WO2024060504A1 - 一种铝镍共掺碳酸钴前驱体及其制备方法与应用 - Google Patents

一种铝镍共掺碳酸钴前驱体及其制备方法与应用 Download PDF

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WO2024060504A1
WO2024060504A1 PCT/CN2023/077140 CN2023077140W WO2024060504A1 WO 2024060504 A1 WO2024060504 A1 WO 2024060504A1 CN 2023077140 W CN2023077140 W CN 2023077140W WO 2024060504 A1 WO2024060504 A1 WO 2024060504A1
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aluminum
nickel
solution
cobalt
concentration
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PCT/CN2023/077140
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French (fr)
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刘更好
李长东
阮丁山
辛勇诚
卢星华
周思源
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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 WO2024060504A1 publication Critical patent/WO2024060504A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • 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
    • C01P2006/11—Powder tap density
    • 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

Definitions

  • the embodiments of the present application relate to the technical field of lithium-ion batteries, such as an aluminum-nickel co-doped cobalt carbonate precursor and its preparation method and application.
  • Lithium cobalt oxide cathode material has high energy density and is mainly used in the 3C field. With the popularity of 5G mobile phones, the requirements for the capacity of lithium-ion batteries continue to increase. Research shows that increasing the charging cut-off voltage can effectively increase battery capacity. For example, by increasing the voltage from 4.45V to 4.48V, the energy density of the corresponding LCO battery can be increased by about 3.5%. However, increasing the voltage causes the material's crystal structure to collapse, causing capacity to fade quickly.
  • Element doping can effectively solve the stability problem of the material's crystal structure.
  • doping with elements such as Al, Mg, Ni, and Mn can effectively improve the cycle performance of lithium cobalt oxide at high voltages.
  • Lithium cobalt oxide cathode material is mainly sintered from a mixture of cobalt tetroxide and lithium carbonate.
  • cobalt tetroxide is mainly produced by thermal decomposition of cobalt carbonate on the market.
  • cobalt carbonate precursor to pre-oxidized cobalt tetroxide to lithium cobalt oxide cathode material Certain physical and chemical properties have certain inheritance, and the quality of cobalt carbonate will largely affect the electrochemical performance of lithium cobalt oxide cathode materials.
  • the current requirements for high-voltage cobalt carbonate precursors in the market are mainly: increasing the Al doping amount and improving the Al uniformity; in the process of preparing doped cobalt carbonate using the liquid phase precipitation method, there are the following problems: high aluminum doping amount, aluminum It is an inactive element and will cause capacity loss; due to the large difference in concentration between each doping ion and cobalt ion, the ion precipitation is not synchronized and the element distribution is uneven. Therefore, it is difficult to simultaneously increase the Al doping amount and improve the Al uniformity.
  • the embodiments of the present application provide an aluminum-nickel co-doped cobalt carbonate precursor and its preparation method and application.
  • the aluminum-nickel co-doped cobalt carbonate precursor prepared by this method is uniformly doped with aluminum and nickel, which not only reduces the risk of low capacity caused by simply increasing the Al content, but also reduces the risk of nucleation in the later stages of the synthesis process and improves the product's quality. Yield.
  • Cobalt salt solution separately prepare cobalt salt solution, nickel salt solution, aluminum salt solution, high-concentration ammonium bicarbonate solution, low-concentration ammonium bicarbonate solution, and ammonium bicarbonate bottom solution; among them, the concentration of cobalt ions in the cobalt salt solution is 100- 130g/L, the concentration of nickel ions in the nickel salt solution is 1-10g/L, the concentration of aluminum ions in the aluminum salt solution is 5-15g/L, and the concentration of ammonium bicarbonate in the high-concentration ammonium bicarbonate solution is 220-240g /L, the concentration of ammonium bicarbonate in the low-concentration ammonium bicarbonate solution is 120-180g/L, and the concentration of ammonium bicarbonate in the ammonium bicarbonate bottom solution is 40-120g/L;
  • Preparing cobalt carbonate seed crystals Add ammonium bicarbonate bottom liquid to the reaction kettle, and then add cobalt salt solution, aluminum salt solution and high-concentration ammonium bicarbonate solution in parallel flow under heating and stirring conditions, and react to generate cobalt carbonate seed crystals;
  • Preparing the aluminum-nickel co-doped cobalt carbonate precursor While heating and stirring, continue to seed the cobalt carbonate crystals in the reaction kettle, and add cobalt salt solution, nickel salt solution, aluminum salt solution and low-concentration ammonium bicarbonate solution in parallel; The material obtained from the reaction is filtered, and the obtained filtrate is washed, dried, and pulverized to obtain an aluminum-nickel co-doped cobalt carbonate precursor.
  • This application first uses cobalt salt solution, aluminum salt solution and high-concentration ammonium bicarbonate solution to prepare spherical cobalt carbonate seeds with good Al doping uniformity, and then adds cobalt salt solution, nickel salt solution, aluminum salt solution and low-concentration carbonic acid ammonium hydrogen solution to prepare a flake aluminum-nickel co-doped cobalt carbonate precursor.
  • high-concentration ammonium bicarbonate solution and cobalt salt solution react, and at the same time, it can also act as a pH buffer to change the pH of the reaction system within a small range; the obtained cobalt carbonate crystals
  • the species has high tap density, good Al uniformity, and high tap density; in the process of preparing the aluminum-nickel co-doped cobalt carbonate precursor, the low-concentration ammonium bicarbonate solution, in addition to providing sufficient carbonate ions, In addition to precipitation, it can also avoid incomplete nickel precipitation in the high-concentration ammonium bicarbonate system due to the solubility product of nickel carbonate being much greater than that of cobalt carbonate and aluminum hydroxide during nickel-cobalt-aluminum co-precipitation, causing the supernatant to The loss of nickel in the medium; the morphology of the obtained aluminum-nickel co-doped cobalt carbonate precursor is flaky, which provides more growth sites for
  • the structure has high porosity and good sintering activity.
  • it provides a channel for the diffusion of nickel, improves the uniformity of nickel distribution, and thereby improves the performance of cobalt tetroxide.
  • a complexing agent is added to the aluminum salt solution, and the complexing agent and the aluminum salt are complexed.
  • the aluminum salt can co-precipitate with cobalt and nickel at a low precipitation rate in the reaction system without causing aluminum segregation; after the complexing agent enters the reaction system, it releases aluminum ions, causing aluminum ions to In the precipitation reaction, the decomplexed complexing agent is discharged from the system as the mother liquor is concentrated, and will not complex with cobalt ions and nickel ions in the reaction system, causing the loss of cobalt and nickel.
  • the heating temperature is 38-45°C.
  • the pH of the bottom liquid is 8-9
  • the pH of the reaction solution is controlled to be 7.5-8.0 during the feeding process
  • the hourly flow rate of the cobalt salt solution is 1%-10 of the reactor volume. %.
  • cobalt carbonate seed crystals with loose structure are obtained by limiting factors such as the temperature of the reaction system of the reaction solution, the pH of the reaction system, and the rotation speed of the reaction system. Among them, if the pH is less than 7, it is not easy to form cobalt carbonate seed crystals. If the pH is greater than 8, the cobalt carbonate seed crystals formed will have dense structures and uneven Al distribution.
  • the doped elements are in The permeability of cobalt carbonate seed crystal is poor, which affects the doping effect of doping elements.
  • the temperature of the reaction system is lower than 38°C, the number of precipitate particles is small and the particle size is small.
  • the reaction temperature is higher than 45°C, the number of precipitate particles is small and the particle size is large.
  • the heating temperature is 45-55°C.
  • the pH of the reaction solution is controlled to be 7.0-7.5 during the feeding process, and the hourly flow rate of the cobalt salt solution is 1%-10% of the reactor volume.
  • the temperature of the reaction system of the reaction solution, the pH of the reaction system, the rotation speed of the reaction system and other factors are limited to prepare an aluminum-nickel co-doped cobalt carbonate precursor with a sheet structure.
  • Cobalt salt solution, nickel salt solution, aluminum salt solution and low-concentration ammonium bicarbonate solution are coated on the cobalt carbonate seed crystal in a co-precipitation manner, which increases the particle size of the cobalt carbonate seed crystal to obtain a lamellar structure of aluminum nickel Co-doped cobalt carbonate precursor.
  • the temperature of the reaction system when the temperature of the reaction system is lower than 45°C or the pH of the reaction system is greater than 7.5, the flake structure cannot be formed; when the temperature of the reaction system is higher than 55°C or the pH of the reaction system is less than 7.0, the number of precipitate particles obtained Less, larger particle size, lower product yield.
  • the present application obtains cobalt carbonate seeds and aluminum-nickel co-doped cobalt carbonate precursors with different morphologies by adjusting the reaction temperature and the pH of the reaction system for preparing cobalt carbonate seeds and preparing aluminum-nickel cobalt carbonate precursors.
  • the temperature for preparing cobalt carbonate seeds is lower than the temperature for preparing aluminum-nickel co-doped cobalt carbonate precursors
  • the pH for preparing cobalt carbonate seeds is higher than the pH for preparing aluminum-nickel co-doped cobalt carbonate precursors.
  • the absolute value of the temperature for preparing cobalt carbonate seeds and the temperature for preparing aluminum-nickel cobalt carbonate precursors is greater than 3°C; the absolute value of the pH for preparing cobalt carbonate seeds and the pH for preparing aluminum-nickel co-doped cobalt carbonate precursors is greater than 0.4.
  • the cobalt salt is at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate.
  • the nickel salt is at least one of nickel sulfate and nickel chloride.
  • the aluminum salt is at least one of aluminum chloride and aluminum sulfate.
  • the D50 of the cobalt carbonate seed crystal is 7-13 ⁇ m. If the D 50 of the cobalt carbonate seed crystal is too large, it will be difficult for nickel ions to enter the inside of the seed crystal during the growth process, resulting in a uniform distribution of elements in the cobalt carbonate precursor and a decrease in the electrochemical performance of the cathode material.
