WO2024130862A1 - 高镍无钴材料及其制备方法 - Google Patents

高镍无钴材料及其制备方法 Download PDF

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Publication number
WO2024130862A1
WO2024130862A1 PCT/CN2023/081847 CN2023081847W WO2024130862A1 WO 2024130862 A1 WO2024130862 A1 WO 2024130862A1 CN 2023081847 W CN2023081847 W CN 2023081847W WO 2024130862 A1 WO2024130862 A1 WO 2024130862A1
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Prior art keywords
nickel cobalt
metal salt
nickel
precursor
free material
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French (fr)
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李爱霞
谢英豪
余海军
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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    • 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
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 present application relates to the technical field of electrode materials, and in particular to a high-nickel cobalt-free material and a preparation method thereof.
  • the synthesis process of the solid-phase method is simple, but the preparation of precursors by dry mixing of raw materials will lead to uneven raw material particle size, large particle size, and high temperature required for synthetic materials, resulting in poor electrochemical performance of the material.
  • the grains will melt to form secondary particles, thereby reducing the specific surface area and electrochemical performance of the high-nickel cobalt-free materials.
  • the purpose of the present application is to overcome the deficiencies in the prior art and to provide a high-nickel-cobalt-free material and a preparation method thereof that can ensure that the high-nickel-cobalt-free material has a higher specific surface area and better electrochemical properties.
  • a method for preparing a high-nickel cobalt-free material comprises the following steps:
  • a high temperature resistant oxide and a metal salt wherein the high temperature resistant oxide comprises SiO 2 and metal-doped TiO 2 , and the metal salt comprises a lithium source, a nickel source and an iron source;
  • the precursor is coated with the high temperature resistant oxide
  • the coated material is subjected to high-temperature sintering operation to obtain a high-nickel, cobalt-free material.
  • the lithium source is lithium sulfate.
  • the nickel source is nickel sulfate.
  • the iron source is ferric sulfate.
  • the alkali solution includes sodium hydroxide and ammonia water.
  • the concentration of the metal salt in the metal salt solution is 1.0 mol/L to 1.2 mol/L.
  • the molar ratio of the SiO 2 and the metal-doped TiO 2 in the high temperature resistant oxide is 1:(0.3-0.5).
  • the mass ratio of the lithium source, the nickel source and the iron source is 1:(0.9-1):(0-0.1).
  • the metal in the metal-doped TiO 2 is Zn, Ce, La or Fe.
  • the metal-doped TiO 2 is obtained by a sol-gel method.
  • the adding of alkali solution to the metal salt solution for mixing and filtering and drying operation comprises the following steps:
  • the alkali solution and the metal salt solution are mixed to obtain a precipitate precursor
  • the precipitate precursor is filtered and dried.
  • the mixing and generating operation of the alkali solution and the metal salt solution is specifically performed by adding a portion of the alkali solution into a reactor, and then, under stirring conditions, simultaneously dropping the metal salt solution and the remaining alkali solution into the reactor for a mixed reaction.
  • the method for preparing the high-nickel cobalt-free material before the step of performing a low-temperature sintering operation on the precipitate, after the step of adding an alkali solution to the metal salt solution for mixing and filtering and drying, the method for preparing the high-nickel cobalt-free material further includes the following steps:
  • the precipitate is pulverized.
  • the method for preparing the high-nickel cobalt-free material further comprises the following steps:
  • the material after high temperature sintering operation is alkaline washed with lithium hydroxide solution.
  • adding lithium hydroxide to the precipitate for low temperature sintering comprises the following steps:
  • the material to be calcined is subjected to a low-temperature preliminary calcination treatment.
  • the material to be calcined is subjected to a low-temperature preliminary calcination treatment at a heating rate of 5°C to 6°C, and the temperature is raised to 380°C to 420°C and calcined for 2.8h to 3.5h.
  • the molar ratio of nickel iron elements to lithium elements in the material to be calcined is 1:1.05-1.2.
  • the precursor is coated with the high temperature resistant oxide, comprising the following steps:
  • the precursor coating is freeze-dried.
  • the coated material is subjected to a high temperature sintering operation, specifically, the coated material is subjected to a high temperature calcination at a heating rate of 5°C to 6°C, and the temperature is raised to 880°C to 920°C and calcined for 8.5h to 10h.
  • a high-nickel cobalt-free material is prepared by the method for preparing the high-nickel cobalt-free material described in any one of the above embodiments.
  • the preparation method of the high-nickel cobalt-free material of the present application configures a lithium source, a nickel source and an iron source to obtain a metal salt solution.
  • the obtained high-nickel cobalt-free material has a higher specific capacity, a higher specific surface area and better electrochemical properties.
  • the metal salt solution is reacted under the action of an alkaline solution to generate a precipitate, thereby better ensuring the mixing uniformity of the lithium, nickel and iron elements in the generated precipitate.
  • lithium hydroxide is added for low-temperature sintering, so that a precursor with a certain sintering pore structure is obtained by pre-sintering (low-temperature sintering).
  • the precursor Before high-temperature sintering, the precursor is coated with a high-temperature resistant oxide so that the outer layer of the precursor particles is coated with the high-temperature resistant oxide to form a layer structure. Then, the coated precursor is subjected to a high-temperature sintering operation, which effectively alleviates the problem of the precursor particles melting during high-temperature sintering to form secondary particles, thereby obtaining a high-nickel cobalt-free material with better electrochemical properties and a higher specific surface area.
  • FIG1 is a flow chart of a method for preparing a high-nickel cobalt-free material according to an embodiment of the present application
  • FIG2 is an electron microscope image of the high-nickel cobalt-free material of Example 1;
  • FIG3 is an electron microscope image of the high-nickel cobalt-free material of Comparative Example 2.
  • the present application provides a method for preparing a high-nickel cobalt-free material.
  • the following further explains the method for preparing a high-nickel cobalt-free material of the present application:
  • the high temperature resistant oxide includes SiO 2 and metal-doped TiO 2
  • the metal salt includes a lithium source, a nickel source, and an iron source. It can be understood that lithium is an indispensable part of the positive electrode material, and the addition of nickel can effectively improve the specific capacity of the positive electrode material.
  • Iron has the effect of increasing the lattice spacing, accelerating the diffusion of Li + in the positive electrode material, and inhibiting the migration of nickel to the lithium layer, thereby reducing
  • the mixing of transition metal cations hinders the transformation of the crystal structure from layered to spinel structure that hinders Li + transmission, and the high-temperature resistant oxide has good high-temperature resistance and can form a high-temperature resistant layer structure on the surface of the particles, reducing the contact of substances within the high-temperature resistant layer structure. Therefore, high-nickel cobalt-free materials are prepared by lithium source, nickel source and iron source, and the obtained high-nickel cobalt-free materials have higher specific capacity, higher specific surface area and better electrochemical properties.
  • the configuration operation on the metal salt is to fully mix the lithium source, the nickel source and the iron source to form a uniform metal salt solution, which better ensures the mixing uniformity of the lithium element, the nickel element and the iron element in the generated precipitate, thereby ensuring the electrochemical performance of the high-nickel cobalt-free material.
  • the precursor is coated with a high temperature resistant oxide.
  • the precursor is coated with a high temperature resistant oxide, so that the precursor having a certain sintered pore structure obtained by pre-sintering is coated with a high temperature resistant oxide before high temperature sintering, so that the outer layer of the precursor particles is coated with the high temperature resistant oxide to form a layer structure, effectively avoiding the problem of grain melting of the precursor particles during high temperature sintering to form secondary particles, thereby ensuring the specific surface area and electrochemical properties of the high nickel cobalt-free material.
  • the above-mentioned method for preparing high-nickel cobalt-free materials enables the lithium source, nickel source and iron source to be configured to obtain a metal salt solution, which is beneficial to achieving high specific capacity and high specific surface area of high nickel cobalt-free materials.
  • the method has the advantages of good accumulation and good electrochemical properties, and then the metal salt solution is reacted under the action of alkali solution to form a precipitate, which better ensures the mixing uniformity of lithium, nickel and iron elements in the generated precipitate, and lithium hydroxide is added after filtration for low-temperature sintering operation, so that the precursor with a certain sintered pore structure obtained by pre-sintering is coated with a high-temperature resistant oxide before high-temperature sintering, so that the outer layer of the precursor particles is coated with a layer structure formed by the high-temperature resistant oxide, and then the coated precursor is subjected to high-temperature sintering operation, which effectively reduces the problem of grain melting and formation of secondary particles during high-temperature sintering of the precursor particles, thereby better achieving the acquisition of high-nickel cobalt-free materials with good electrochemical properties and high specific surface area.
  • the lithium source is lithium sulfate.
  • the nickel source is nickel sulfate.
  • the iron source is ferric sulfate.
  • the alkali solution includes sodium hydroxide and ammonia.
  • the concentration of the metal salt in the metal salt solution is 1.0 mol/L to 1.2 mol/L.
