WO2022111093A1 - 一种三元正极材料及其制备方法和应用 - Google Patents

一种三元正极材料及其制备方法和应用 Download PDF

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WO2022111093A1
WO2022111093A1 PCT/CN2021/123409 CN2021123409W WO2022111093A1 WO 2022111093 A1 WO2022111093 A1 WO 2022111093A1 CN 2021123409 W CN2021123409 W CN 2021123409W WO 2022111093 A1 WO2022111093 A1 WO 2022111093A1
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positive electrode
sintering
preparation
compound
electrode material
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French (fr)
Inventor
赵文誉
阮丁山
刘婧婧
黄国捍
夏阳
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Priority to EP21896595.2A priority Critical patent/EP4253326A4/en
Publication of WO2022111093A1 publication Critical patent/WO2022111093A1/zh
Priority to US18/202,921 priority patent/US20230303407A1/en
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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
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • 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
    • 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
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
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    • 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
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    • C01P2004/51—Particles with a specific particle size distribution
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    • C01—INORGANIC CHEMISTRY
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    • 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
    • C01P2006/40—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 disclosure belongs to the field of lithium ion battery materials, and in particular relates to a ternary positive electrode material and a preparation method and application thereof.
  • the lithium-ion battery is generally composed of a positive electrode, a negative electrode, a separator and an electrolyte.
  • the performance of the positive electrode material directly determines the energy density, safety performance and service life of the lithium-ion battery.
  • lithium intercalation compounds are generally used for the positive electrode of lithium ion batteries, such as LiMn 2 O 4 , LiFePO 4 , LiCoO 2 , and ternary positive electrode material Li(Ni x Co y Mn z )O 2 .
  • ternary cathode materials have become the research focus of major battery manufacturers because of their higher energy density advantages.
  • the ternary cathode material will introduce micropowder during the preparation process, especially the single crystal ternary cathode material after the crushing process has a significant increase in the content of micropowder and surface defects. More micropowder and high residual lithium will affect the stirring and coating of the material in the electrode preparation process, making it easy to gel during the stirring process, and the coating thickness will be uneven, which will easily cause the battery capacity to be too low or If it is too high, lithium precipitation will be formed during the battery cycle, which will affect the battery life.
  • the present disclosure provides a ternary positive electrode material and a preparation method and application thereof in view of the deficiencies of the current traditional ternary positive electrode materials.
  • the nano-scale coating agent of the preparation method is uniformly dispersed in the solvent by stirring, and is brought to the surface of the substrate by the solvent, and the reaction between niobium compound, boron compound or titanium compound and residual lithium on the surface is introduced in the second sintering process , so as to bond the surrounding micropowder and reattach to the surface defect position of the sintered material.
  • the reaction will consume part of the residual lithium, and the generated lithium niobate, lithium borate or lithium titanate will evenly coat the surface of the material.
  • the preparation method will significantly reduce the content of micropowder and residual lithium on the surface of the material, which is helpful for stirring and coating during the electrode preparation process, and at the same time, the adhered micropowder will effectively repair the surface defects of the material, and cooperate with the coating layer to improve the three Cycling performance and rate capability of cathode materials.
  • a ternary positive electrode material its chemical formula is LiNi x Co y Mn (1-xy) MO 2 , wherein 0.5 ⁇ x ⁇ 1, y ⁇ 0, M contains elements selected from at least one of niobium, boron or titanium .
  • the D50 of the ternary cathode material is 3-6 ⁇ m
  • the K 90 is 1.0-1.6
  • the voltage window is 2.8-4.25V
  • the initial capacity is 198-202mAh/g at 0.1C rate
  • the 1C rate cycle is 50
  • Post-lap capacity retention is 90-96%.
  • a preparation method of a ternary positive electrode material comprising the following steps:
  • the compound is at least one of a niobium compound, a boron compound or a titanium compound.
  • the chemical formula of the precursor of nickel cobalt manganese is Ni x Co y Mn (1-xy) (OH) 2 , wherein 0.5 ⁇ x ⁇ 1, y ⁇ 0, and 1-xy>0.
  • the lithium source is at least one of LiOH or Li 2 CO 3 .
  • the adjusting pH to acidity is adjusting pH to 2-6.
  • step (1) the molar ratio of Li in the lithium source to the total metal elements in the precursor is (1-1.3):1.
  • the mass ratio of the ball mill is (0.5-2): 1, the rotation speed of the ball mill is 100-500rpm, and the time of the ball mill is 1-4h.