  • the D50 of the material obtained from the reaction is 15-20 ⁇ m. If the D 50 of the material obtained by the reaction is too large, it is not conducive to the improvement of the material's cycle rate performance; if the D 50 of the material obtained by the reaction is too small, the protective effect on the material is not obvious, and there are few active sites for nickel, which increases the loss of nickel. .
  • the washing solvent is pure water or ammonium bicarbonate solution.
  • the washing solvent is ammonium bicarbonate solution
  • the concentration of the ammonium bicarbonate solution is 10-50g/L. Washing with an ammonium bicarbonate solution with a concentration of 10-50g/L can avoid the introduction of other impurities and reduce the impact of impurities on the cobalt carbonate precursor.
  • the solute of the washing solvent is the same as the solute of the precipitant used to prepare the cobalt carbonate precursor. It is beneficial to improve the stability of the cobalt carbonate precursor, thereby improving the electrochemical performance and stability of the cathode material.
  • the washing temperature of the filter material obtained in this application is a conventional washing temperature. Those skilled in the art can select an appropriate temperature according to actual needs. Preferably, the washing temperature is 25-80°C. Washing within the above temperature range can further clean the filter surface, improve the purity of the cobalt carbonate precursor, and further improve the electrochemical performance of the cathode material.
  • an embodiment of the present application provides an aluminum-nickel co-doped cobalt carbonate precursor, which is prepared by the preparation method of the aluminum-nickel co-doped cobalt carbonate precursor.
  • embodiments of the present application provide cobalt tetroxide, which is prepared by calcining the aluminum-nickel co-doped cobalt carbonate precursor.
  • the preparation method of cobalt trioxide in the present application is a conventional calcination method, which can be a single calcination or a double calcination. Those skilled in the art can select a suitable method according to actual needs.
  • the calcination temperature and time can also be adjusted according to the calcination method in the relevant technology. For example, the step of a single calcination is calcination at 500-700°C for 2.5-6.5h.
  • the steps of the double calcination are: calcination at 250-350°C for 2-4h, and then continue to heat up to 500-700°C for calcination for 2-4h.
  • the external nickel element migrates inward along the lamellar structure with high porosity and good sintering activity, further improving the tetroxide
  • the uniformity of the distribution of doping elements in cobalt oxide improves the performance of cobalt tetroxide.
  • the aluminum-nickel co-doped cobalt carbonate precursor is calcined in an air atmosphere or an oxygen atmosphere.
  • the oxygen atmosphere preferably has an oxygen concentration of, for example, 10% by volume or more and 50% by volume or less.
  • This application first uses cobalt salt solution, aluminum salt solution and high-concentration ammonium bicarbonate solution to prepare spherical cobalt carbonate seeds with good Al doping uniformity, and then adds cobalt salt solution, nickel salt solution, aluminum salt solution and low-concentration ammonium bicarbonate solution to prepare a flake aluminum-nickel co-doped cobalt carbonate precursor.
  • high-concentration ammonium bicarbonate solution and cobalt salt solution react, and at the same time, it can also act as a pH buffer to change the pH of the reaction system within a small range; the obtained cobalt carbonate crystals
  • the species has high tap density, good uniformity of Al, and high tap density.
  • the low-concentration ammonium bicarbonate solution in addition to providing sufficient carbonate ions for precipitation, can also avoid the high-concentration ammonium bicarbonate system due to nickel and cobalt.
  • the solubility product of nickel carbonate is much greater than that of cobalt carbonate and aluminum hydroxide, resulting in incomplete nickel precipitation, resulting in the loss of nickel in the supernatant liquid; the morphology of the obtained aluminum-nickel co-doped cobalt carbonate precursor is flake-like, Provide more growth sites for nickel co-precipitation and reduce nickel loss.
  • the structure has high porosity and good sintering activity. In the process of preparing cobalt tetroxide, it provides channels for the diffusion of nickel and improves the uniformity of nickel distribution. This further improves the performance of cobalt tetroxide.
  • the aluminum-nickel co-doped cobalt carbonate precursor of the present application has a low reaction temperature, low energy consumption, and can better control the nucleus production during synthesis, which can better ensure a better yield.
  • Figure 1 is a morphology diagram of the cobalt carbonate seed crystal and the aluminum-nickel co-doped cobalt carbonate precursor obtained in Example 1; a is the scanning electron microscope image of the cobalt carbonate seed crystal, and b and c are the morphology of the aluminum-nickel co-doped cobalt carbonate precursor. Scanning electron microscope image, d is the CP cross-sectional view of aluminum-nickel co-doped cobalt carbonate precursor;
  • Figure 2 is a morphology diagram of the cobalt carbonate seed crystal and the aluminum-nickel co-doped cobalt carbonate precursor obtained in Example 2; a is the scanning electron microscope image of the cobalt carbonate seed crystal, and b and c are the morphology of the aluminum-nickel co-doped cobalt carbonate precursor. Scanning electron microscope image, d is the CP cross-sectional view of aluminum-nickel co-doped cobalt carbonate precursor;
  • Figure 3 is a morphology diagram of the cobalt carbonate seed crystal and the aluminum-nickel co-doped cobalt carbonate precursor obtained in Example 3; a is the scanning electron microscope image of the cobalt carbonate seed crystal, and b and c are the morphology of the aluminum-nickel co-doped cobalt carbonate precursor. Scanning electron microscope image, d is the CP cross-sectional view of aluminum-nickel co-doped cobalt carbonate precursor;
  • Figure 4 is a morphology diagram of the cobalt carbonate seed crystal and the aluminum-nickel co-doped cobalt carbonate precursor obtained in Comparative Example 1; a is the scanning electron microscope image of the cobalt carbonate seed crystal, and b and c are the morphology of the aluminum-nickel co-doped cobalt carbonate precursor. Scanning electron microscope image, d is the CP cross-sectional view of aluminum-nickel co-doped cobalt carbonate precursor;
  • Figure 5 is a morphology diagram of the cobalt carbonate seed crystal and the aluminum-nickel co-doped cobalt carbonate precursor obtained in Comparative Example 2; a is the scanning electron microscope image of the cobalt carbonate seed crystal, and b and c are the morphology of the aluminum-nickel co-doped cobalt carbonate precursor. Scanning electron microscope image, d is the CP cross-sectional view of aluminum-nickel co-doped cobalt carbonate precursor;
  • Figure 6 is a morphology diagram of the cobalt carbonate seed crystal and the aluminum-nickel co-doped cobalt carbonate precursor obtained in Comparative Example 6; a is the scanning electron microscope image of the cobalt carbonate seed crystal, and b and c are the morphology of the aluminum-nickel co-doped cobalt carbonate precursor. Scanning electron microscope image, d is the CP cross-sectional view of aluminum-nickel co-doped cobalt carbonate precursor.
  • This embodiment provides a method for preparing an aluminum-nickel co-doped cobalt carbonate precursor, which includes the following steps:
  • Preparation of cobalt carbonate seed crystals adding ammonium bicarbonate bottom liquid to a 300L reactor, wherein the volume of the ammonium bicarbonate bottom liquid is based on the volume of the bottom liquid submerging the stirring paddle at the bottom, and the pH value of the bottom liquid is 8.2, and then stirring at a temperature of 41.8°C and a frequency of 20Hz, and adding cobalt chloride solution, aluminum sulfate solution and high-concentration ammonium bicarbonate solution in parallel; wherein the flow rate of the cobalt chloride solution is 7.5L/h, and the flow rate of the aluminum sulfate solution is 0.75L/h; adjusting the flow rate of the high-concentration ammonium bicarbonate solution by a PLC control system to maintain the pH value of the seed crystal synthesis stage at 7.6-8.0, and parallel flow for 15h until the D 50 of the material generated by the reaction is 9 ⁇ m, and stopping the feeding to obtain cobalt carbonate seed crystals;
  • Preparation of aluminum-nickel co-doped cobalt carbonate precursor Raise the reaction temperature to 45.5°C, stir at a frequency of 20Hz, continue to add cobalt chloride solution, nickel sulfate solution, and aluminum sulfate to the cobalt carbonate seeds in the reaction kettle in parallel flow solution and low-concentration ammonium bicarbonate solution; among them, the flow rate of cobalt chloride solution is 15L/h, the flow rate of aluminum sulfate solution is 1.5L/h, and the flow rate of nickel sulfate solution is 1.5L/h; the low concentration is adjusted through the PLC control system The flow rate of concentrated ammonium bicarbonate solution maintains the pH value at the seed growth stage at 7.0-7.2; when the volume of the reaction solution in the reaction kettle reaches 80% of the volume of the reaction kettle, start concentrating and remove the supernatant. During the concentration process , the volume of the reaction solution is maintained at 80% of the reactor volume, until the D 50 of the material generated by the reaction
  • concentration of ammonium bicarbonate in the ammonium bicarbonate solution is 25g/L and the washing time is 30 minutes; centrifuge again and the obtained filter material
  • the material was dried at 110°C for 12 hours until the moisture content of the filtered material was less than 1.1%, and then passed through a 300-mesh vibrating sieve to obtain an aluminum-nickel co-doped cobalt carbonate precursor.
  • This embodiment provides a method for preparing an aluminum-nickel co-doped cobalt carbonate precursor, which includes the following steps:
  • Preparation of cobalt carbonate seed crystal Add ammonium bicarbonate bottom liquid to the 300L reaction kettle. The volume of the ammonium bicarbonate bottom liquid is subject to submerging the bottom stirring paddle. The pH value of the bottom liquid is 8.2, and then the temperature is 41.5°C and the frequency Stir under 20Hz conditions, and add cobalt chloride solution, aluminum sulfate solution and high-concentration ammonium bicarbonate solution in parallel flow; among them, the flow rate of cobalt chloride solution is 10.3L/h, and the flow rate of aluminum sulfate solution is 0.75L/h; pass The PLC control system adjusts the flow rate of the high-concentration ammonium bicarbonate solution to maintain the pH value of the seed crystal synthesis stage at 7.7-8.1, and flows for 15 hours until the D50 of the material generated by the reaction is 8.5 ⁇ m. Stop feeding and obtain cobalt carbonate seed crystals;
  • Preparation of aluminum-nickel co-doped cobalt carbonate precursor Raise the reaction temperature to 45.3°C, stir at a frequency of 20 Hz, and continue to add cobalt chloride solution, nickel sulfate solution, and sulfur to the cobalt carbonate seed in the reactor.