  • the molar ratio of SiO2 and metal-doped TiO2 in the high temperature resistant oxide is 1:(0.3-0.5). It can be understood that the high temperature resistant oxide is attached to the precursor for high temperature sintering, which not only makes the high temperature resistant oxide act as a physical barrier layer to inhibit the melting of the precursor crystals to form secondary particles, but also makes the molar ratio of SiO2 and metal-doped TiO2 in the high temperature resistant oxide be 1:(0.3-0.5) for high temperature sintering with the precursor.
  • the conductivity of ions and electrons at the positive electrode interface is improved, and the transmission of lithium ions and electrons on the surface of the positive electrode particles during the electrochemical reaction is effectively promoted, and the electrochemical performance of the high nickel cobalt-free materials can be further improved.
  • the metal in the metal-doped TiO 2 is Zn, Ce, La or Fe.
  • the molar ratio of metal to TiO 2 in the metal-doped TiO 2 is (0.01-3):100.
  • a sol-gel method is used to obtain a high temperature resistant oxide.
  • obtaining a high temperature resistant oxide comprises the following steps:
  • liquid A and liquid B wherein liquid A includes anhydrous ethanol and butyl titanate, and liquid B includes anhydrous ethanol, acetic acid, deionized water, and metal nitrate;
  • the solution to be aged after the aging treatment is dried and roasted.
  • the volume ratio of anhydrous ethanol to butyl titanate in liquid A is (7-8):(2-3).
  • the volume ratio of anhydrous ethanol, acetic acid, deionized water and metal nitrate in liquid B is (7-8):1:(2-3):(0.5-1).
  • liquid A is added dropwise to liquid B for stirring and mixing, specifically, liquid A is added dropwise to liquid B, and then acid is added and stirred until the pH value is ⁇ 2.0.
  • the acid solution is nitric acid, and further, the acid solution is a 10% nitric acid solution.
  • the droplet speed of adding liquid A to liquid B is 0.3 mL/min to 0.7 mL/min, further, the droplet speed is 0.5 mL/min, and further, the droplet time is 2 h to 2.2 h.
  • the solution to be aged is subjected to an aging treatment, specifically, the solution to be aged is naturally aged, and further, the aging time is 2h to 2.2h.
  • the aged solution is dried and calcined, comprising the following steps:
  • the dried solution is subjected to calcination.
  • the aged solution is dried at a temperature of 75°C to 85°C, and further, the aged solution is dried in an oven, and further, the drying time is 2.8h to 3.2h.
  • the dried solution is calcined at a temperature of 500° C. to 520° C., and further, the dried solution is calcined in a muffle furnace. Furthermore, the calcination time is 2.8 h to 3.2 h.
  • the dried solution is calcined in an oxygen atmosphere.
  • the lithium source, the nickel source and the iron source are configured by adding the metal salt into deionized water for mixing and stirring.
  • the mass ratio of the lithium source, the nickel source and the iron source is 1:(0.9-1):(0-0.1).
  • the mass ratio of the lithium source, the nickel source and the iron source is 1:0.98:0.02.
  • adding alkali solution to the metal salt solution for mixing and filtering and drying comprises the following steps:
  • the alkali solution and the metal salt solution are mixed to obtain a precipitate precursor
  • the precipitate precursor is filtered and dried.
  • the alkali solution and the metal salt solution are mixed and generated by adding part of the alkali solution into the reactor, and then, under stirring, the metal salt solution and the remaining alkali solution are simultaneously added dropwise into the reactor for a mixed reaction.
  • the alkali solution includes 8 mol/L sodium hydroxide solution and 12 mol/L ammonia solution.
  • adding part of the alkali solution into the reactor specifically includes adding part of 8 mol/L sodium hydroxide solution and part of 12 mol/L ammonia solution into the reactor until the pH of the alkali solution in the reactor is 11-12.
  • the metal salt solution and the remaining alkali solution are simultaneously added dropwise to the reactor for mixed reaction at a stirring speed of 200 r/min to 500 r/min.
  • the metal salt solution and the remaining alkali solution are simultaneously added dropwise to the reactor to mix and react until the pH value is 11 to 12, wherein the dropping speed is 0.5 mL/min to 1.0 mL/min, and further, the dropping speed is 0.8 mL/min.
  • a mixture of 8 mol/L sodium hydroxide solution and 12 mol/L ammonia solution and a metal salt solution are simultaneously added dropwise to a reactor for mixed reaction.
  • the metal salt solution and the remaining alkali solution are simultaneously dripped under stirring conditions. Add to the reactor and mix and react for 5h to 7h. The reaction temperature is 45°C to 55°C.
  • filtering and drying the precipitate precursor is specifically performed by adding the precipitate precursor into a vacuum oven for drying at 90° C. to 110° C.
  • the precipitate precursor is added into a vacuum oven for drying for 5 h to 6 h.
  • the precipitate is pulverized, specifically by placing the precipitate in a ball mill for ball milling.
  • the precipitate is crushed until the particle size of the precipitate is 3 ⁇ m to 5 ⁇ m.
  • the method for preparing a high-nickel cobalt-free material before the step of performing a low-temperature sintering operation on the precipitate and after the step of adding an alkali solution to the metal salt solution to perform a drying operation, the method for preparing a high-nickel cobalt-free material further comprises the following steps:
  • the precipitate is crushed.
  • the method for preparing the high-nickel cobalt-free material further comprises the following steps:
  • the material obtained after the high temperature sintering operation is subjected to alkaline washing treatment using lithium hydroxide solution.
  • lithium hydroxide is added to the precipitate for low temperature sintering, comprising the following steps:
  • the material to be calcined is subjected to a preliminary calcination treatment at a low temperature.
  • the material to be calcined is subjected to a low-temperature preliminary calcination treatment at a heating rate of 5°C to 6°C, and when the temperature is raised to 380°C to 420°C, the material is kept at this temperature and calcined for 2.8h to 3.5h.
  • the material to be calcined is subjected to a low-temperature preliminary calcination treatment in an oxygen atmosphere.
  • the molar ratio of nickel iron elements to lithium elements in the calcined material is 1:1.05-1.2.
  • the molar ratio of nickel iron elements to lithium elements in the calcined material is 1:1:1.1.
  • the method for preparing a high nickel cobalt-free material before the step of coating the precursor with a high temperature resistant oxide and after the step of performing a low temperature preliminary calcination on the calcined material, the method for preparing a high nickel cobalt-free material further includes the following step: cooling the precursor.
  • the precursor is cooled to room temperature.
  • the precursor is coated with a high temperature resistant oxide, comprising the following steps:
  • the precursor is spray-frozen by using a high temperature resistant oxide to obtain a precursor coating
  • the precursor coating is freeze-dried.
  • a high temperature resistant oxide is used to spray freeze the precursor, specifically: the precursor is placed in a fluidized bed, the temperature of the fluidized bed is adjusted to below -4°C, and then, atomized high temperature resistant oxide is introduced into the fluidized bed to spray coat the precursor, so that the high temperature resistant oxide adheres to and freezes around the precursor.
  • the spray amount of the high temperature resistant oxide is 2% of the total mass of the precursor, ensuring sufficient coverage of the precursor.
  • the precursor coating is freeze-dried at a temperature of -40°C to -45°C for 20h to 24h.
  • the coated material is subjected to a high temperature sintering operation in an oxygen atmosphere.
  • lithium hydroxide solution is used to perform alkaline washing on the material after high temperature sintering operation. It can be understood that the material after high temperature sintering operation is treated with lithium hydroxide to make SiO2 in the precursor react to generate silicate treatment, and the formed lithium ions will not introduce impurities into the precursor, that is, the content of SiO2 in the precursor is effectively reduced, thereby reducing the decrease in the gram capacity of the high nickel cobalt-free material, and better ensuring the high nickel cobalt-free material. High specific capacity.
  • the material after high-temperature sintering operation is alkaline washed for 25 minutes to 35 minutes with a lithium hydroxide solution of 0.5 mol/L to 0.6 mol/L, thereby ensuring the reduction of the content of SiO2 of the high-temperature resistant oxide in the precursor, that is, while ensuring the high specific capacity of the high-nickel cobalt-free material, it is further ensured that the high-temperature resistant oxide in the precursor has an improvement effect on the electrochemical properties of the high-nickel cobalt-free material.
  • the present application also provides a high-nickel cobalt-free material, which is prepared by the preparation method of the high-nickel cobalt-free material of any of the above embodiments.
  • the above-mentioned high-nickel cobalt-free material is prepared by the preparation method of high-nickel cobalt-free material, has a high specific surface area and good electrochemical properties, thereby better ensuring the cycle performance and capacity retention rate of the lithium-ion battery containing the high-nickel cobalt-free material.
  • the preparation method of the high-nickel cobalt-free material of the present application configures the lithium source, the nickel source and the iron source to obtain a metal salt solution, which is beneficial to realizing the high-nickel cobalt-free material with high specific capacity, high specific surface area and good electrochemical performance. Then, the metal salt solution is reacted under the action of alkaline solution to generate a precipitate, which better ensures the mixing uniformity of the lithium, nickel and iron elements in the generated precipitate.