  • the first sintering is divided into two stages of sintering: the heating rate of the first stage sintering is 1-10°C/min, and the temperature of the first stage sintering is 400°C-800°C °C, the time is 2 ⁇ 8h, the temperature of the second stage sintering is 650°C ⁇ 1100°C, and the calcination time is 8 ⁇ 16h.
  • the atmosphere of the first sintering is air or oxygen.
  • step (2) the pulverization is jet pulverization.
  • the niobium compound is at least one of Nb 2 O 5 , NbS 2 , C 10 H 25 NbO 5 and C 4 H 4 NNbO 9 .
  • the boron compound is at least one of B 2 O 3 , H 3 BO 3 , LiBO 2 and Li 2 B 4 O 7 .
  • the titanium compound is at least one of TiO 2 , Li 2 TiO 3 and titanate.
  • step (3) the mass ratio of the sinter and the compound is (0.28-1):100.
  • the mass ratio of the sintered material and the mixed solution is (0.1-5):1.
  • step (3) the mass ratio of organic solvent and water in the mixed solution is (0.2-100):1.
  • the mass ratio of the organic solvent and water in the mixed solution is set to (0.2-100):1, because this ratio will effectively avoid the situation that the residual lithium on the surface of the material is washed and the lattice lithium is taken out.
  • the organic solvent is at least one of ethanol, acetone and isopropanol.
  • the constant temperature bath is one of a water bath or an oil bath.
  • the temperature of the constant temperature bath is 50°C to 150°C.
  • step (3) the rotational speed of the stirring is 50-500 rpm.
  • step (2) will bring micropowder, and in step (3), adding described sinter and compound to organic solvent and water mixed solution to mix and stir solve the problem of micropowder, and can also evenly disperse and coat agent and the purpose of reducing residual lithium.
  • the heating rate of the second sintering is 1-10°C/min
  • the temperature of the second sintering is 400°C-700°C
  • the time of the second sintering is 2 ⁇ 10h.
  • the atmosphere of the second sintering is air or oxygen.
  • Embodiments of the present disclosure further provide a lithium-ion battery, including the above-mentioned ternary positive electrode material.
  • the surrounding micropowder is bonded and reattached to the defect position on the surface of the material, which can greatly reduce the content of micropowder in the material.
  • the reaction will consume part of the residual lithium on the surface, and the generated lithium niobate, lithium borate or lithium titanate will be uniformly coated on the surface of the material, so as to obtain a ternary cathode material with excellent cycle and rate performance.
  • the liquid phase stirring can achieve the effect of uniformly dispersing the coating agent, and a suitable ratio of organic solvent and water can effectively avoid the situation that the residual lithium on the surface of the material is washed and the lattice lithium is taken out.
  • the method of the embodiment of the present disclosure significantly reduces the micropowder content of the material and the residual lithium on the surface, which is conducive to the simple and easy operation of stirring and coating in the electrode preparation process, without the need to introduce other complicated equipment, and the coating layer will increase the ternary Cycling performance and rate capability of cathode materials.
  • Example 1 is an XRD pattern of the ternary cathode material prepared in Example 1 of the disclosure
  • FIG. 3 is a graph showing the cycle stability of the ternary cathode materials prepared in Examples 1-3 and Comparative Examples 1-2 of the present disclosure at a voltage of 2.8-4.25V and a rate of 1C.
  • the conventional conditions or the conditions suggested by the manufacturer are used.
  • the raw materials and reagents used without the manufacturer's indication are conventional products that can be purchased from the market.
  • step (2) After taking out the bead mixture in step (1) and removing the ball mill beads, place it in a clean saggar and place it in a box furnace with a heating rate of 5°C/min, and keep it at 500°C for 4 hours first, The temperature was kept at 810°C for 12 hours, and after naturally cooling to room temperature, the calcined material was taken out for jet pulverization and sieving to obtain the sintered material;
  • the chemical formula of the ternary positive electrode material of this embodiment is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ⁇ LiNbO 3 .
  • step (2) After taking out the bead mixture in step (1) and removing the ball mill beads, place it in a clean saggar and place it in a box furnace with a heating rate of 5°C/min, and keep it at 500°C for 4 hours first, The temperature was kept at 810°C for 12 hours, and after naturally cooling to room temperature, the calcined material was taken out for jet pulverization and sieving to obtain the sintered material;
  • the chemical formula of the ternary positive electrode material of this embodiment is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ⁇ LiNbO 3 .
  • step (2) After taking out the bead mixture in step (1) and removing the ball mill beads, place it in a clean saggar and place it in a box furnace with a heating rate of 5°C/min, and keep it at 500°C for 4 hours first, The temperature was kept at 810°C for 12 hours, and after naturally cooling to room temperature, the calcined material was taken out for jet pulverization and sieving to obtain the sintered material;
  • the chemical formula of the ternary positive electrode material of this embodiment is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ⁇ LiNbO 3 .