  • Aluminum sulfate solution and low-concentration ammonium bicarbonate solution wherein the flow rate of the cobalt chloride solution is 20.6 L/h, the flow rate of the aluminum sulfate solution is 1.5 L/h, and the flow rate of the nickel sulfate solution is 1.5 L/h; the flow rate of the low-concentration ammonium bicarbonate solution is adjusted by a PLC control system to maintain a pH value of 7.1-7.3 in the seed crystal growth stage; when the volume of the reaction solution in the reactor is 83% of the volume of the reactor, concentration is started, and the supernatant is removed. During the concentration process, the volume of the reaction solution is maintained at 83% of the volume of the reactor until the D 50 of the material generated by the reaction is 18.2 ⁇ m, and the feeding is stopped to obtain a cobalt carbonate slurry;
  • the obtained cobalt carbonate slurry was centrifugally filtered, and the obtained filter material was washed with an ammonium bicarbonate solution with a temperature of 60°C.
  • the concentration of ammonium bicarbonate in the ammonium bicarbonate solution was 22g/L, and the washing time was 30 minutes; centrifuge again and the obtained filter material was washed.
  • the material was dried at 110°C for 12 hours until the moisture content of the filtered material was less than 1.1%, and then passed through a 300-mesh vibrating sieve to obtain an aluminum-nickel co-doped cobalt carbonate precursor.
  • This embodiment provides a method for preparing an aluminum-nickel co-doped cobalt carbonate precursor, which includes the following steps:
  • Preparation of cobalt carbonate seed crystals Add ammonium bicarbonate bottom liquid to the 300L reaction kettle. The volume of the ammonium bicarbonate bottom liquid is subject to submerging the bottom stirring paddle. The pH value of the bottom liquid is 8.1, and then the temperature is 40.7°C and the frequency is Stir under 20Hz conditions, and add cobalt chloride solution, aluminum sulfate solution and high-concentration ammonium bicarbonate solution in parallel flow; among them, the flow rate of cobalt chloride solution is 8.3L/h, and the flow rate of aluminum sulfate solution is 0.75L/h; pass The PLC control system adjusts the flow rate of the high-concentration ammonium bicarbonate solution to maintain the pH value of the seed crystal synthesis stage at 7.7-8.1, and flows for 15 hours until the D 50 of the material generated by the reaction is 7.9 ⁇ m. Stop feeding and obtain cobalt carbonate seed crystals;
  • Preparation of aluminum-nickel co-doped cobalt carbonate precursor Raise the reaction temperature to 45.6°C, stir at a frequency of 20Hz, continue to add cobalt chloride solution, nickel sulfate solution, and aluminum sulfate to the cobalt carbonate seeds in the reaction kettle in parallel flow solution and low-concentration ammonium bicarbonate solution; among them, the flow rate of cobalt chloride solution is 16.5L/h, the flow rate of aluminum sulfate solution is 1.5L/h, and the flow rate of nickel sulfate solution is 1.5L/h; adjusted by PLC control system The flow rate of the low-concentration ammonium bicarbonate solution maintains the pH value at the seed growth stage at 7.1-7.3; when the When the volume of the reaction solution reaches 81% of the volume of the reaction kettle, start concentrating and remove the supernatant. During the concentration process, the volume of the reaction solution is maintained at 81% of the volume of the reaction kettle until the D 50 of the material generated by the reaction is
  • the obtained cobalt carbonate slurry was centrifugally filtered, and the obtained filtrate was washed with an ammonium bicarbonate solution with a temperature of 60°C.
  • the concentration of ammonium bicarbonate in the ammonium bicarbonate solution was 23g/L, and the washing time was 30 minutes; centrifuge again and the obtained filter
  • the material was dried at 110°C for 12 hours until the moisture content of the filtered material was less than 2.2%, and then passed through a 300-mesh vibrating sieve to obtain an aluminum-nickel co-doped cobalt carbonate precursor.
  • This embodiment provides a method for preparing an aluminum-nickel co-doped cobalt carbonate precursor, which includes the following steps:
  • the concentration of ammonium bicarbonate in the low-concentration ammonium bicarbonate solution is 120g/L.
  • concentration of ammonium bicarbonate in the bottom ammonium bicarbonate solution is 120g/L.
  • concentration of ammonium is 80g/L;
  • Preparation of cobalt carbonate seed crystals Add ammonium bicarbonate bottom liquid to the 300L reaction kettle. The volume of the ammonium bicarbonate bottom liquid is subject to submerging the bottom stirring paddle. The pH value of the bottom liquid is 8.5, and then the temperature is 38.1°C and the frequency is Stir under 20Hz conditions, and add cobalt chloride solution, aluminum sulfate solution and high-concentration ammonium bicarbonate solution in parallel flow; among them, the flow rate of cobalt chloride solution is 3.5L/h, and the flow rate of aluminum sulfate solution is 0.27L/h; pass The PLC control system adjusts the flow rate of the high-concentration ammonium bicarbonate solution to maintain the pH value of the seed crystal synthesis stage at 7.7-8.1, and flows for 15 hours until the D50 of the material generated by the reaction is 7.2 ⁇ m. Stop feeding and obtain cobalt carbonate seed crystals;
  • Preparation of aluminum-nickel co-doped cobalt carbonate precursor Raise the reaction temperature to 54.8°C, stir at a frequency of 20Hz, continue to add cobalt chloride solution, nickel sulfate solution, and aluminum sulfate to the cobalt carbonate seeds in the reaction kettle in parallel flow solution and low-concentration ammonium bicarbonate solution; among them, the flow rate of cobalt chloride solution is 16.5L/h, the flow rate of aluminum sulfate solution is 1.2L/h, and the flow rate of nickel sulfate solution is 0.45L/h; adjusted by PLC control system The flow rate of the low-concentration ammonium bicarbonate solution maintains the pH value at the seed growth stage at 7.1-7.3; when the volume of the reaction solution in the reaction kettle reaches 81% of the volume of the reaction kettle, concentration begins, the supernatant is removed, and the concentration process , the volume of the reaction solution is maintained at 81% of the reactor volume, until the D 50 of the material generated by the
  • concentration of ammonium bicarbonate in the ammonium bicarbonate solution is 10g/L and the washing time is 60 minutes; centrifuge again and the obtained filter
  • the material was dried at 90°C for 12 hours until the moisture content of the filtered material was less than 2.2%, and then passed through a 300-mesh vibrating sieve to obtain an aluminum-nickel co-doped cobalt carbonate precursor.
  • This embodiment provides a method for preparing an aluminum-nickel co-doped cobalt carbonate precursor, which includes the following steps:
  • Preparation of cobalt carbonate seed crystal Add ammonium bicarbonate bottom liquid to the 300L reaction kettle. The volume of the ammonium bicarbonate bottom liquid is subject to submerging the bottom stirring paddle. The pH value of the bottom liquid is 8.1, and then the temperature is 44.7°C and the frequency is Stir under 20Hz conditions, and add cobalt chloride solution, aluminum sulfate solution and high-concentration ammonium bicarbonate solution in parallel flow; among them, the flow rate of cobalt chloride solution is 15L/h, and the flow rate of aluminum sulfate solution is 3.47L/h; through PLC The control system adjusts the flow rate of the high-concentration ammonium bicarbonate solution to maintain the pH value of the seed crystal synthesis stage at 7.7-8.1, and flows for 15 hours until the D50 of the material generated by the reaction is 7.9 ⁇ m. Stop feeding and obtain cobalt carbonate seed crystals;
  • Preparation of aluminum-nickel co-doped cobalt carbonate precursor Raise the reaction temperature to 50.6°C, stir at a frequency of 20Hz, continue to add cobalt chloride solution, nickel sulfate solution, and aluminum sulfate to the cobalt carbonate seeds in the reaction kettle in parallel.
  • the flow rate of cobalt chloride solution is 16.5L/h
  • the flow rate of aluminum sulfate solution is 3.84L/h
  • the flow rate of nickel sulfate solution is 4.5L/h
  • the flow rate of the low-concentration ammonium bicarbonate solution maintains the pH value at the seed growth stage at 7.1-7.3; when the volume of the reaction solution in the reaction kettle reaches 81% of the volume of the reaction kettle, concentration begins, the supernatant is removed, and the concentration process , the volume of the reaction solution is maintained at 81% of the reactor volume, until the D 50 of the material generated by the reaction is 15.4 ⁇ m, stop feeding, and obtain cobalt carbonate slurry;
  • the obtained cobalt carbonate slurry is centrifugally filtered, and the obtained filter material is washed with an ammonium bicarbonate solution with a temperature of 60°C.
  • the concentration of ammonium bicarbonate in the ammonium bicarbonate solution is 50g/L, and the washing time is 10 minutes; centrifuge again and the obtained filter material is washed.
  • the filter material is dried at 100°C for 12 hours until the moisture content of the filter material is less than 2.2%, and then passed through 300 mesh vibration. Sieve to obtain aluminum-nickel co-doped cobalt carbonate precursor.
  • Example 1 The only difference between this comparative example and Example 1 is that it does not contain low-concentration ammonium bicarbonate solution.
  • Example 1 The only difference between this comparative example and Example 1 is that it does not contain high-concentration ammonium bicarbonate solution.
  • Example 1 The only difference between this comparative example and Example 1 is that the aluminum sulfate solution does not contain a complexing agent.