  • lithium hydroxide is added for low-temperature sintering, so that before the pre-sintering to obtain a precursor with a certain sintered pore structure, the precursor is coated with a high-temperature resistant oxide before high-temperature sintering, so that the outer layer of the precursor particles is coated with the high-temperature resistant oxide to form a layer structure, and then the coated precursor is subjected to high-temperature sintering, which effectively reduces the problem of the precursor particles melting during high-temperature sintering to form secondary particles, thereby better achieving the acquisition of high-nickel cobalt-free materials with good electrochemical properties and high specific surface area.
  • Lithium sulfate, nickel sulfate and iron sulfate were obtained according to the stoichiometric ratio of LiNi 0.98 Fe 0.02 O 2 , that is, the molar ratio was 1:0.98:0.02, and deionized water was added to prepare a mixed solution with a total metal salt concentration of 1.0 mol/L;
  • step (3) (4) coating the surface of the material obtained in step (3) with a layer of high temperature resistant oxide (a mixture of Fe- TiO2 and SiO2 , wherein the molar ratio of Fe- TiO2 to SiO2 is 1:0.4) by spray freezing coating: placing the material obtained in step (3) in a fluidized bed, lowering the temperature of the fluidized bed to -4°C, introducing an atomized liquid containing the high temperature resistant oxide (the spray amount of the high temperature resistant oxide is 2% of the total mass of the precursor after the initial calcination), so that the atomized liquid is coated and frozen on the surface after the initial calcination, and then freeze-drying the material coated with the high temperature resistant oxide at -40°C for 24 hours;
  • a layer of high temperature resistant oxide a mixture of Fe- TiO2 and SiO2 , wherein the molar ratio of Fe- TiO2 to SiO2 is 1:0.4
  • step (4) placing the material obtained in step (4) in an oxygen atmosphere, heating the temperature to 900° C. at a rate of 5° C./min and maintaining the temperature for 9 h to obtain a high-nickel cobalt-free material coated with Fe-TiO 2 and SiO 2 ;
  • Lithium sulfate, nickel sulfate and iron sulfate were obtained according to the stoichiometric ratio of LiNi 0.98 Fe 0.02 O 2 , that is, the molar ratio was 1:0.98:0.02, and deionized water was added to prepare a mixed solution with a total metal salt concentration of 1.0 mol/L;
  • step (3) (4) coating the surface of the material obtained in step (3) with a layer of high temperature resistant oxide (a mixture of La- TiO2 and SiO2 , wherein the molar ratio of La- TiO2 to SiO2 is 1:0.4) by a spray freezing coating method: placing the material obtained in step (3) in a fluidized bed, lowering the temperature of the fluidized bed to -4°C, introducing an atomized liquid containing the high temperature resistant oxide (the spray amount of the high temperature resistant oxide is 2% of the total mass of the precursor after the initial calcination), so that the atomized liquid is coated and frozen on the surface after the initial calcination, and then freeze-drying the material coated with the high temperature resistant oxide at -40°C for 24 hours;
  • a layer of high temperature resistant oxide a mixture of La- TiO2 and SiO2 , wherein the molar ratio of La- TiO2 to SiO2 is 1:0.4
  • step (4) placing the material obtained in step (4) in an oxygen atmosphere, heating the temperature to 900° C. at a rate of 5° C./min and maintaining the temperature for 9 h to obtain a high-nickel cobalt-free material coated with La-TiO 2 and SiO 2 ;
  • Lithium sulfate, nickel sulfate and iron sulfate were obtained according to the stoichiometric ratio of LiNi 0.98 Fe 0.02 O 2 , that is, the molar ratio was 1:0.98:0.02, and deionized water was added to prepare a mixed solution with a total metal salt concentration of 1.0 mol/L;
  • step (3) (4) coating the surface of the material obtained in step (3) with a layer of high temperature resistant oxide (a mixture of Ce- TiO2 and SiO2 , wherein the molar ratio of Ce- TiO2 to SiO2 is 1:0.4) by a spray freezing coating method: placing the material obtained in step (3) in a fluidized bed, lowering the temperature of the fluidized bed to -4°C, introducing an atomized liquid containing the high temperature resistant oxide (the spray amount of the high temperature resistant oxide is 2% of the total mass of the precursor after the initial calcination), so that the atomized liquid is coated and frozen on the surface after the initial calcination, and then freeze-drying the material coated with the high temperature resistant oxide at -40°C for 24 hours;
  • a layer of high temperature resistant oxide a mixture of Ce- TiO2 and SiO2 , wherein the molar ratio of Ce- TiO2 to SiO2 is 1:0.4
  • step (4) placing the material obtained in step (4) in an oxygen atmosphere, heating the temperature to 900° C. at a heating rate of 5° C./min and maintaining the temperature for 9 h to obtain a high-nickel cobalt-free material coated with Ce-TiO 2 and SiO 2 ;
  • Lithium sulfate, nickel sulfate and iron sulfate were obtained according to the stoichiometric ratio of LiNi 0.98 Fe 0.02 O 2 , that is, the molar ratio was 1:0.98:0.02, and deionized water was added to prepare a mixed solution with a total metal salt concentration of 1.0 mol/L;
  • step (3) (4) coating the surface of the material obtained in step (3) with a layer of high temperature resistant oxide (a mixture of Zn- TiO2 and SiO2 , wherein the molar ratio of Zn- TiO2 to SiO2 is 1:0.4) by spray freezing coating: placing the material obtained in step (3) in a fluidized bed, lowering the temperature of the fluidized bed to -4°C, introducing an atomized liquid containing the high temperature resistant oxide (the spray amount of the high temperature resistant oxide is 2% of the total mass of the precursor after the initial calcination), so that the atomized liquid is coated and frozen on the surface after the initial calcination, and then freeze-drying the material coated with the high temperature resistant oxide at -40°C for 24 hours;
  • a layer of high temperature resistant oxide a mixture of Zn- TiO2 and SiO2 , wherein the molar ratio of Zn- TiO2 to SiO2 is 1:0.4
  • step (4) placing the material obtained in step (4) in an oxygen atmosphere, heating the temperature to 900° C. at a heating rate of 5° C./min and keeping the temperature for 9 h to obtain a high-nickel cobalt-free material coated with Zn-TiO 2 and SiO 2 ;
  • Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the Fe element is not doped and the Fe-TiO 2 /SiO 2 is not coated.
  • a mixture of sodium hydroxide and ammonia water (the concentration of the sodium hydroxide solution is 8 mol/L, and the concentration of the ammonia solution is 12 mol/L) is added to the reactor to control the pH of the solution at 11.5 ⁇ 0.2, and then the sodium hydroxide solution and ammonia water (the volume ratio of the two is 4:1) and the metal salt solution are added dropwise to the reactor while stirring.
  • the reaction temperature is 50°C
  • the reaction time is 6 hours
  • the pH is controlled at 11.5 ⁇ 0.2.
  • the precipitate is filtered and washed to obtain a precipitate, and the precipitate is dried in a vacuum oven at 100°C for 5 hours and then ball-milled to obtain a precursor powder;
  • Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that it is not coated with M-TiO2/SiO2.
  • Lithium sulfate, nickel sulfate, and iron sulfate are obtained according to the stoichiometric ratio of LiNi 0.98 Fe 0.02 O 2 , that is, the molar ratio is 1:0.98:0.02, and deionized water is added to prepare a mixed solution with a total metal salt concentration of 1.0 mol/L;
  • step (3) (4) coating the surface of the material obtained in step (3) with a layer of high temperature resistant oxide (a mixture of Fe- TiO2 and SiO2 , wherein the molar ratio of Fe- TiO2 to SiO2 is 1:0.4) by a spray freezing coating method: placing the material obtained in step (3) in a fluidized bed, lowering the temperature of the fluidized bed to -4°C, introducing an atomized liquid containing the high temperature resistant oxide (the spray amount of the high temperature resistant oxide is 2% of the total mass of the precursor after the initial calcination), so that the atomized liquid is coated and frozen on the surface after the initial calcination, and then freeze-drying the precursor coated with the high temperature resistant oxide at -40°C for 24 hours;
  • a layer of high temperature resistant oxide a mixture of Fe- TiO2 and SiO2 , wherein the molar ratio of Fe- TiO2 to SiO2 is 1:0.4
  • step (4) The material obtained in step (4) is placed in an oxygen atmosphere, heated at a rate of 5°C/min, and heated to 900°C for 9 hours to obtain a high-nickel cobalt-free material coated with M- TiO2 and SiO2 .
  • Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that no alkaline washing step is performed.