  • step (2) After taking out the bead mixture in step (1) and removing the ball mill beads, place it in a clean saggar and place it in a box furnace with a heating rate of 5°C/min, and keep it at 500°C for 4h first, The temperature was kept at 810°C for 12 hours, and after naturally cooling to room temperature, the calcined material was taken out for jet pulverization and sieving to obtain the sintered material;
  • the chemical formula of the ternary positive electrode material in this embodiment is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ⁇ Li 3 BO 3 .
  • step (2) After taking out the bead mixture in step (1) and removing the ball mill beads, place it in a clean saggar and place it in a box furnace with a heating rate of 5°C/min, and keep it at 500°C for 4 hours first, The temperature was kept at 810°C for 12 hours, and after naturally cooling to room temperature, the calcined material was taken out for jet pulverization and sieving to obtain the sintered material;
  • the chemical formula of the ternary positive electrode material of this embodiment is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ⁇ Li 2 TiO 3 .
  • the preparation method of the ternary cathode material of this comparative example includes the following steps:
  • step (2) After taking out the bead mixture in step (1) and removing the ball mill beads, place it in a clean saggar and place it in a box furnace with a heating rate of 5°C/min, and keep it at 500°C for 4 hours first, The temperature was kept at 810°C for 12 hours, and after naturally cooling to room temperature, the calcined material was taken out for jet pulverization and sieving to obtain the sintered material;
  • the chemical formula of the ternary positive electrode material of this embodiment is LiNi 0.8 Co 0.1 Mn 0.1 O 2 ⁇ LiNbO 3 .
  • step (2) After taking out the bead mixture in step (1) and removing the ball mill beads, place it in a clean sagger and transfer it to a box furnace, the heating rate is 5°C/min, the temperature is kept at 500°C for 4 hours, and the temperature is 810°C. Incubate for 12h, naturally cool to room temperature, take out the calcined material for jet pulverization and sieving to obtain the sintered material;
  • step (3) Mix 0.43 g of Nb 2 O 5 with 100 g of the sintered material in step (2), transfer it to a box furnace, the heating rate is 5 °C/min, keep at 600 °C for 6 hours, and naturally cool at room temperature to obtain three Element cathode material.
  • each particle size of the finished material is larger than that of the sintered material.
  • the micropowder adheres to the defect position of the sintered material, which indicates that the preparation method of the embodiment of the present disclosure can effectively reduce the content of the micropowder and repair the surface in the material. defect.
  • the ternary positive electrode materials prepared in Examples 1-5 and Comparative Examples 1-2 were mixed evenly with conductive agent acetylene black and binder PVDF, and then an appropriate amount of N-methylpyrrolidone (NMP) solvent was added dropwise to prepare a slurry, It was evenly coated on the treated aluminum foil substrate, and after drying, it was punched into a circular positive electrode plate and assembled into a button battery for the test of buckling performance.
  • NMP N-methylpyrrolidone
  • the initial capacity and capacity retention rate of Examples 1-3 are better than those of Comparative Examples 1 and 2.
  • the I (003) /I (104) of Example 1 has the highest strength, which proves that the Li + /Ni 2+ mixing is the least, the layered structure is relatively complete, the initial capacity is also the highest, and the capacity retention rate is the best.
  • the I (003) /I (104) of Comparative Example 1 has the lowest strength, the lowest initial capacity, and the worst capacity retention rate, indicating that the ratio of organic solvent and water has a certain influence on its charge deduction performance.