  • This embodiment provides a method for preparing an aluminum-nickel co-doped cobalt carbonate precursor, which includes the following steps:
  • Preparation of cobalt carbonate seed crystals Add ammonium bicarbonate bottom liquid to the 300L reaction kettle. The volume of the ammonium bicarbonate bottom liquid is subject to submerging the bottom stirring paddle. The pH value of the bottom liquid is 8.2, and then the temperature is 41.8°C and the frequency is Stir under 20Hz conditions, and add the mixed solution and high-concentration ammonium bicarbonate solution in parallel; the flow rate of the mixed solution is 7.5L/h; adjust the flow rate of the high-concentration ammonium bicarbonate solution through the PLC control system to maintain the pH in the seed synthesis stage The value is 7.6-8.0, flow in parallel for 15 hours, until the D 50 of the material generated by the reaction is 9 ⁇ m, stop feeding, and obtain cobalt carbonate seed crystal;
  • Preparation of aluminum-nickel co-doped cobalt carbonate precursor Raise the reaction temperature to 45.5°C, stir at a frequency of 20 Hz, continue to add cobalt carbonate seeds in the reaction kettle, and add the mixed solution and low-concentration ammonium bicarbonate solution in parallel; where , the flow rate of the mixed solution is 15L/h; the flow rate of the low-concentration ammonium bicarbonate solution is adjusted through the PLC control system to maintain the pH value of the seed growth stage at 7.0-7.2; when the volume of the reaction solution in the reaction kettle is the volume of the reaction kettle At 80%, start concentrating and remove the supernatant. During the concentration process, the volume of the reaction solution is maintained at 80% of the reactor volume until the D 50 of the material generated by the reaction is 18.3 ⁇ m. Stop feeding to obtain cobalt carbonate slurry. ;
  • concentration of ammonium bicarbonate in the ammonium bicarbonate solution is 25g/L and the washing time is 30 minutes; centrifuge again and the obtained filter material
  • the filter material was dried at 110°C for 12 hours until the moisture content of the filter material was less than 1.1%, and then passed through a 300-mesh vibrating sieve to obtain an aluminum-nickel co-doped cobalt carbonate precursor.
  • This embodiment provides a method for preparing an aluminum-nickel co-doped cobalt carbonate precursor, which includes the following steps:
  • Preparation of cobalt carbonate seed crystal Add sodium carbonate bottom liquid to the 300L reaction kettle. The volume of the sodium carbonate bottom liquid is subject to submerging the bottom stirring paddle. The pH value of the bottom liquid is 8.2, and then the temperature is 41.8°C and the frequency is 20Hz.
  • Preparation of aluminum-nickel co-doped cobalt carbonate precursor Raise the reaction temperature to 45.5°C, stir at a frequency of 20Hz, continue to add cobalt chloride solution, nickel sulfate solution, and aluminum sulfate to the cobalt carbonate seeds in the reaction kettle in parallel flow solution and low-concentration sodium carbonate solution; among them, the flow rate of cobalt chloride solution is 15L/h, the flow rate of aluminum sulfate solution is 1.5L/h, and the flow rate of nickel sulfate solution is 1.5L/h; the low concentration is adjusted through the PLC control system The flow rate of the sodium carbonate solution maintains the pH value at the seed growth stage at 7.0-7.2; when the volume of the reaction solution in the reaction kettle reaches 80% of the volume of the reaction kettle, start concentrating and remove the supernatant. During the concentration process, the reaction The volume of the solution is maintained at 80% of the volume of the reactor until the D 50 of the material generated by the reaction is 18.3 ⁇
  • This embodiment provides a method for preparing an aluminum-nickel co-doped cobalt carbonate precursor, which includes the following steps:
  • Preparation of cobalt carbonate seed crystal Add sodium carbonate bottom liquid to the 300L reaction kettle. The volume of the sodium carbonate bottom liquid is subject to submerging the bottom stirring paddle. The pH value of the bottom liquid is 8.5, and then the temperature is 45.3°C and the frequency is 20Hz. Stir at high speed, add the mixed solution and sodium carbonate solution in parallel flow, the flow rate of the mixed solution is 7.5L/h; adjust the flow rate of the sodium carbonate solution through the PLC control system to maintain the pH value of the seed synthesis stage at 7.3-7.4, and flow in parallel for 15 hours. Until the D 50 of the material generated by the reaction is 7.3 ⁇ m, stop feeding and obtain cobalt carbonate seed crystal;
  • Preparation of aluminum-nickel co-doped cobalt carbonate precursor Raise the reaction temperature to 45.7°C, stir at a frequency of 20 Hz, continue to add the cobalt carbonate seed crystal in the reaction kettle, add the mixed solution and sodium carbonate solution in parallel flow, the flow rate of the mixed solution is 15L/h, and the flow rate of the sodium carbonate solution is adjusted through the PLC control system to maintain the pH value of the seed growth stage at 7.2-7.4; at the same time, ammonia water is added in parallel to control the concentration of ammonia water in the reaction system to 0.5-1g/L; when the reaction When the volume of the reaction solution in the kettle is 80% of the volume of the reaction kettle, start concentrating and remove the supernatant. During the concentration process, the volume of the reaction solution is maintained at 80% of the volume of the reaction kettle until the material generated by the reaction reaches D 50 is 18.3 ⁇ m, stop feeding and obtain cobalt carbonate slurry;
  • Figure 1 is a scanning electron microscope image of the aluminum-nickel co-doped cobalt carbonate precursor obtained in Example 1.
  • Figure 2 is a scanning electron microscope image of the aluminum-nickel co-doped cobalt carbonate precursor obtained in Example 2.
  • Figure 3 is a scanning electron microscope image of the aluminum-nickel co-doped cobalt carbonate precursor obtained in Example 1.
  • Figure 4 is a SEM image of the aluminum-nickel co-doped cobalt carbonate precursor obtained in Comparative Example 1.
  • Figure 5 is a SEM image of the aluminum-nickel co-doped cobalt carbonate precursor obtained in Comparative Example 2.
  • Figure 6 is a scanning electron microscope image of the aluminum-nickel co-doped cobalt carbonate precursor obtained in Comparative Example 6. It can be seen from Figures 1-3 that in Examples 1-3 The surface of the aluminum-nickel co-doped cobalt carbonate precursor is a lamellar cutting accumulation, with no fine powder, no nucleation, good particle sphericity, and good particle size uniformity; the CP cross-sectional view shows that the interior is smooth, no segregation, the elements are evenly distributed, and the inner layer of the particles Tight, and the outer layer has a certain porosity, which is related to the fact that the inner layer of the aluminum-nickel co-doped cobalt carbonate precursor is massive and the outer layer is a flake structure.
  • the outer layer of the aluminum-nickel co-doped cobalt carbonate precursor obtained in Comparative Example 1 is severely segregated.
  • the CP cross-sectional view shows that the inner and outer layers of the particles are severely segregated, with radial segregation, uneven distribution of elements, and a tight structure in the inner layer of the particles. This is related to the block structure of primary particles.
  • the surface of the aluminum-nickel co-doped cobalt carbonate precursor obtained in Comparative Example 2 is a mixture of particles and flaky cutting structures.
  • the CP cross-section shows severe intra-particle segregation, uneven distribution of elements, and tight inner layers of particles.
  • the outer layer has a certain porosity, which is related to the fact that the inner layer of cobalt carbonate is massive and the outer layer contains a flaky structure. It can be seen from Figure 6 that the surface of the aluminum-nickel co-doped cobalt carbonate precursor particles obtained in Comparative Example 6 is severely segregated, and there is a certain degree of nucleation; the CP cross-sectional view shows severe segregation within the particles, uneven distribution of elements, and a tight structure within the particles. This It is related to the fast structure of primary particles.
  • the aluminum-nickel co-doped cobalt carbonate precursor obtained in Examples 1-5 and Comparative Examples 1-6 was heated to 300°C at a rate of 3°C/min in an air atmosphere, and calcined for 3 hours; and then continued at a rate of 3°C/min. The temperature was increased to 700°C, calcined for 3 hours, and then cooled in the furnace to obtain cobalt tetroxide. The obtained tricobalt tetroxide is mixed with lithium carbonate and calcined to form lithium cobalt oxide.
  • a button battery was prepared. The charge and discharge voltage range was 3.0-4.65V.
  • the first discharge specific capacity was tested at a rate of 0.1C and cycled for 50 weeks at a rate of 0.5C. Test the battery's capacity retention rate. The test results are shown in Table 1.
  • the batteries prepared by the aluminum-nickel co-doped cobalt carbonate precursor of Examples 1-6 have higher capacity and better cycle performance.