  • the battery is assembled in a glove box filled with high-purity Ar gas, with the metal lithium sheet as the negative electrode, the polypropylene microporous membrane as the diaphragm, and 1MLiPF6 dimethyl carbonate (DMC)-ethylene carbonate (EC)-ethyl methyl carbonate (EMC) as the electrolyte, and a 2032-type button battery shell is used to assemble the button battery in an Ar-protected glove box;
  • DMC dimethyl carbonate
  • EC ethylene carbonate
  • EMC electrolyte
  • FIG2 is an electron microscope image of the high-nickel cobalt-free material of Example 1
  • FIG3 is an electron microscope image of the high-nickel cobalt-free material of Comparative Example 2. It can be seen from FIG2 and FIG3 that the high-nickel cobalt-free material of Example 1 has a smaller particle size than that of Comparative Example 2 and has a higher specific surface area.

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Abstract

本申请提供一种高镍无钴材料及其制备方法。所述高镍无钴材料的制备方法包括如下步骤：获取耐高温氧化物和金属盐，其中，耐高温氧化物包括SiO2和金属掺杂TiO2，金属盐包括锂源、镍源和铁源；对金属盐进行配置操作，得到金属盐溶液；向金属盐溶液中加入碱液进行混合生成-过滤干燥操作，得到沉淀物；向沉淀物中加入氢氧化锂进行低温烧结操作，得到前驱体；采用耐高温氧化物对前驱体进行包覆处理；对包覆处理后的材料进行高温烧结操作，得到高镍无钴材料。本申请的高镍无钴材料的制备方法确保了高镍无钴材料具备较高的比表面积以及较好的电化学性能。

Description

高镍无钴材料及其制备方法 技术领域
本申请涉及电极材料技术领域，特别是涉及一种高镍无钴材料及其制备方法。
背景技术
高压钴酸锂充电截止电压提高到4.4V时，放电比容量可以提高到160mAh/g，是目前最理想的正极材料之一，但钴是稀缺资源，价格昂贵且波动大，供应不稳定，对环境有害，以及锰的存在，均导致了锂离子电池存在高成本、高毒性和过渡金属严重溶解等问题。
在受政策及终端长续航里程诉求等影响下，新能源汽车动力电池对高能量密度锂离子电池需求的日益增长，由于镍可以提供较高的比容量，镍含量越高，比容量也越大，能较好地代替锂离子电池中钴的使用，进而大大地加快了高镍无钴材料发展和应用，高镍无钴材料的制备方法有固相法、共沉淀法、溶胶-凝胶法，其中固相法的合成工艺简单，但是采用原料干法混合方式制备前驱体，会导致原料颗粒大小不均匀，颗粒尺寸大，且合成材料所需温度较高，使得材料电化学性能较差，而且在实际生产中发现，掺杂了Ni的Li2CuO2正极材料在高温结晶过程中，由于颗粒细小会发生晶粒熔融形成二次颗粒，进而降低了高镍无钴材料的比表面积以及电化学性能。
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。
本申请的目的是克服现有技术中的不足之处，提供一种能确保高镍无钴材料具备较高的比表面积以及较好的电化学性能的高镍无钴材料及其制备方法。
本申请的目的是通过以下技术方案来实现的：
一种高镍无钴材料的制备方法，包括如下步骤：
获取耐高温氧化物和金属盐，其中，所述耐高温氧化物包括SiO2和金属掺杂TiO2，所述金属盐包括锂源、镍源和铁源；
对所述金属盐进行配置操作，得到金属盐溶液；
向所述金属盐溶液中加入碱液进行混合生成-过滤干燥操作，得到沉淀物；
向所述沉淀物中加入氢氧化锂进行低温烧结操作，得到前驱体；
采用所述耐高温氧化物对所述前驱体进行包覆处理；
对包覆处理后的材料进行高温烧结操作，得到高镍无钴材料。
在其中一个实施例中，所述锂源为硫酸锂。
在其中一个实施例中，所述镍源为硫酸镍。
在其中一个实施例中，所述铁源为硫酸铁。
在其中一个实施例中，所述碱液包括氢氧化钠和氨水。
在其中一个实施例中，所述金属盐溶液中金属盐的浓度为1.0mol/L～1.2mol/L。
在其中一个实施例中，所述耐高温氧化物中的所述SiO2和所述金属掺杂TiO2的摩尔比为1：(0.3～0.5)。
在其中一个实施例中，所述锂源、镍源和铁源的质量比为1:(0.9～1):(0～0.1)。
在其中一个实施例中，所述金属掺杂TiO2中的所述金属为Zn、Ce、La或Fe。
在其中一个实施例中，采用溶胶凝胶法获取所述金属掺杂TiO2。
在其中一个实施例中，所述向所述金属盐溶液中加入碱液进行混合生成-过滤干燥操作，包括如下步骤：
将所述碱液和所述金属盐溶液进行混合生成操作，得到沉淀物前驱体；
将所述沉淀物前驱体进行过滤干燥处理。
在其中一个实施例中，所述将所述碱液和所述金属盐溶液进行混合生成操作，具体为将部分所述碱液加入至反应釜中，接着，在搅拌条件下，将所述金属盐溶液和剩余的所述碱液同步滴加至所述反应釜中混合反应。
在其中一个实施例中，在对所述沉淀物进行低温烧结操作的步骤之前，在向所述金属盐溶液中加入碱液进行混合生成-过滤干燥操作的步骤之后，所述高镍无钴材料的制备方法还包括如下步骤：
对所述沉淀物进行粉碎处理。
在其中一个实施例中，在所述得到高镍无钴材料的步骤之前，在对包覆处理后的材料进行高温烧结操作的步骤之后，所述高镍无钴材料的制备方法还包括如下步骤：
采用氢氧化锂溶液对高温烧结操作后的材料进行碱洗处理。
在其中一个实施例中，向所述沉淀物中加入氢氧化锂进行低温烧结操作，包括如下步骤：
向所述沉淀物中加入氢氧化锂进行混合操作，得到待煅烧物；
对所述待煅烧物进行低温初步煅烧处理。
在其中一个实施例中，在升温速率为5℃～6℃的条件下，对所述待煅烧物进行低温初步煅烧处理，升温至380℃～420℃保温煅烧2.8h～3.5h。
在其中一个实施例中，所述待煅烧物中的镍铁元素和锂元素的摩尔比为1：1.05～1.2。
在其中一个实施例中，采用所述耐高温氧化物对所述前驱体进行包覆处理，包括如下步骤：
采用所述耐高温氧化物对所述前驱体进行喷雾冻结操作，得到前驱体包覆物；
对所述前驱体包覆物进行冷冻干燥处理。
在其中一个实施例中，对包覆处理后的材料进行高温烧结操作，具体为在升温速率为5℃～6℃的条件下对包覆处理后的材料进行高温煅烧，升温至880℃～920℃保温煅烧8.5h～10h。
一种高镍无钴材料，通过上述任一实施例所述的高镍无钴材料的制备方法制备得到。
与现有技术相比，本申请至少具有以下优点：
本申请的高镍无钴材料的制备方法，使得锂源、镍源和铁源进行配置操作得到金属盐溶液，得到的高镍无钴材料具有较高的比容量、较高的比表面积和较好的电化学性能，接着使得金属盐溶液在碱液的作用下反应生成沉淀物，较好地确保了生成的沉淀物中锂元素、镍元素和铁元素的混合均匀性，过滤后加入氢氧化锂进行低温烧结操作，使得在预烧(低温烧结)得到具有一定的烧结孔隙结构的前驱体，未进行高温烧结前即对该前驱体采用耐高温氧化物进行包覆处理，以使前驱体颗粒外层包覆耐高温氧化物形成层结构，接着对包覆处理后的前驱体进行高温烧结操作，有效地减轻了前驱体颗粒在高温烧结时发生晶粒熔融而形成二次颗粒的问题，进而获得了具有较好的电化学性能和较高的比表面积的高镍无钴材料。