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Abstract

本公开属于电池材料领域，公开了一种三元正极材料及其制备方法和应用，该三元正极材料的化学式为LiNi xCo yMn (1-x-y)MO 2，其中0.5≤x≤1，y≥0，M含有的元素选自铌、硼或钛中的至少一种。本公开通过引入铌化合物、硼化合物或钛化合物与表面残余锂的反应过程，以此粘合周围的微粉并重新附着到材料表面缺陷位置，可大幅度降低材料中的微粉含量并修复表面缺陷，同时反应将消耗部分的表面残余锂，生成的铌酸锂、硼酸锂或钛酸锂将均匀包覆在材料表面，从而获得循环和倍率性能较优异的三元正极材料。

Description

一种三元正极材料及其制备方法和应用 技术领域
本公开属于锂离子电池材料领域，具体涉及一种三元正极材料及其制备方法和应用。
背景技术
在电动汽车领域，人们普遍关心电动汽车的续航里程，随着各种电动汽车自燃事件的发生，人们也越来越重视电动汽车的安全性能。电动汽车最关键的部件在于锂离子电池，锂离子电池一般由正极、负极、隔膜和电解液组成，其中正极材料的性能直接决定了锂离子电池的能量密度、安全性能和使用寿命。目前锂离子电池正极普遍采用插锂化合物，如LiMn 2O 4、LiFePO 4、LiCoO 2、三元正极材料Li(Ni xCo yMn z)O 2。其中，三元正极材料因其具有更高的能量密度优势而成为了各大电池厂家的研究重点。
三元正极材料在制备过程中会引入微粉，尤其是单晶三元正极材料经过破碎工艺后微粉含量显著增加，表面缺陷也增加。较多的微粉和较高的残余锂将影响材料在电极制备过程中的搅浆和涂布，使得搅浆过程中容易产生凝胶化现象，涂布厚薄不均，容易引起电池容量过低或过高，在电池循环过程中形成析锂，影响电池寿命。
发明内容
本公开针对目前传统三元正极材料存在的不足，提供一种三元正极材料及其制备方法和应用。该制备方法的纳米级包覆剂通过搅拌均匀分散在溶剂中，并通过溶剂将其带到基材表面，通过第二次烧结过程中引入铌化合物、硼化合物或钛化合物与表面残余锂的反应，以此粘合周围的微粉并重新附着到烧料的表面缺陷位置，同时反应将消耗部分的残余锂，生成的铌酸锂、硼酸锂或钛酸锂将均匀包覆在材料表面。因此，该制备方法将明显降低材料的微粉含量和表面残余锂，有助于电极制备过程中的搅浆和涂布，同时粘附的微粉将有效修复材料表面缺陷，协同包覆层从而提高三元正极材料的循环性能和倍率性能。
有鉴于此，本公开采用以下技术方案：
一种三元正极材料，其化学式为LiNi xCo yMn (1-x-y)MO 2，其中0.5≤x≤1，y≥0，M含有的元素选自铌、硼或钛中的至少一种。
在一些实施例中，所述三元正极材料的D50为3-6μm，K 90为1.0-1.6，电压窗口在2.8-4.25V，0.1C倍率下初始容量198-202mAh/g，1C倍率循环50圈后容量保持率为90-96％。
一种三元正极材料的制备方法，包括如下步骤：
(1)将锂源、镍钴锰的前驱体混合，进行球磨，得到混合物；
(2)将所述混合物进行第一次烧结、粉碎、过筛，得到烧料；
(3)将所述烧料和化合物加入有机溶剂和水的混合液中混合，搅拌，蒸干，得到蒸干料；
(4)将所述蒸干料进行第二次烧结，冷却，即得所述三元正极材料；
步骤(3)中，所述化合物为铌化合物、硼化合物或钛化合物中的至少一种。
在一些实施例中，步骤(1)中，所述镍钴锰的前驱体的化学式为Ni xCo yMn (1-x-y)(OH) 2，其中0.5≤x≤1，y≥0，且1-x-y＞0。
在一些实施例中，步骤(1)中，所述锂源为LiOH或Li 2CO 3中的至少一种。
在一些实施例中，步骤(1)中，所述调pH至酸性是将pH调至2-6。
在一些实施例中，步骤(1)中，所述锂源中的Li和前驱体中总的金属元素的摩尔比为(1-1.3)：1。
在一些实施例中，步骤(1)中，所述球磨的珠料质量比为(0.5-2)：1，所述球磨的转速为100～500rpm，所述球磨的时间为1～4h。
在一些实施例中，步骤(2)中，所述第一次烧结分为两段烧结：第一段烧结的升温速率为1～10℃/min，第一段烧结的温度为400℃～800℃，时间为2～8h，第二段烧结的温度为650℃～1100℃，煅烧时间为8～16h。
在一些实施例中，步骤(2)中，所述第一次烧结的气氛为空气或氧气。
在一些实施例中，步骤(2)中，所述粉碎为气流粉碎。
在一些实施例中，步骤(3)中，所述铌化合物为Nb 2O 5、NbS 2、C 10H 25NbO 5和C 4H 4NNbO 9中至少一种。