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Abstract

本文公布一种铝镍共掺碳酸钴前驱体及其制备方法与应用，属于锂离子电池技术领域。本申请先使用钴盐溶液、铝盐溶液和高浓度碳酸氢铵溶液制备得到Al掺杂均匀性好的球形碳酸钴晶种，再加入钴盐溶液、镍盐溶液、铝盐溶液和低浓度碳酸氢铵溶液，制备得到片状的铝镍共掺碳酸钴前驱体。该制备方法不仅减少了单纯提高Al含量增加带来的低容风险，而且减少了合成过程中后期产核的风险，提高产品的收率，还提高了铝镍共掺碳酸钴前驱体中铝镍元素分布均匀性。

Description

一种铝镍共掺碳酸钴前驱体及其制备方法与应用 技术领域
本申请实施例涉及锂离子电池技术领域，例如一种铝镍共掺碳酸钴前驱体及其制备方法与应用。
背景技术
钴酸锂正极材料能量密度高，主要应用在3C领域，伴随着5G手机的普及，对锂离子电池的容量的要求不断提高。研究表明，提高充电截止电压，能有效提高电池容量。例如，将电压从4.45V提高至4.48V，相应LCO电池的能量密度能提高约3.5％。但是，提高电压会造成材料的晶体结构坍塌，导致容量衰减很快。
元素掺杂能有效解决材料晶体结构的稳定性问题，例如通过Al、Mg、Ni、Mn等元素掺杂能有效改善钴酸锂在高电压下的循环性能。钴酸锂正极材料主要由四氧化三钴和碳酸锂混料烧结而成，其中四氧化三钴在市场上主要由碳酸钴热分解而成，从碳酸钴前驱体到预氧化后的四氧化三钴再到钴酸锂正极材料，某些理化性能具有一定的继承性，碳酸钴的好坏很大程度上会影响到钴酸锂正极材料的电化学性能。
市场上对于高电压碳酸钴前驱体的要求目前主要在：提高Al掺杂量以及改善Al均匀性；采用液相沉淀法制备掺杂碳酸钴的过程中，存在以下问题：掺铝量高，铝是非活性元素，会带来容量的损失；由于各掺杂离子与钴离子浓度积存在较大差异，导致离子沉淀不同步，元素分布不均匀。因此，难以同时提高Al掺杂量以及改善Al均匀性。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请实施例提供一种铝镍共掺碳酸钴前驱体及其制备方法与应用。该方法制得的铝镍共掺碳酸钴前驱体中铝镍掺杂均匀，不仅减少了单纯提高Al含量增加带来的低容风险，而且减少了合成过程中后期产核的风险，提高产品的收率。
本申请实施例采取的技术方案为：一种铝镍共掺碳酸钴前驱体的制备方法，包括以下步骤：
配制溶液：分别配制钴盐溶液、镍盐溶液、铝盐溶液、高浓度碳酸氢铵溶液、低浓度碳酸氢铵溶液，碳酸氢铵底液；其中，钴盐溶液中钴离子的浓度为100-130g/L，镍盐溶液中镍离子的浓度为1-10g/L，铝盐溶液中铝离子的浓度为5-15g/L，高浓度碳酸氢铵溶液中碳酸氢铵的浓度为220-240g/L，低浓度碳酸氢铵溶液中碳酸氢铵的浓度为120-180g/L，碳酸氢铵底液中碳酸氢铵的浓度为40-120g/L；
制备碳酸钴晶种：向反应釜中加入碳酸氢铵底液，然后在加热搅拌条件下，并流加入钴盐溶液、铝盐溶液和高浓度碳酸氢铵溶液，反应生成碳酸钴晶种；
制备铝镍共掺碳酸钴前驱体：在加热搅拌的状态下，继续向反应釜中的碳酸钴晶种，并流加入钴盐溶液、镍盐溶液、铝盐溶液和低浓度碳酸氢铵溶液；反应所得物料进行过滤，所得滤质进行洗涤、干燥、粉碎，得到铝镍共掺碳酸钴前驱体。
本申请先使用钴盐溶液、铝盐溶液和高浓度碳酸氢铵溶液制备得到Al掺杂均匀性好的球形碳酸钴晶种，再加入钴盐溶液、镍盐溶液、铝盐溶液和低浓度碳酸氢铵溶液，制备得到片状的铝镍共掺碳酸钴前驱体。制备碳酸钴晶种的过程中，高浓度碳酸氢铵溶液和钴盐溶液发生反应，同时还能起到pH缓冲剂的作用，使反应体系的pH在较小的范围内变化；所得碳酸钴晶种的振实密度高，Al的均匀性好，还具有高的振实密度；在制备铝镍共掺碳酸钴前驱体的过程中，低浓度碳酸氢铵溶液，除了提供足够的碳酸根离子用于沉淀之外，还能够避免在高浓度的碳酸氢铵体系中，由于镍钴铝共沉淀时由于碳酸镍溶度积远大于碳酸钴和氢氧化铝，导致镍沉淀不完全，造成上清液中镍的损失；所得铝镍共掺碳酸钴前驱体的形貌为片状，为镍的共沉淀提供更多的生长位点，降低镍的损失，该结构的孔隙率高且烧结活性好，在制备四氧化三钴的过程中，为镍的扩散提供通道，提高镍的分布均匀性，进而提高四氧化三钴的性能。
优选地，所述铝盐溶液中含有络合剂，络合剂和铝的摩尔比为络合剂：铝＝0.5-1:10；优选地，所述络合剂为乙二胺四乙酸二钠、柠檬酸铵、柠檬酸、酒石酸、磺基水杨酸中的至少一种。
本申请在铝盐溶液中加入络合剂，络合剂和铝盐进行络合，在制备铝镍共掺 碳酸钴前驱体的时候，铝盐在反应体系中能够以较低的沉淀速率与钴镍实现共沉淀，而不至于发生铝偏析；络合剂进入反应体系后，释放铝离子，使铝离子发生沉淀反应，解络合后的络合剂随着母液浓缩排出体系，不会在反应体系中与钴离子、镍离子络合，造成钴镍的流失。
优选地，所述制备碳酸钴晶种中，加热的温度为38-45℃。
优选地，所述制备碳酸钴晶种中，底液的pH为8-9，加料过程中控制反应溶液的pH为7.5-8.0，钴盐溶液每小时的流量为反应釜体积的1％-10％。
本申请通过对反应溶液的反应体系的温度、反应体系的pH、反应体系的转速等因素进行限定，制得结构疏松的碳酸钴晶种。其中，若pH小于7，不容易形成碳酸钴晶种，若pH大于8，形成的碳酸钴晶种结致密，Al分布不均匀，在制备铝镍共掺碳酸钴前驱时，掺杂的元素在碳酸钴晶种上的渗透性差，影响掺杂元素的掺杂效果。反应体系的温度低于38℃时，沉淀物颗粒多，粒径小，反应温度高于45℃时，沉淀物颗粒的数量少，粒径大。
优选地，所述制备铝镍共掺碳酸钴前驱体中，加热的温度为45-55℃。
优选地，所述制备铝镍共掺碳酸钴前驱体中，加料过程中控制反应溶液的pH为7.0-7.5，钴盐溶液每小时的流量为反应釜体积的1％-10％。
本申请通过对反应溶液的反应体系的温度、反应体系的pH、反应体系的转速等因素进行限定，制得片状结构的铝镍共掺碳酸钴前驱体。钴盐溶液、镍盐溶液、铝盐溶液和低浓度碳酸氢铵溶液以共沉淀的方式包覆在碳酸钴晶种上，是碳酸钴晶种的粒径增大，得到片状结构的铝镍共掺碳酸钴前驱体。其中，当反应体系的温度低于45℃或反应体系的pH大于7.5时，不能形成片状结构；当反应体系的温度高于55℃或反应体系的pH小于7.0时，所得沉淀物颗粒的数量少，粒径大，产品收率低。
本申请通过调节制备碳酸钴晶种和制备铝镍共掺碳酸钴前驱体的反应温度和反应体系的pH来获得形貌不同的碳酸钴晶种和铝镍共掺碳酸钴前驱体。其中，制备碳酸钴晶种的温度小于制备铝镍共掺碳酸钴前驱体的温度，制备碳酸钴晶种的pH大于制备铝镍共掺碳酸钴前驱体的pH。优选地，制备碳酸钴晶种的温度与制备铝镍共掺碳酸钴前驱体的温度的绝对值大于3℃；制备碳酸钴晶种的pH与制备铝镍共掺碳酸钴前驱体的pH的绝对值为大于0.4。
优选地，所述钴盐为氯化钴、硫酸钴、硝酸钴中的至少一种。
优选地，所述镍盐为硫酸镍、氯化镍中的至少一种。
优选地，所述铝盐为氯化铝、硫酸铝中的至少一种。
优选地，所述碳酸钴晶种的D50为7-13μm。若碳酸钴晶种的D50过大，则会使得镍离子在生长过程难以进入晶种内部，导致碳酸钴前驱体的元素分布均匀，使得正极材料的电化学性能下降。
优选地，所述反应所得物料的D50为15-20μm。若反应所得物料的D50过大，不利于材料循环倍率性能的提高；若是反应所得物料的D50过小，对材料的保护作用不明显，镍的活性位点少，增大了镍的损失。
优选地，所述洗涤的溶剂为纯水或碳酸氢铵溶液。
在洗涤过程中，使用纯水或碳酸氢铵溶液洗涤，可以将所得滤质表面的杂质清洗干净。优选地，所述洗涤溶剂为碳酸氢铵溶液，碳酸氢铵溶液的浓度为10-50g/L。使用浓度为10-50g/L碳酸氢铵溶液洗涤，可以避免引入其他杂质，减少杂质对碳酸钴前驱体的影响，而且洗涤溶剂的溶质与制备碳酸钴前驱体使用的沉淀剂的溶质相同，有利于提高碳酸钴前驱体的稳定性，从而提高正极材料的电化学性能和稳定性。
本申请所得滤质的洗涤温度为常规的洗涤温度，本领域技术人员可以根据实际需要选择合适的温度，优选地，所述洗涤的温度为25-80℃。在上述温度范围内进行洗涤，可以进一步将滤质表面的清洗干净，提高碳酸钴前驱体的纯度，进一步提高正极材料的电化学性能。
第二方面，本申请实施例提供一种铝镍共掺碳酸钴前驱体，由所述铝镍共掺碳酸钴前驱体的制备方法制得。
第三方面，本申请实施例提供一种四氧化三钴，由所述的铝镍共掺碳酸钴前驱体经煅烧制得。