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
为了更清楚地说明本申请实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本申请的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本申请一实施方式的高镍无钴材料的制备方法的流程图；
图2为实施例1的高镍无钴材料的电镜图；
图3为对比例2的高镍无钴材料的电镜图。
具体实施方式
为了便于理解本申请，下面将参照相关附图对本申请进行更全面的描述。附图中给出了本申请的较佳实施方式。但是，本申请可以以许多不同的形式来实现，并不限于本文所描述的实施方式。相反地，提供这些实施方式的目的是使对本申请的公开内容理解的更加透彻全面。
需要说明的是，当元件被称为“固定于”另一个元件，它可以直接在另一个元件上或者也可以存在居中的元件。当一个元件被认为是“连接”另一个元件，它可以是直接连接到另一个元件或者可能同时存在居中元件。本文所使用的术语“垂直的”、“水平的”、“左”、“右”以及类似的表述只是为了说明的目的，并不表示是唯一的实施方式。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本申请。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
本申请提供一种高镍无钴材料的制备方法。为了更好地理解本申请的高镍无钴材料的制备方法，以下对本申请的高镍无钴材料的制备方法做进一步的解释说明：
一实施方式的高镍无钴材料的制备方法包括如下步骤：
S100、获取耐高温氧化物和金属盐，其中，耐高温氧化物包括SiO2和金属掺杂TiO2，金属盐包括锂源、镍源和铁源。可以理解，锂为正极材料中不可或缺的部分，镍的加入能有效提高正极材料的比容量，铁具有增加晶格间距的作用，加快了Li+在正极材料中的扩散，同时抑制了镍向锂层的迁移，进而减少了 过渡金属阳离子的混排，且阻碍了晶体结构从层状向阻碍Li+传输的尖晶石状结构转变，而耐高温氧化物具有较好的耐高温性能，且能在颗粒表面形成耐高温的层结构，减少了耐高温的层结构内的物质的接触，因此，通过锂源、镍源和铁源进行高镍无钴材料的制备，得到的高镍无钴材料具有较高的比容量、较高的比表面积和较好的电化学性能。
S200、对金属盐进行配置操作，得到金属盐溶液。可以理解，对金属盐进行配置操作，即使得锂源、镍源和铁源充分混合形成均匀的金属盐溶液，较好地确保了生成的沉淀物中锂元素、镍元素和铁元素的混合均匀性，进而确保了高镍无钴材料的电化学性能。
S300、向金属盐溶液中加入碱液进行混合生成-过滤干燥操作，得到沉淀物。可以理解，金属盐溶液在碱液的作用下实现了沉淀物的充分生成，即确保了高镍无钴材料的生成率。
S400、向沉淀物中加入氢氧化锂进行低温烧结操作，得到前驱体，获得了锂元素、镍元素和铁元素均匀分散的前驱体。
S500、采用耐高温氧化物对前驱体进行包覆处理。可以理解，在向沉淀物中加入氢氧化锂进行低温烧结操作得到前驱体后即采用耐高温氧化物对前驱体进行包覆处理，使得在预烧得到具有一定的烧结孔隙结构的前驱体未进行高温烧结前即对该前驱体采用耐高温氧化物进行包覆处理，以使前驱体颗粒外层包覆耐高温氧化物形成层结构，有效地避免了前驱体颗粒在高温烧结时发生晶粒熔融而形成二次颗粒的问题，进而确保了高镍无钴材料的比表面积和电化学性能。
S600、对包覆处理后的材料进行高温烧结操作，得到高镍无钴材料。可以理解，对包覆处理后的材料进行高温烧结操作，获得了具有较好的电化学性能和较高的比表面积的高镍无钴材料。
上述的高镍无钴材料的制备方法，使得锂源、镍源和铁源进行配置操作得到金属盐溶液，有利于在实现高镍无钴材料具有较高的比容量、较高的比表面 积和较好的电化学性能，接着使得金属盐溶液在碱液的作用下反应生成沉淀物，较好地确保了生成的沉淀物中锂元素、镍元素和铁元素的混合均匀性，过滤后加入氢氧化锂进行低温烧结操作，使得在预烧得到具有一定的烧结孔隙结构的前驱体未进行高温烧结前即对该前驱体采用耐高温氧化物进行包覆处理，以使前驱体颗粒外层包覆耐高温氧化物形成的层结构，接着对包覆处理后的前驱体进行高温烧结操作，有效地减轻了前驱体颗粒在高温烧结时发生晶粒熔融而形成二次颗粒的问题，进而较好地实现了具有较好的电化学性能和较高的比表面积的高镍无钴材料的获得。
在其中一个实施例中，锂源为硫酸锂。
在其中一个实施例中，镍源为硫酸镍。
在其中一个实施例中，铁源为硫酸铁。
在其中一个实施例中，碱液包括氢氧化钠和氨水。
在其中一个实施例中，金属盐溶液中金属盐的浓度为1.0mol/L～1.2mol/L。
在其中一个实施例中，耐高温氧化物中的SiO2和金属掺杂TiO2的摩尔比为1：(0.3～0.5)。可以理解，使得耐高温氧化物附着于前驱体中进行高温烧结，不仅较好地使得耐高温氧化物作为物理阻隔层抑制前驱体结晶的熔融而形成二次颗粒，而且配合使得耐高温氧化物中的SiO2和金属掺杂TiO2的摩尔比为1：(0.3～0.5)用于配合前驱体进行高温烧结，针对含有高温烧结后得到的高镍无钴材料的锂电池，提升了正极界面离子与电子的传导能力，有效的促进了电化学反应过程中锂离子与电子在正极颗粒表面的传输，并且还可进一步地提升的高镍无钴材料的电化学性能。
在其中一个实施例中，金属掺杂TiO2中的金属为Zn、Ce、La或Fe。
在其中一个实施例中，金属掺杂TiO2中金属与TiO2的摩尔比为(0.01-3)：100。
在其中一个实施例中，采用溶胶凝胶法获取耐高温氧化物。
在其中一个实施例中，获取耐高温氧化物，包括如下步骤：
获取A液和B液，A液包括无水乙醇和钛酸丁酯，B液包括无水乙醇、醋酸、去离子水和硝酸金属盐；
将A液滴加至B液中进行搅拌混合操作，得到待陈化溶液；
对待陈化溶液进行陈化处理；
对陈化处理后的待陈化溶液进行烘干焙烧处理。
在其中一个实施例中，A液中的无水乙醇和钛酸丁酯的体积比为(7～8):(2～3)。
在其中一个实施例中，B液中的无水乙醇、醋酸、去离子水和硝酸金属盐的体积比为(7～8):1:(2～3)：(0.5～1)。
在其中一个实施例中，将A液滴加至B液中进行搅拌混合操作，具体为将A液滴加至B液中，接着加入酸液搅拌至pH≤2.0。
在其中一个实施例中，酸液为硝酸，进一步地，酸液为10％的硝酸溶液。
在其中一个实施例中，将A液滴加至B液中滴加速度为0.3mL/min～0.7mL/min，进一步地，滴加速度速度为0.5mL/min，更进一步地，滴加时间为2h～2.2h。
在其中一个实施例中，对待陈化溶液进行陈化处理，具体为将待陈化溶液自然陈化，进一步地，陈化时间为2h～2.2h。
在其中一个实施例中，对陈化处理后的溶液进行烘干焙烧处理，包括如下步骤：
对陈化处理后的溶液进行烘干处理；
对烘干处理后的溶液进行焙烧处理。
在其中一个实施例中，在温度为75℃～85℃的条件下，对陈化处理后的溶液进行烘干处理，进一步地，在烘箱中对陈化处理后的溶液进行烘干处理，更进一步地，烘干时间为2.8h～3.2h。
在其中一个实施例中，在温度为500℃～520℃的条件下，对烘干处理后的溶液进行焙烧处理，进一步地，在马弗炉中对烘干处理后的溶液进行焙烧处理， 更进一步地，焙烧时间为2.8h～3.2h。
在其中一个实施例中，在氧气气氛中，对烘干处理后的溶液进行焙烧处理。
在其中一个实施例中，对锂源、镍源和铁源进行配置操作，具体为将金属盐加入至去离子水中进行混合搅拌。
在其中一个实施例中，锂源、镍源和铁源的质量比为1:(0.9～1):(0～0.1)。
在其中一个实施例中，锂源、镍源和铁源的质量比为1:0.98:0.02。
在其中一个实施例中，向金属盐溶液中加入碱液进行混合生成-过滤干燥操作，包括如下步骤：
将碱液和金属盐溶液进行混合生成操作，得到沉淀物前驱体；
将沉淀物前驱体进行过滤干燥处理。
