20 2023-03-23 Carbonate de cobalt dopé à l'aluminium et sa méthode de préparation WO2024060557A1 (fr)

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