本申请四氧化三钴的制备方法为常规的煅烧方法，可以为一次煅烧，也可以为两次煅烧，本领域技术人员可以根据实际需要选择合适方法。煅烧的温度和时间也可根据相关技术中的煅烧方法进行调整，例如一次煅烧的步骤为在500-700℃下煅烧2.5-6.5h。两次煅烧的步骤为：在250-350℃下煅烧2-4h，后继续升温至500-700℃下煅烧2-4h。
由于铝镍共掺碳酸钴前驱体中镍元素内外浓度存在的差异，煅烧过程中，外部镍元素沿着孔隙率高且烧结活性好的片状结构向内迁移，进一步提高四氧 化三钴中掺杂元素分布的均匀性，提高四氧化三钴的性能。
在煅烧过程中，铝镍共掺碳酸钴前驱体用空气气氛或氧气气氛煅烧。氧气气氛优选具有氧浓度，例如10％体积以上，50％体积以下。
与相关技术相比，本申请的有益效果为：本申请先使用钴盐溶液、铝盐溶液和高浓度碳酸氢铵溶液制备得到Al掺杂均匀性好的球形碳酸钴晶种，再加入钴盐溶液、镍盐溶液、铝盐溶液和低浓度碳酸氢铵溶液，制备得到片状的铝镍共掺碳酸钴前驱体。制备碳酸钴晶种的过程中，高浓度碳酸氢铵溶液和钴盐溶液发生反应，同时还能起到pH缓冲剂的作用，使反应体系的pH在较小的范围内变化；所得碳酸钴晶种的振实密度高，Al的均匀性好，还具有高的振实密度。在制备铝镍共掺碳酸钴前驱体的过程中，低浓度碳酸氢铵溶液，除了提供足够的碳酸根离子用于沉淀之外，还能够避免在高浓度的碳酸氢铵体系中，由于镍钴铝共沉淀时由于碳酸镍溶度积远大于碳酸钴和氢氧化铝，导致镍沉淀不完全，造成上清液中镍的损失；所得铝镍共掺碳酸钴前驱体的形貌为片状，为镍的共沉淀提供更多的生长位点，降低镍的损失，该结构的孔隙率高且烧结活性好，在制备四氧化三钴的过程中，为镍的扩散提供通道，提高镍的分布均匀性，进而提高四氧化三钴的性能。
本申请铝镍共掺碳酸钴前驱体的反应温度较低，能耗低，且合成期间能够控制较好的控制产核，能够更好的保证较好的收率。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1为实施例1所得碳酸钴晶种、铝镍共掺碳酸钴前驱体的形貌图；其中a为碳酸钴晶种的扫描电镜图，b、c为铝镍共掺碳酸钴前驱体的扫描电镜图，d为铝镍共掺碳酸钴前驱体的CP截面图；
图2为实施例2所得碳酸钴晶种、铝镍共掺碳酸钴前驱体的形貌图；其中a为碳酸钴晶种的扫描电镜图，b、c为铝镍共掺碳酸钴前驱体的扫描电镜图，d为铝镍共掺碳酸钴前驱体的CP截面图；
图3为实施例3所得碳酸钴晶种、铝镍共掺碳酸钴前驱体的形貌图；其中a为碳酸钴晶种的扫描电镜图，b、c为铝镍共掺碳酸钴前驱体的扫描电镜图，d为铝镍共掺碳酸钴前驱体的CP截面图；
图4为对比例1所得碳酸钴晶种、铝镍共掺碳酸钴前驱体的形貌图；其中a为碳酸钴晶种的扫描电镜图，b、c为铝镍共掺碳酸钴前驱体的扫描电镜图，d为铝镍共掺碳酸钴前驱体的CP截面图；
图5为对比例2所得碳酸钴晶种、铝镍共掺碳酸钴前驱体的形貌图；其中a为碳酸钴晶种的扫描电镜图，b、c为铝镍共掺碳酸钴前驱体的扫描电镜图，d为铝镍共掺碳酸钴前驱体的CP截面图；
图6为对比例6所得碳酸钴晶种、铝镍共掺碳酸钴前驱体的形貌图；其中a为碳酸钴晶种的扫描电镜图，b、c为铝镍共掺碳酸钴前驱体的扫描电镜图，d为铝镍共掺碳酸钴前驱体的CP截面图。
具体实施方式
为更好的说明本申请的目的、技术方案和优点，下面将结合具体实施例和附图对本申请作进一步的说明。
实施例1
本实施例提供了一种铝镍共掺碳酸钴前驱体的制备方法，包括以下步骤：
配制溶液：分别配制氯化钴溶液、硫酸镍溶液、硫酸铝溶液、高浓度碳酸氢铵溶液、低浓度碳酸氢铵溶液，碳酸氢铵底液；其中，氯化钴溶液中钴离子的浓度为130g/L，硫酸镍溶液中镍离子的浓度为3g/L，硫酸铝溶液中铝离子的浓度为12.8g/L，络合剂和铝离子的摩尔比为络合剂：铝＝1:10，高浓度碳酸氢铵溶液中碳酸氢铵的浓度为237g/L，低浓度碳酸氢铵溶液中碳酸氢铵的浓度为120g/L，碳酸氢铵底液中碳酸氢铵的浓度为40g/L；
制备碳酸钴晶种：向300L反应釜中加入碳酸氢铵底液，碳酸氢铵底液的体积以淹没最下层搅拌桨为准，底液的pH值为8.2，然后在温度为41.8℃、频率20Hz条件下搅拌，并流加入氯化钴溶液、硫酸铝溶液和高浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为7.5L/h，硫酸铝溶液的流量为0.75L/h；通过PLC控制系统调节高浓度碳酸氢铵溶液的流量维持晶种合成阶段的pH值为7.6-8.0，并流15h，直到反应生成的物料的D50为9μm，停止投料，得到碳酸钴晶种；
制备铝镍共掺碳酸钴前驱体：将反应温度升至45.5℃，在频率20Hz条件下搅拌，继续反应釜中的碳酸钴晶种中，并流加入氯化钴溶液、硫酸镍溶液、硫酸铝溶液和低浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为15L/h，硫酸铝溶液的流量为1.5L/h，硫酸镍溶液的流量为1.5L/h；通过PLC控制系统调节低浓度碳酸氢铵溶液的流量维持晶种生长阶段的pH值为7.0-7.2；当反应釜内的反应溶液的体积为反应釜体积的80％时，开始浓缩，除掉上清液，浓缩过程中，反应溶液的体积保持在反应釜体积的80％，直到反应生成的物料的D50为18.3μm，停止投料，得到碳酸钴浆料；
将所得碳酸钴浆料离心过滤，所得滤质用温度为60℃的碳酸氢铵溶液洗涤，碳酸氢铵溶液中碳酸氢铵的浓度为25g/L，洗涤时间为30min；再次离心过滤，所得滤质在110℃下干燥12h，至滤质的水分含量小于1.1％后，过300目振动筛，得到铝镍共掺碳酸钴前驱体。
实施例2
本实施例提供了一种铝镍共掺碳酸钴前驱体的制备方法，包括以下步骤：
配制溶液：分别配制氯化钴溶液、硫酸镍溶液、硫酸铝溶液、高浓度碳酸氢铵溶液、低浓度碳酸氢铵溶液，碳酸氢铵底液；其中，氯化钴溶液中钴离子的浓度为100g/L，硫酸镍溶液中镍离子的浓度为3g/L，硫酸铝溶液中铝离子的浓度为12.8g/L,络合剂和铝离子的摩尔比为络合剂：铝＝1:10，高浓度碳酸氢铵溶液中碳酸氢铵的浓度为237g/L，低浓度碳酸氢铵溶液中碳酸氢铵的浓度为142g/L，碳酸氢铵底液中碳酸氢铵的浓度为40g/L；
制备碳酸钴晶种：向300L反应釜中加入碳酸氢铵底液，碳酸氢铵底液的体积以淹没最下层搅拌桨为准，底液的pH值为8.2，然后在温度为41.5℃、频率20Hz条件下搅拌，并流加入氯化钴溶液、硫酸铝溶液和高浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为10.3L/h，硫酸铝溶液的流量为0.75L/h；通过PLC控制系统调节高浓度碳酸氢铵溶液的流量维持晶种合成阶段的pH值为7.7-8.1，并流15h，直到反应生成的物料的D50为8.5μm，停止投料，得到碳酸钴晶种；
制备铝镍共掺碳酸钴前驱体：将反应温度升至45.3℃，在频率20Hz条件下搅拌，继续反应釜中的碳酸钴晶种中，并流加入氯化钴溶液、硫酸镍溶液、硫 酸铝溶液和低浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为20.6L/h，硫酸铝溶液的流量为1.5L/h，硫酸镍溶液的流量为1.5L/h；通过PLC控制系统调节低浓度碳酸氢铵溶液的流量维持晶种生长阶段的pH值为7.1-7.3；当反应釜内的反应溶液的体积为反应釜体积的83％时，开始浓缩，除掉上清液，浓缩过程中，反应溶液的体积保持在反应釜体积的83％，直到反应生成的物料的D50为18.2μm，停止投料，得到碳酸钴浆料；
将所得碳酸钴浆料离心过滤，所得滤质用温度为60℃的碳酸氢铵溶液洗涤，碳酸氢铵溶液中碳酸氢铵的浓度为22g/L，洗涤时间为30min；再次离心过滤，所得滤质在110℃下干燥12h,至滤质的水分含量小于1.1％后，过300目振动筛，得到铝镍共掺碳酸钴前驱体。
实施例3
本实施例提供了一种铝镍共掺碳酸钴前驱体的制备方法，包括以下步骤：
配制溶液：分别配制氯化钴溶液、硫酸镍溶液、硫酸铝溶液、高浓度碳酸氢铵溶液、低浓度碳酸氢铵溶液，碳酸氢铵底液；其中，氯化钴溶液中钴离子的浓度为120g/L，硫酸镍溶液中镍离子的浓度为3g/L，硫酸铝溶液中铝离子的浓度为12.8g/L，络合剂和铝离子的摩尔比为络合剂：铝＝1:10，络合剂为乙二胺四乙酸二钠，高浓度碳酸氢铵溶液中碳酸氢铵的浓度为237g/L，低浓度碳酸氢铵溶液中碳酸氢铵的浓度为142g/L，碳酸氢铵底液中碳酸氢铵的浓度为40g/L；