在其中一个实施例中，将碱液和金属盐溶液进行混合生成操作，具体为将部分碱液加入至反应釜中，接着，在搅拌条件下，将金属盐溶液和剩余的碱液同步滴加至反应釜中混合反应。
在其中一个实施例中，碱液包括8mol/L的氢氧化钠溶液和12mol/L的氨水溶液。
在其中一个实施例中，将部分碱液加入至反应釜中具体为将部分8mol/L的氢氧化钠溶液和部分12mol/L的氨水溶液加入至反应釜中至反应釜中的碱液的pH为11～12。
在其中一个实施例中，在搅拌速度为的200r/min～500r/min条件下，将金属盐溶液和剩余的碱液同步滴加至反应釜中混合反应。
在其中一个实施例中，在搅拌条件下，将金属盐溶液和剩余的碱液同步滴加至反应釜中混合反应至pH为11～12，其中，滴加速度为0.5mL/min～1.0mL/min，进一步地，滴加速度为0.8mL/min。
在其中一个实施例中，在搅拌条件下，将8mol/L的氢氧化钠溶液和12mol/L的氨水溶液的混合液与金属盐溶液同步滴加至反应釜中混合反应。
在其中一个实施例中，在搅拌条件下，将金属盐溶液和剩余的碱液同步滴 加至反应釜中混合反应5h～7h，反应温度为45℃～55℃。
在其中一个实施例中，将沉淀物前驱体进行过滤干燥处理具体为在90℃～110℃条件下，将沉淀物前驱体加入至真空烘箱中进行干燥。
在其中一个实施例中，将沉淀物前驱体加入至真空烘箱中进行干燥5h～6h。
在其中一个实施例中，对沉淀物进行粉碎处理，具体为将沉淀物置于球磨机中进行球磨。
在其中一个实施例中，对沉淀物进行粉碎处理至沉淀物的粒径为3μu～5μm。
在其中一个实施例中，在对沉淀物进行低温烧结操作的步骤之前，且在向金属盐溶液中加入碱液进行生成干燥操作的步骤之后，高镍无钴材料的制备方法还包括如下步骤：
对沉淀物进行粉碎处理。
在其中一个实施例中，在得到高镍无钴材料的步骤之前，且在对包覆处理后的材料进行高温烧结操作的步骤之后，高镍无钴材料的制备方法还包括如下步骤：
采用氢氧化锂溶液对高温烧结操作后得到的材料进行碱洗处理。
在其中一个实施例中，向沉淀物中加入氢氧化锂进行低温烧结操作，包括如下步骤：
向沉淀物中加入氢氧化锂进行混合操作，得到待煅烧物；
对待煅烧物进行低温初步煅烧处理。
在其中一个实施例中，在升温速率为5℃～6℃的条件下，对待煅烧物进行低温初步煅烧处理，升温至380℃～420℃时保温煅烧2.8h～3.5h。
在其中一个实施例中，在氧气气氛中对待煅烧物进行低温初步煅烧处理。
在其中一个实施例中，待煅烧物中的镍铁元素和锂元素的摩尔比为1：1.05～1.2。
在其中一个实施例中，待煅烧物中的镍铁元素和锂元素的摩尔比为1：1：1.1。
在其中一个实施例中，在采用耐高温氧化物对前驱体进行包覆处理的步骤之前，且在对待煅烧物进行低温初步煅烧处理的步骤之后，高镍无钴材料的制备方法还包括如下步骤：对前驱体进行冷却处理。
在其中一个实施例中，对前驱体进行冷却处理至室温。
在其中一个实施例中，采用耐高温氧化物对前驱体进行包覆处理，包括如下步骤：
采用耐高温氧化物对前驱体进行喷雾冻结操作，得到前驱体包覆物；
对前驱体包覆物进行冷冻干燥处理。
在其中一个实施例中，采用耐高温氧化物对前驱体进行喷雾冻结操作，具体为：将前驱体置于流化床中，调整流化床的温度至低于-4℃，接着，向流化床内通入雾化的耐高温氧化物对前驱体进行喷雾包覆，以使耐高温氧化物于前驱体外周附着冻结。
在其中一个实施例中，耐高温氧化物的喷雾量为前驱体总质量的2％，确保了前驱体的充分包覆。
在其中一个实施例中，在温度为-40℃～-45℃的条件下，对前驱体包覆物进行冷冻干燥处理20h～24h。
在其中一个实施例中，对包覆处理后的材料进行高温烧结操作，具体为在升温速率为5℃～6℃的条件下对包覆处理后的材料进行高温煅烧，升温至880℃～920℃时保温煅烧8.5h～10h。
在其中一个实施例中，在氧气气氛中对包覆处理后的材料进行高温烧结操作。
在其中一个实施例中，采用0.5mol/L的氢氧化锂溶液对高温烧结操作后的材料进行碱洗处理。可以理解，采用氢氧化锂对高温烧结操作后的材料进行间隙处理，以使前驱体中耐高温氧化物的SiO2反应生成硅酸处理，而形成的锂离子也不会给前驱体引入杂质，即有效地减少了前驱体中耐高温氧化物的SiO2的含量，进而减轻了高镍无钴材料的克容量下降，较好地确保了高镍无钴材料的 高比容量。
在其中一个实施例中，采用0.5mol/L～0.6mol/L的氢氧化锂溶液对高温烧结操作后的材料进行碱洗处理25min～35min，确保了在前驱体中耐高温氧化物的SiO2的含量的减少的情况下，即在确保了高镍无钴材料的高比容量的情况下，进一步确保了前驱体中耐高温氧化物对高镍无钴材料的电化学性能起到的提升效果。
本申请还提供一种高镍无钴材料，通过上述任一实施例的高镍无钴材料的制备方法制备得到。
上述的高镍无钴材料，采用高镍无钴材料的制备方法制备得到，具有较高的比表面积和较好的电化学性能，进而较好地确保了含有高镍无钴材料的锂离子电池的循环性能和容量保持率。
与现有技术相比，本申请至少具有以下优点：
本申请的高镍无钴材料的制备方法，使得锂源、镍源和铁源进行配置操作得到金属盐溶液，有利于在实现高镍无钴材料具有较高的比容量、较高的比表面积和较好的电化学性能，接着使得金属盐溶液在碱液的作用下反应生成沉淀物，较好地确保了生成的沉淀物中锂元素、镍元素和铁元素的混合均匀性，过滤后加入氢氧化锂进行低温烧结操作，使得在预烧得到具有一定的烧结孔隙结构的前驱体未进行高温烧结前即对该前驱体采用耐高温氧化物进行包覆处理，以使前驱体颗粒外层包覆耐高温氧化物形成的层结构，接着对包覆处理后的前驱体进行高温烧结操作，有效地减轻了前驱体颗粒在高温烧结时发生晶粒熔融而形成二次颗粒的问题，进而较好地实现了具有较好的电化学性能和较高的比表面积的高镍无钴材料的获得。
以下列举一些具体实施例，需注意的是，下列实施例并没有穷举所有可能的情况，并且下述实施例中所用的材料如无特殊说明，均可从商业途径得到。
实施例1
(1)采用溶胶凝胶法制备Fe-TiO2粉末：将A液(无水乙醇：钛酸丁酯体积比＝7:2)缓慢滴加到B液(无水乙醇：醋酸：去离子水：硝酸铁体积比＝7:1:2：0.5，用10％HNO3调节pH≤2.0)，搅拌2h后，自然陈化12h。随后，放在80℃烘箱中干燥3h后置于500℃马弗炉中焙烧3h(氧气气氛)；其中，铁元素和钛元素的掺杂比为0.1％；
按照LiNi0.98Fe0.02O2化学计量比分别获取硫酸锂，硫酸镍和硫酸铁，即摩尔比分别为1:0.98:0.02，加入去离子水配置成金属盐总浓度为1.0mol/L的混合溶液；
(2)在反应釜中加入氢氧化钠溶液和氨水(氢氧化钠溶液浓度为8mol/L，氨水溶液浓度为12mol/L)，使得溶液中的pH控制在11.5±0.2，然后在搅拌的情况下往反应釜中同时滴加氢氧化钠溶液和氨水(二者体积占比为4:1)和金属盐溶液，反应温度50℃，反应时间6h，控制pH在11.5±0.2，最后，过滤洗涤得到沉淀，将沉淀在100℃真空烘箱中干燥5h后进行球磨处理，得到前驱体粉体；
(3)将前驱体粉体和氢氧化锂混合(镍铁元素和锂元素的摩尔比为1：1.1)，进行初次煅烧，即在氧气气氛中，升温速率为5℃/min，升温至400℃下进行第一次煅烧3h，随后冷却；
(4)采用喷雾冷冻涂覆法在步骤(3)得到的材料表面涂覆一层耐高温氧化物(Fe-TiO2和SiO2混合物，其中Fe-TiO2和SiO2的摩尔比为1：0.4)：将步骤(3)得到的材料放置在流化床，降低流化床的温度至-4℃，通入含有耐高温氧化物的雾化后的料液(耐高温氧化物的喷雾量相对于初次煅烧后的前驱体总质量的2％)，使其在初次煅烧后的表面进行涂覆冻结，随后对经耐高温氧化物涂覆后的材料进行在-40℃下冷冻干燥24h；
(5)将步骤(4)中得到的材料，置于氧气气氛中，升温速率为5℃/min，升温至900℃中保温9h，得到Fe-TiO2和SiO2共同包覆的高镍无钴材料；
(6)将高镍无钴材料放在0.5mol/L氢氧化锂溶液中水洗30min。
实施例2