制备碳酸钴晶种：向300L反应釜中加入碳酸氢铵底液，碳酸氢铵底液的体积以淹没最下层搅拌桨为准，底液的pH值为8.1，然后在温度为40.7℃、频率20Hz条件下搅拌，并流加入氯化钴溶液、硫酸铝溶液和高浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为8.3L/h，硫酸铝溶液的流量为0.75L/h；通过PLC控制系统调节高浓度碳酸氢铵溶液的流量维持晶种合成阶段的pH值为7.7-8.1，并流15h，直到反应生成的物料的D50为7.9μm，停止投料，得到碳酸钴晶种；
制备铝镍共掺碳酸钴前驱体：将反应温度升至45.6℃，在频率20Hz条件下搅拌，继续反应釜中的碳酸钴晶种中，并流加入氯化钴溶液、硫酸镍溶液、硫酸铝溶液和低浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为16.5L/h，硫酸铝溶液的流量为1.5L/h，硫酸镍溶液的流量为1.5L/h；通过PLC控制系统调节低浓度碳酸氢铵溶液的流量维持晶种生长阶段的pH值为7.1-7.3；当反应釜内的 反应溶液的体积为反应釜体积的81％时，开始浓缩，除掉上清液，浓缩过程中，反应溶液的体积保持在反应釜体积的81％，直到反应生成的物料的D50为18.4μm，停止投料，得到碳酸钴浆料；
将所得碳酸钴浆料离心过滤，所得滤质用温度为60℃的碳酸氢铵溶液洗涤，碳酸氢铵溶液中碳酸氢铵的浓度为23g/L，洗涤时间为30min；再次离心过滤，所得滤质在110℃下干燥12h,至滤质的水分含量小于2.2％后，过300目振动筛，得到铝镍共掺碳酸钴前驱体。
实施例4
本实施例提供了一种铝镍共掺碳酸钴前驱体的制备方法，包括以下步骤：
配制溶液：分别配制氯化钴溶液、硫酸镍溶液、硫酸铝溶液、高浓度碳酸氢铵溶液、低浓度碳酸氢铵溶液，碳酸氢铵底液；其中，氯化钴溶液中钴离子的浓度为120g/L，硫酸镍溶液中镍离子的浓度为10g/L，硫酸铝溶液中铝离子的浓度为15g/L，络合剂和铝离子的摩尔比为络合剂：铝＝1：10，络合剂为柠檬酸铵，高浓度碳酸氢铵溶液中碳酸氢铵的浓度为220g/L，低浓度碳酸氢铵溶液中碳酸氢铵的浓度为120g/L，碳酸氢铵底液中碳酸氢铵的浓度为80g/L；
制备碳酸钴晶种：向300L反应釜中加入碳酸氢铵底液，碳酸氢铵底液的体积以淹没最下层搅拌桨为准，底液的pH值为8.5，然后在温度为38.1℃、频率20Hz条件下搅拌，并流加入氯化钴溶液、硫酸铝溶液和高浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为3.5L/h，硫酸铝溶液的流量为0.27L/h；通过PLC控制系统调节高浓度碳酸氢铵溶液的流量维持晶种合成阶段的pH值为7.7-8.1，并流15h，直到反应生成的物料的D50为7.2μm，停止投料，得到碳酸钴晶种；
制备铝镍共掺碳酸钴前驱体：将反应温度升至54.8℃，在频率20Hz条件下搅拌，继续反应釜中的碳酸钴晶种中，并流加入氯化钴溶液、硫酸镍溶液、硫酸铝溶液和低浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为16.5L/h，硫酸铝溶液的流量为1.2L/h，硫酸镍溶液的流量为0.45L/h；通过PLC控制系统调节低浓度碳酸氢铵溶液的流量维持晶种生长阶段的pH值为7.1-7.3；当反应釜内的反应溶液的体积为反应釜体积的81％时，开始浓缩，除掉上清液，浓缩过程中，反应溶液的体积保持在反应釜体积的81％，直到反应生成的物料的D50为19.6μm，停止投料，得到碳酸钴浆料；
将所得碳酸钴浆料离心过滤，所得滤质用温度为50℃的碳酸氢铵溶液洗涤，碳酸氢铵溶液中碳酸氢铵的浓度为10g/L，洗涤时间为60min；再次离心过滤，所得滤质在90℃下干燥12h,至滤质的水分含量小于2.2％后，过300目振动筛，得到铝镍共掺碳酸钴前驱体。
实施例5
本实施例提供了一种铝镍共掺碳酸钴前驱体的制备方法，包括以下步骤：
配制溶液：分别配制氯化钴溶液、硫酸镍溶液、硫酸铝溶液、高浓度碳酸氢铵溶液、低浓度碳酸氢铵溶液，碳酸氢铵底液；其中，氯化钴溶液中钴离子的浓度为120g/L；硫酸镍溶液中镍离子的浓度为1g/L；硫酸铝溶液中铝离子的浓度为5g/L，络合剂和铝离子的摩尔比为络合剂：铝＝0.5:10，络合剂为酒石酸；高浓度碳酸氢铵溶液中碳酸氢铵的浓度为230g/L；低浓度碳酸氢铵溶液中碳酸氢铵的浓度为179g/L；碳酸氢铵底液中碳酸氢铵的浓度为120g/L；
制备碳酸钴晶种：向300L反应釜中加入碳酸氢铵底液，碳酸氢铵底液的体积以淹没最下层搅拌桨为准，底液的pH值为8.1，然后在温度为44.7℃、频率20Hz条件下搅拌，并流加入氯化钴溶液、硫酸铝溶液和高浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为15L/h，硫酸铝溶液的流量为3.47L/h；通过PLC控制系统调节高浓度碳酸氢铵溶液的流量维持晶种合成阶段的pH值为7.7-8.1，并流15h，直到反应生成的物料的D50为7.9μm，停止投料，得到碳酸钴晶种；
制备铝镍共掺碳酸钴前驱体：将反应温度升至50.6℃，在频率20Hz条件下搅拌，继续反应釜中的碳酸钴晶种中，并流加入氯化钴溶液、硫酸镍溶液、硫酸铝溶液和低浓度碳酸氢铵溶液；其中，氯化钴溶液的流量为16.5L/h，硫酸铝溶液的流量为3.84L/h，硫酸镍溶液的流量为4.5L/h；通过PLC控制系统调节低浓度碳酸氢铵溶液的流量维持晶种生长阶段的pH值为7.1-7.3；当反应釜内的反应溶液的体积为反应釜体积的81％时，开始浓缩，除掉上清液，浓缩过程中，反应溶液的体积保持在反应釜体积的81％，直到反应生成的物料的D50为15.4μm，停止投料，得到碳酸钴浆料；
将所得碳酸钴浆料离心过滤，所得滤质用温度为60℃的碳酸氢铵溶液洗涤，碳酸氢铵溶液中碳酸氢铵的浓度为50g/L，洗涤时间为10min；再次离心过滤，所得滤质在100℃下干燥12h,至滤质的水分含量小于2.2％后，过300目振动 筛，得到铝镍共掺碳酸钴前驱体。
对比例1
本对比例与实施例1的唯一区别在于，不含有低浓度碳酸氢铵溶液。
对比例2
本对比例与实施例1的唯一区别在于，不含有高浓度碳酸氢铵溶液。
对比例3
本对比例与实施例1的唯一区别在于，硫酸铝溶液中不含有络合剂。
对比例4
本实施例提供了一种铝镍共掺碳酸钴前驱体的制备方法，包括以下步骤：
配制溶液：分别配制混合溶液、高浓度碳酸氢铵溶液、低浓度碳酸氢铵溶液，碳酸氢铵底液；其中，混合溶液中，钴离子的浓度为130g/L，镍离子的浓度为0.3g/L，铝离子的浓度为1.28g/L，络合剂和铝离子的摩尔比为络合剂：铝＝1:10，高浓度碳酸氢铵溶液中碳酸氢铵的浓度为237g/L，低浓度碳酸氢铵溶液中碳酸氢铵的浓度为120g/L，碳酸氢铵底液中碳酸氢铵的浓度为40g/L；
制备碳酸钴晶种：向300L反应釜中加入碳酸氢铵底液，碳酸氢铵底液的体积以淹没最下层搅拌桨为准，底液的pH值为8.2，然后在温度为41.8℃、频率20Hz条件下搅拌，并流加入混合溶液和高浓度碳酸氢铵溶液；其中，混合溶液的流量为7.5L/h；通过PLC控制系统调节高浓度碳酸氢铵溶液的流量维持晶种合成阶段的pH值为7.6-8.0，并流15h，直到反应生成的物料的D50为9μm，停止投料，得到碳酸钴晶种；
制备铝镍共掺碳酸钴前驱体：将反应温度升至45.5℃，在频率20Hz条件下搅拌，继续反应釜中的碳酸钴晶种中，并流加入混合溶液和低浓度碳酸氢铵溶液；其中，混合溶液的流量为15L/h；通过PLC控制系统调节低浓度碳酸氢铵溶液的流量维持晶种生长阶段的pH值为7.0-7.2；当反应釜内的反应溶液的体积为反应釜体积的80％时，开始浓缩，除掉上清液，浓缩过程中，反应溶液的体积保持在反应釜体积的80％，直到反应生成的物料的D50为18.3μm，停止投料，得到碳酸钴浆料；
将所得碳酸钴浆料离心过滤，所得滤质用温度为60℃的碳酸氢铵溶液洗涤，碳酸氢铵溶液中碳酸氢铵的浓度为25g/L，洗涤时间为30min；再次离心过滤，所得滤质在110℃下干燥12h,至滤质的水分含量小于1.1％后，过300目振动筛，得到铝镍共掺碳酸钴前驱体。
对比例5
本实施例提供了一种铝镍共掺碳酸钴前驱体的制备方法，包括以下步骤：
配制溶液：分别配制氯化钴溶液、硫酸镍溶液、硫酸铝溶液、高浓度碳酸钠溶液、低浓度碳酸钠溶液，碳酸钠底液；其中，氯化钴溶液中钴离子的浓度为130g/L，硫酸镍溶液中镍离子的浓度为3g/L，硫酸铝溶液中铝离子的浓度为12.8g/L，络合剂和铝离子的摩尔比为络合剂：铝＝1:10，高浓度碳酸钠溶液中碳酸钠的浓度为237g/L，低浓度碳酸钠溶液中碳酸钠的浓度为120g/L，碳酸钠底液中碳酸钠的浓度为40g/L；