(1)采用溶胶凝胶法制备La-TiO2粉末：将A液(无水乙醇：钛酸丁酯体积比＝7:2)缓慢滴加到B液(无水乙醇：醋酸：去离子水：硝酸镧体积比＝7:1:2：0.5，用10％HNO3调节pH≤2.0)，搅拌2h后，自然陈化12h。随后，放在80℃烘箱中干燥3h后置于500℃马弗炉中焙烧3h(氧气气氛)；其中，铁元素和钛元素的掺杂比为0.7％；
按照LiNi0.98Fe0.02O2化学计量比分别获取硫酸锂，硫酸镍和硫酸铁，即摩尔比分别为1:0.98:0.02，加入去离子水配置成金属盐总浓度为1.0mol/L的混合溶液；
(2)在反应釜中加入氢氧化钠溶液和氨水(氢氧化钠溶液浓度为8mol/L，氨水溶液浓度为12mol/L)，使得溶液中的pH控制在11.5±0.2，然后在搅拌的情况下往反应釜中同时滴加氢氧化钠溶液和氨水(二者体积占比为4:1)和金属盐溶液，反应温度50℃，反应时间6h，控制pH在11.5±0.2，最后，过滤洗涤得到沉淀，将沉淀在100℃真空烘箱中干燥5h后进行球磨处理，得到前驱体粉体；
(3)将前驱体粉体和氢氧化锂混合(镍铁元素和锂元素的摩尔比为1：1.1)，进行初次煅烧，即在氧气气氛中，升温速率为5℃/min，升温至400℃下进行第一次煅烧3h，随后冷却；
(4)采用喷雾冷冻涂覆法在步骤(3)得到的材料表面涂覆一层耐高温氧化物(La-TiO2和SiO2混合物，其中La-TiO2和SiO2的摩尔比为1：0.4)：将步骤(3)得到的材料放置在流化床，降低流化床的温度至-4℃，通入含有耐高温氧化物的雾化后的料液(耐高温氧化物的喷雾量相对于初次煅烧后的前驱体总质量的2％)，使其在初次煅烧后的表面进行涂覆冻结，随后对经耐高温氧化物涂覆后的材料进行在-40℃下冷冻干燥24h；
(5)将步骤(4)中得到的材料，置于氧气气氛中，升温速率为5℃/min，升温至900℃中保温9h，得到La-TiO2和SiO2共同包覆的高镍无钴材料；
(6)将高镍无钴材料放在0.5mol/L氢氧化锂溶液中水洗30min。
实施例3
(1)采用溶胶凝胶法制备Ce-TiO2粉末：将A液(无水乙醇：钛酸丁酯体积比＝7:2)缓慢滴加到B液(无水乙醇：醋酸：去离子水：硝酸铜体积比＝7:1:2：0.5，用10％HNO3调节pH≤2.0)，搅拌2h后，自然陈化12h。随后，放在80℃烘箱中干燥3h后置于500℃马弗炉中焙烧3h(氧气气氛)；其中，铁元素和钛元素的掺杂比为2％；
按照LiNi0.98Fe0.02O2化学计量比分别获取硫酸锂，硫酸镍和硫酸铁，即摩尔比分别为1:0.98:0.02，加入去离子水配置成金属盐总浓度为1.0mol/L的混合溶液；
(2)在反应釜中加入氢氧化钠溶液和氨水(氢氧化钠溶液浓度为8mol/L，氨水溶液浓度为12mol/L)，使得溶液中的pH控制在11.5±0.2，然后在搅拌的情况下往反应釜中同时滴加氢氧化钠溶液和氨水(二者体积占比为4:1)和金属盐溶液，反应温度50℃，反应时间6h，控制pH在11.5±0.2，最后，过滤洗涤得到沉淀，将沉淀在100℃真空烘箱中干燥5h后进行球磨处理，得到前驱体粉体；
(3)将前驱体粉体和氢氧化锂混合(镍铁元素和锂元素的摩尔比为1：1.1)，进行初次煅烧，即在氧气气氛中，升温速率为5℃/min，升温至400℃下进行第一次煅烧3h，随后冷却；
(4)采用喷雾冷冻涂覆法在步骤(3)得到的材料表面涂覆一层耐高温氧化物(Ce-TiO2和SiO2混合物，其中Ce-TiO2和SiO2的摩尔比为1：0.4)：将步骤(3)得到的材料放置在流化床，降低流化床的温度至-4℃，通入含有耐高温氧化物的雾化后的料液(耐高温氧化物的喷雾量相对于初次煅烧后的前驱体总质量的2％)，使其在初次煅烧后的表面进行涂覆冻结，随后对经耐高温氧化物涂覆后的材料进行在-40℃下冷冻干燥24h；
(5)将步骤(4)中得到的材料，置于氧气气氛中，升温速率为5℃/min，升温至900℃中保温9h，得到Ce-TiO2和SiO2共同包覆的高镍无钴材料；
(6)将高镍无钴材料放在0.5mol/L氢氧化锂溶液中水洗30min。
实施例4
(1)采用溶胶凝胶法制备Zn-TiO2粉末：将A液(无水乙醇：钛酸丁酯体积比＝7:2)缓慢滴加到B液(无水乙醇：醋酸：去离子水：硝酸锌体积比＝7:1:2：0.5，用10％HNO3调节pH≤2.0)，搅拌2h后，自然陈化12h。随后，放在80℃烘箱中干燥3h后置于500℃马弗炉中焙烧3h(氧气气氛)；其中，铁元素和钛元素的掺杂比为3％；
按照LiNi0.98Fe0.02O2化学计量比分别获取硫酸锂，硫酸镍和硫酸铁，即摩尔比分别为1:0.98:0.02，加入去离子水配置成金属盐总浓度为1.0mol/L的混合溶液；
(2)在反应釜中加入氢氧化钠溶液和氨水(氢氧化钠溶液浓度为8mol/L，氨水溶液浓度为12mol/L)，使得溶液中的pH控制在11.5±0.2，然后在搅拌的情况下往反应釜中同时滴加氢氧化钠溶液和氨水(二者体积占比为4:1)和金属盐溶液，反应温度50℃，反应时间6h，控制pH在11.5±0.2，最后，过滤洗涤得到沉淀，将沉淀在100℃真空烘箱中干燥5h后进行球磨处理，得到前驱体粉体；
(3)将前驱体粉体和氢氧化锂混合(镍铁元素和锂元素的摩尔比为1：1.1)，进行初次煅烧，即在氧气气氛中，升温速率为5℃/min，升温至400℃下进行第一次煅烧3h，随后冷却；
(4)采用喷雾冷冻涂覆法在步骤(3)得到的材料表面涂覆一层耐高温氧化物(Zn-TiO2和SiO2混合物，其中Zn-TiO2和SiO2的摩尔比为1：0.4)：将步骤(3)得到的材料放置在流化床，降低流化床的温度至-4℃，通入含有耐高温氧化物的雾化后的料液(耐高温氧化物的喷雾量相对于初次煅烧后的前驱体总质量的2％)，使其在初次煅烧后的表面进行涂覆冻结，随后对经耐高温氧化物涂覆后的材料进行在-40℃下冷冻干燥24h；
(5)将步骤(4)中得到的材料，置于氧气气氛中，升温速率为5℃/min，升温至900℃中保温9h，得到Zn-TiO2和SiO2共同包覆的高镍无钴材料；
(6)将高镍无钴材料放在0.5mol/L氢氧化锂溶液中水洗30min。
对比例1
(1)按照LiNiO2化学计量比分别获取硫酸锂和硫酸镍，即摩尔比分别为1:1，加入去离子水配置成金属盐总浓度为1.0mol/L混合溶液；
(2)在反应釜中加入氢氧化钠和氨水混合液(氢氧化钠溶液浓度为8mol/L，氨水溶液浓度为12mol/L)，使溶液pH为11.5±0.2，然后在搅拌的情况下往反应釜中同时滴加氢氧化钠溶液和氨水(二者体积比为4:1)和金属盐溶液，反应温度50℃，反应时间6h，控制pH在11.5±0.2，最后，过滤洗涤得到沉淀，将前沉淀在100℃真空烘箱中干燥5h后进行球磨处理，得到前驱体粉体；
(3)将前驱体粉体和氢氧化锂混合(镍铁元素和锂元素的摩尔比为1：1.1)，进行初次煅烧，即在氧气气氛中，升温速率为5℃/min，升温至400℃下进行第一次煅烧3h，随后升温至900℃中保温9h，得到高镍无钴材料；
(4)将高镍无钴材料放在0.5mol/L氢氧化锂溶液中水洗30min。
对比例1与实施例1的区别在于未掺杂Fe元素和未经Fe-TiO2/SiO2包覆。
对比例2
(1)按照LiNi0.98Fe0.02O2化学计量比分别获取硫酸锂、硫酸镍和硫酸铁，即摩尔比分别为1:0.98:0.02；加入去离子水配置成金属盐总浓度为1.0mol/L混合溶液；
(2)在反应釜中加入氢氧化钠和氨水混合液(氢氧化钠溶液浓度为8mol/L，氨水溶液浓度为12mol/L)以溶液的pH控制在11.5±0.2，然后在搅拌的情况下往反应釜中同时滴加氢氧化钠溶液和氨水(二者体积比为4:1)和金属盐溶液，反应温度50℃，反应时间6h，控制pH在11.5±0.2，最后，过滤洗涤得到沉淀，将沉淀在100℃真空烘箱中干燥5h后进行球磨处理，得到前驱体粉体；
(3)将前驱体粉体和氢氧化锂混合(镍铁元素和锂元素的摩尔比为1：1.1)，进行初次煅烧，即在氧气气氛中，升温速率为5℃/min，升温至400℃下进行第一次煅烧3h，随后升温至900℃中保温9h，得到高镍无钴材料；
(4)将高镍无钴材料放在0.5mol/L氢氧化锂溶液中水洗30min。
对比例2与实施例1的区别在于没有经过M-TiO2/SiO2包覆。
对比例3
(1)采用溶胶凝胶法制备Fe-TiO2粉末：将A液(无水乙醇：钛酸丁酯体积比＝7:2)缓慢滴加到B液(无水乙醇：醋酸：去离子水：硝酸铁体积比＝7:1:2：0.5，用10％HNO3调节pH≤2.0)，搅拌2h后，自然陈化12h。随后，放在80℃烘箱中干燥3h后置于500℃马弗炉中焙烧3h(氧气气氛)；
按照LiNi0.98Fe0.02O2化学计量比分别获取硫酸锂，硫酸镍，和硫酸铁，即摩尔比分别为1:0.98:0.02，加入去离子水配置成金属盐总浓度为1.0mol/L的混合溶液；
(2)在反应釜中加入氢氧化钠和氨水混合液(氢氧化钠溶液浓度为8mol/L，氨水溶液浓度为12mol/L)，以使pH为11.5±0.2，然后在搅拌的情况下往反应釜中同时滴加氢氧化钠溶液和氨水(二者体积比为4:1)和金属盐溶液，反应温度50℃，反应时间6h，控制pH在11.5±0.2，最后，过滤洗涤得到沉淀，将沉淀在100℃真空烘箱中干燥5h后进行球磨处理，得到前驱体粉体；
(3)将前驱体粉体和氢氧化锂混合(镍铁元素和锂元素的摩尔比为1：1.1)，进行初次煅烧，即在氧气气氛中，升温速率为5℃/min，升温至400℃下进行第一次煅烧3h，随后冷却；
(4)采用喷雾冷冻涂覆法在步骤(3)得到的材料表面涂覆一层耐高温氧化物(Fe-TiO2和SiO2混合物，其中Fe-TiO2和SiO2的摩尔比为1：0.4)：将步骤(3)得到的材料放置在流化床，降低流化床的温度至-4℃，通入含有耐高温氧化物的雾化后的料液(耐高温氧化物的喷雾量相对于初次煅烧后的前驱体总质量的2％)，使其在初次煅烧后的表面进行涂覆冻结，随后对经耐高温氧化物涂覆后的前驱体进行在-40℃下冷冻干燥24h；
(5)将步骤(4)中得到的材料，置于氧气气氛中，升温速率为5℃/min，升温至900℃中保温9h，得到M-TiO2和SiO2共同包覆的高镍无钴材料。
对比例3与实施例1的区别在于未经过碱洗步骤。
以下对实施例1至4和对比例1至3的高镍无钴材料配成扣式电池进行锂离子电池电化学性能测试，其步骤如下：按照质量比9.2：0.5：0.3的分别称取高镍无钴材料、乙炔黑和聚偏四氟乙烯，然后加入N-甲基吡咯烷酮(浓度与一般的正极浆料的浓度相同)，混合研磨均匀后，涂覆由于铝箔上，经70℃鼓风干燥9h后，在100℃真空干燥12h，随后，在充满高纯度Ar气体的手套箱中装配电池，金属锂片为负极，聚丙烯微孔膜作为隔膜，1MLiPF6的碳酸二甲酯(DMC)-乙烯碳酸酯(EC)-碳酸甲乙酯(EMC)为电解液，采用2032型扣式电池壳在Ar保护的手套箱中组装成扣式电池；
使得各扣式电池在25℃、2.5V～4.5V的条件下进行电化学性能测试，结果如表1所示：
表1：扣式电池的电化学性能
由表1可以看到，实施例1至4的高镍无钴材料相比较于对比例1至3的均高镍无钴材料均具有较高的放电比容量、较好的循环性能和较好的循环容量保持率；
由表1还可以看到，对比例1和对比例2的区别在于有无Fe掺杂，而经过Fe掺杂后的高镍无钴材料的循环性能和循环容量保持率均增加；
由表1还可以看到，对比例2和实施例1的区别在于有无包覆层，可以看到经过M-TiO2/SiO2包覆的正极材料的首圈放电比容量、100次循环后放电比容量、循环保持率明显增加；
由表1还可以看到，实施例1至4经过M-TiO2/SiO2包覆和碱洗的高镍无钴材料循环性能和循环容量保持率较优，而对比例3未经过碱洗的高镍无钴材料的首圈放电比容量、100次循环后放电比容量、循环保持率均低于实施例1至4；
图2为实施例1的高镍无钴材料的电镜图；图3为对比例2的高镍无钴材料的电镜图，从图2和图3中可以看出，实施例1的高镍无钴材料相比较于对比例2的粒径较小，具有较高的比表面积。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (10)

  1. 一种高镍无钴材料的制备方法，其中，包括如下步骤：
    获取耐高温氧化物和金属盐，其中，所述耐高温氧化物包括SiO2和金属掺杂TiO2，所述金属盐包括锂源、镍源和铁源；
    对所述金属盐进行配置操作，得到金属盐溶液；
    向所述金属盐溶液中加入碱液进行混合生成-过滤干燥操作，得到沉淀物；
    向所述沉淀物中加入氢氧化锂进行低温烧结操作，得到前驱体；
    采用所述耐高温氧化物对所述前驱体进行包覆处理；
    对包覆处理后的材料进行高温烧结操作，得到所述高镍无钴材料。
  2. 根据权利要求1所述的高镍无钴材料的制备方法，其中，所述锂源为硫酸锂；
    可选地，所述镍源为硫酸镍；
    可选地，所述铁源为硫酸铁；
    可选地，所述碱液包括氢氧化钠和氨水；
    可选地，所述金属盐溶液中金属盐的浓度为1.0mol/L～1.2mol/L；
    可选地，所述耐高温氧化物中的所述SiO2和所述金属掺杂TiO2的摩尔比为1：(0.3～0.5)，
    可选地，所述锂源、镍源和铁源的质量比为1:(0.9～1):(0～0.1)；
    可选地，所述金属掺杂TiO2中的所述金属为Zn、Ce、La或Fe。
  3. 根据权利要求1所述的高镍无钴材料的制备方法，其中，采用溶胶凝胶法获取所述金属掺杂TiO2。
  4. 根据权利要求1所述的高镍无钴材料的制备方法，其中，向所述金属盐溶液中加入碱液进行混合生成-过滤干燥操作，包括如下步骤：
    将所述碱液和所述金属盐溶液进行混合生成操作，得到沉淀物前驱体；
    将所述沉淀物前驱体进行过滤干燥处理。
  5. 根据权利要求4所述的高镍无钴材料的制备方法，其中，所述将所述碱液和所述金属盐溶液进行混合生成操作，具体为将部分所述碱液加入至反应釜中， 接着在搅拌条件下，将所述金属盐溶液和剩余的所述碱液同步滴加至所述反应釜中混合反应。
  6. 根据权利要求1所述的高镍无钴材料的制备方法，其中，在对所述沉淀物进行低温烧结操作的步骤之前，在向所述金属盐溶液中加入碱液进行混合生成-过滤干燥操作的步骤之后，还包括如下步骤：
    对所述沉淀物进行粉碎处理；
    可选地，在得到所述高镍无钴材料之前，在对包覆处理后的材料进行高温烧结操作之后，还包括如下步骤：
    采用氢氧化锂溶液对高温烧结操作后的材料进行碱洗处理。
  7. 根据权利要求1所述的高镍无钴材料的制备方法，其中，所述向所述沉淀物中加入氢氧化锂进行低温烧结操作，包括如下步骤：
    向所述沉淀物中加入氢氧化锂进行混合操作，得到待煅烧物；
    对所述待煅烧物进行低温初步煅烧处理。
  8. 根据权利要求7所述的高镍无钴材料的制备方法，其中，在升温速率为5℃～6℃的条件下，对所述待煅烧物进行低温初步煅烧处理，升温至380℃～420℃保温煅烧2.8h～3.5h；
    可选地，所述待煅烧物中的镍铁元素和锂元素的摩尔比为1：1.05～1.2。
  9. 根据权利要求1至8中任一项所述的高镍无钴材料的制备方法，其中，所述包覆处理包括如下步骤：
    采用所述耐高温氧化物对所述前驱体进行喷雾冻结操作，得到前驱体包覆物；
    对所述前驱体包覆物进行冷冻干燥处理；
    可选地，对所述包覆处理后的材料进行高温烧结操作，具体为在升温速率为5℃～6℃的条件下对所述包覆处理后的材料进行高温煅烧，升温至880℃～920℃保温煅烧8.5h～10h。
  10. 一种高镍无钴材料，其中，通过权利要求1至9中任一项所述的高镍无 钴材料的制备方法制备得到。
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CN113809294A (zh) * 2021-08-27 2021-12-17 西安理工大学 无钴高镍三元正极材料、制法和用于制备电池正极的方法

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CN119324216A (zh) * 2024-10-21 2025-01-17 北京理工大学 一种硫酸铁锂包覆的高镍层状正极材料的制备和应用

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