制备碳酸钴晶种：向300L反应釜中加入碳酸钠底液，碳酸钠底液的体积以淹没最下层搅拌桨为准，底液的pH值为8.2，然后在温度为41.8℃、频率20Hz条件下搅拌，并流加入氯化钴溶液、硫酸铝溶液和高浓度碳酸钠溶液；其中，氯化钴溶液的流量为7.5L/h，硫酸铝溶液的流量为0.75L/h；通过PLC控制系统调节高浓度碳酸钠溶液的流量维持晶种合成阶段的pH值为7.6-8.0，并流15h，直到反应生成的物料的D50为9μm，停止投料，得到碳酸钴晶种；
制备铝镍共掺碳酸钴前驱体：将反应温度升至45.5℃，在频率20Hz条件下搅拌，继续反应釜中的碳酸钴晶种中，并流加入氯化钴溶液、硫酸镍溶液、硫酸铝溶液和低浓度碳酸钠溶液；其中，氯化钴溶液的流量为15L/h，硫酸铝溶液的流量为1.5L/h，硫酸镍溶液的流量为1.5L/h；通过PLC控制系统调节低浓度碳酸钠溶液的流量维持晶种生长阶段的pH值为7.0-7.2；当反应釜内的反应溶液的体积为反应釜体积的80％时，开始浓缩，除掉上清液，浓缩过程中，反应溶液的体积保持在反应釜体积的80％，直到反应生成的物料的D50为18.3μm，停止投料，得到碳酸钴浆料；
将所得碳酸钴浆料离心过滤，所得滤质用温度为60℃的纯水液洗涤，纯水溶液中纯水的浓度为25g/L，洗涤时间为30min；再次离心过滤，所得滤质在110℃下干燥12h,至滤质的水分含量小于1.1％后，过300目振动筛，得到铝镍 共掺碳酸钴前驱体。
对比例6
本实施例提供了一种铝镍共掺碳酸钴前驱体的制备方法，包括以下步骤：
配制溶液：分别配制混合盐溶液、碳酸钠溶液、氨水溶液、碳酸钠底液，其中，混合溶液中，氯化钴中钴离子的浓度为130g/L,铝离子的浓度为1.28g/L，硫酸镍溶液中镍的浓度为0.3g/L；碳酸钠溶液中碳酸钠的浓度为120g/L，氨水溶液中氨水的质量分数为10％，碳酸钠底液中碳酸钠的浓度为40g/L；
制备碳酸钴晶种：向300L反应釜中加入碳酸钠底液，碳酸钠底液的体积以淹没最下层搅拌桨为准，底液的pH值为8.5，然后在温度为45.3℃、频率20Hz条件下搅拌，并流加入混合溶液和碳酸钠溶液，混合溶液的流量为7.5L/h；通过PLC控制系统调节碳酸钠溶液的流量维持晶种合成阶段的pH值为7.3-7.4，并流15h，直到反应生成的物料的D50为7.3μm，停止投料，得到碳酸钴晶种；
制备铝镍共掺碳酸钴前驱体：将反应温度升至45.7℃，在频率20Hz条件下搅拌，继续反应釜中的碳酸钴晶种中，并流加入混合溶液和碳酸钠溶液，混合溶液的流量为15L/h，通过PLC控制系统调节碳酸钠溶液的流量维持晶种生长阶段的pH值为7.2-7.4；同时并流加入氨水，控制反应体系中氨水的浓度为0.5-1g/L；当反应釜内的反应溶液的体积为反应釜体积的80％时，开始浓缩，除掉上清液，浓缩过程中，反应溶液的体积保持在反应釜体积的80％，直到反应生成的物料的D50为18.3μm，停止投料，得到碳酸钴浆料；
将所得碳酸钴浆料离心过滤，所得滤质用温度为60℃的纯水洗涤，洗涤时间为30min；再次离心过滤，所得滤质在110℃下干燥12h,至滤质的水分含量为2.6％后，过300目振动筛，得到铝镍共掺碳酸钴前驱体。
实验例1
测试所得碳酸钴晶种、铝镍共掺碳酸钴前驱体的形貌，结果如图1-6所示。图1为实施例1所得铝镍共掺碳酸钴前驱体的扫描电镜图，图2为实施例2所得铝镍共掺碳酸钴前驱体的扫描电镜图，图3为实施例1所得铝镍共掺碳酸钴前驱体的扫描电镜图，图4为对比例1所得铝镍共掺碳酸钴前驱体的扫描电镜图，图5为对比例2所得铝镍共掺碳酸钴前驱体的扫描电镜图，图6为对比例6所得铝镍共掺碳酸钴前驱体的扫描电镜图。从图1-3中可知看出，实施例1-3所 得铝镍共掺碳酸钴前驱体的表面为片状扦插堆积，无微粉，无产核，颗粒球形度好，粒度均一性好；CP截面图显示内部光滑，无偏析，元素分布均匀，颗粒内层紧密，外层有一定孔隙率，这与铝镍共掺碳酸钴前驱体内层为块状，外层为片状结构有关。从图4中可以看出，对比例1所得铝镍共掺碳酸钴前驱体外层严重偏析，CP截面图显示颗粒内外层偏析严重，有放射状偏析，元素分布不均匀，颗粒内层为紧密结构，这和一次颗粒为块状结构有关。从图5中可以看出，对比例2所得铝镍共掺碳酸钴前驱体表面为颗粒和片状扦插结构相混合，CP截面图显示颗粒内偏析严重，元素分布不均匀，颗粒内层紧密，外层有一定孔隙率，这和碳酸钴内层为块状而外层含有片状结构有关。从图6中可知看出，对比例6所得铝镍共掺碳酸钴前驱体颗粒表面严重偏析，有一定产核；CP截面图显示颗粒内偏析严重，元素分布不均匀，颗粒内紧密结构，这和一次颗粒为快状结构有关。
实验例2
将实施例1-5和对比例1-6所得铝镍共掺碳酸钴前驱体，在空气氛围中，以3℃/min的速率升温至300℃，煅烧3h；然后继续以3℃/min的速率升温至700℃，煅烧3h，随炉冷却后得到四氧化三钴。所得四氧化三钴分别与碳酸锂混合，煅烧制成钴酸锂。以钴酸锂为正极，金属锂片为负极，制备成扣式电池，充放电电压的范围为3.0-4.65V，在0.1C倍率下测试首次放电比容量，在0.5C倍率下循环50周，测试电池的容量保持率。测试结果如表1所示。
表1

从表1中可以看出，与对比例相比，实施例1-6的铝镍共掺碳酸钴前驱体所制得的电池具有较高的容量和较好的循环性能。
最后所应当说明的是，以上实施例用以说明本申请的技术方案而非对本申请保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普通技术人员应当理解，可以对本申请的技术方案进行修改或者同等替换，而不脱离本申请技术方案的实质和范围。

Claims (10)

  1. 一种铝镍共掺碳酸钴前驱体的制备方法，其包括以下步骤：
    配制溶液：分别配制钴盐溶液、镍盐溶液、铝盐溶液、高浓度碳酸氢铵溶液、低浓度碳酸氢铵溶液，碳酸氢铵底液；其中，钴盐溶液中钴离子的浓度为100-130g/L，镍盐溶液中镍离子的浓度为1-10g/L，铝盐溶液中铝离子的浓度为5-15g/L，高浓度碳酸氢铵溶液中碳酸氢铵的浓度为220-240g/L，低浓度碳酸氢铵溶液中碳酸氢铵的浓度为120-180g/L，碳酸氢铵底液中碳酸氢铵的浓度为40-120g/L；
    制备碳酸钴晶种：向反应釜中加入碳酸氢铵底液，然后在加热搅拌条件下，并流加入钴盐溶液、铝盐溶液和高浓度碳酸氢铵溶液，反应生成碳酸钴晶种；
    制备铝镍共掺碳酸钴前驱体：在加热搅拌的状态下，继续向反应釜中的碳酸钴晶种，并流加入钴盐溶液、镍盐溶液、铝盐溶液和低浓度碳酸氢铵溶液；反应所得物料进行过滤，所得滤质进行洗涤、干燥、粉碎，得到铝镍共掺碳酸钴前驱体。
  2. 如权利要求1所述的制备方法，其中，所述铝盐溶液中含有络合剂，络合剂和铝的摩尔比为络合剂：铝＝(0.5-1):10；优选地，所述络合剂为乙二胺四乙酸二钠、柠檬酸铵、柠檬酸、酒石酸、磺基水杨酸中的至少一种。
  3. 如权利要求1所述的制备方法，其中，所述制备碳酸钴晶种，加热的温度为38-45℃。
  4. 如权利要求1所述的制备方法，其中，所述制备碳酸钴晶种，底液的pH为8-9，加料过程中控制反应溶液的pH为7.5-8.1，钴盐溶液每小时的流量为反应釜体积的1％-5％。
  5. 如权利要求1所述的制备方法，其中，所述制备铝镍共掺碳酸钴前驱体，加热的温度为45-55℃。
  6. 如权利要求1所述的制备方法，其中，所述制备铝镍共掺碳酸钴前驱体，加料过程中控制反应溶液的pH为7.0-7.5，钴盐溶液每小时的流量为反应釜体积的1％-5％。
  7. 如权利要求1所述的制备方法，其中，如下(a)-(g)中的至少一项：
    (a)所述钴盐为氯化钴、硫酸钴、硝酸钴中的至少一种；
    (b)所述镍盐为硫酸镍、氯化镍中的至少一种；
    (c)所述铝盐为氯化铝、硫酸铝中的至少一种；
    (d)所述碳酸钴晶种的D50为7-13μm；
    (e)所述反应所得物料的D50为15-20μm；
    (f)所述洗涤的溶剂为纯水或碳酸氢铵溶液；
    (g)所述洗涤的温度为25-80℃。
  8. 一种铝镍共掺碳酸钴前驱体，其中，由权利要求1-7任一项所述制备方法制得。
  9. 一种正极材料前驱体，其中，所述正极材料前驱体的制备原料包括权利要求8所述的铝镍共掺碳酸钴前驱体。
  10. 一种正极材料，其中，所述正极材料的制备原料包括权利要求9所述的正极材料前驱体或权利要求8所述的铝镍共掺碳酸钴前驱体。
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