在一些实施例中，步骤(3)中，所述硼化合物为B 2O 3、H 3BO 3、LiBO 2和Li 2B 4O 7中至少一种。
在一些实施例中，步骤(3)中，所述钛化合物为TiO 2、Li 2TiO 3和钛酸酯中至少一种。
在一些实施例中，步骤(3)中，所述烧料和化合物的质量比为(0.28-1):100。
在一些实施例中，步骤(3)中，所述烧料和混合液的质量比为(0.1-5)：1。
在一些实施例中，步骤(3)中，所述混合液中有机溶剂和水的质量比为(0.2-100):1。
将混合液中的有机溶剂和水的质量比设置为(0.2-100):1，是因为在这个比例下将有效避免材料表面残锂洗过而带出晶格锂的情况。
在另一实施例中，步骤(3)中，所述有机溶剂为乙醇、丙酮和异丙醇中至少一种。
在一些实施例中，步骤(3)中，所述恒温浴锅为水浴锅或油浴锅中的一种。
在一些实施例中，步骤(3)中，所述恒温浴锅的温度为50℃～150℃。
在一些实施例中，步骤(3)中，所述搅拌的转速为50～500rpm。
步骤(2)中的气流粉碎会带来微粉，而步骤(3)中的将所述烧料和化合物加入有机溶剂和水混合液中混合和搅拌解决了微粉的问题，还可均匀分散包覆剂和降残锂的目的。
在一些实施例中，步骤(4)中，所述第二次烧结的升温速率为1～10℃/min，第二次烧结的温度为400℃～700℃，第二次烧结的时间为2～10h。
在一些实施例中，步骤(4)中，所述第二次烧结的气氛为空气或氧气。
本公开实施例还提供一种锂离子电池，包括上述的三元正极材料。
本公开实施例的优点：
1.本公开实施例通过引入铌化合物、硼化合物或钛化合物与表面残余锂的反应过程，以此粘合周围的微粉并重新附着到材料表面的缺陷位置，可大幅度降低材料中的微粉含量，同时反应将消耗部分的表面残余锂，生成的铌酸锂、硼酸锂或钛酸锂将均匀包覆在材料表面，从而获得循环和倍率性能较优异的三元正极材。
2.本公开实施例通过液相搅拌可达到均匀分散包覆剂的作用，合适的有机溶剂和水比例将有效避免材料表面残锂洗过而带出晶格锂的情况。
3、本公开实施例的方法明显降低材料的微粉含量和表面残余锂，有助于电极制备过程中的搅浆和涂布简单易操作，无需引入其它复杂设备，同时包覆层将提高三元正极材料的循环性能和倍率性能。
附图说明
图1为本公开实施例1制备的三元正极材料的XRD图；
图2为本公开实施例1-3和对比例1制备的三元正极材料的SEM图；
图3为本公开实施例1-3和对比例1-2制备的三元正极材料在电压为2.8-4.25V，1C倍率下的循环稳定性曲线图。
具体实施方式
为了对本公开进行深入的理解，下面结合实例对本公开若干实验方案进行描述，以进一步的说明本公开的特点和优点，任何不偏离本公开主旨的变化或者改变能够为本领域的技术人员理解，本公开的保护范围由所属权利要求范围确定。
本公开实施例中未注明具体条件者，按照常规条件或者制造商建议的条件进行。所用 未注明生产厂商者的原料、试剂等，均为可以通过市售购买获得的常规产品。
实施例1
本实施例的三元正极材料的制备方法，包括如下步骤：
(1)称取300g的Ni 0.8Co 0.1Mn 0.1(OH) 2、142.53g的LiOH·H 2O和442.53g的球磨珠放置于球磨罐中，球磨转速300rpm，时间1h，得到珠料混合物；
(2)取出步骤(1)中的珠料混合物并除去球磨珠后，放置于干净的匣钵中并转置到箱式炉中，升温速率为5℃/min，先在500℃保温4h，再在810℃保温12h，自然冷却至室温后，取出煅烧料做气流粉碎、过筛，得到烧料；
(3)取0.43g的Nb 2O 5与100g步骤(3)中的烧料依次分散到100.43g的醇水混合液中(水：乙醇＝1:5)，并转置到油浴锅中搅拌(转速为300rpm，温度90℃)，直至混合液蒸干，得到蒸干料；
(4)取出(3)中的蒸干料并放置于干净的匣钵中，转置到箱式炉，升温速率为5℃/min，600℃保温6h，室温下自然冷却，得到三元正极材料。
本实施例的三元正极材料的化学式为LiNi 0.8Co 0.1Mn 0.1O 2·LiNbO 3。
实施例2
本实施例的三元正极材料的制备方法，包括如下步骤：
(1)称取300g的Ni 0.8Co 0.1Mn 0.1(OH) 2、142.53g的LiOH·H 2O和442.53g的球磨珠放置于球磨罐中，球磨转速300rpm，时间1h，得到珠料混合物；
(2)取出步骤(1)中的珠料混合物并除去球磨珠后，放置于干净的匣钵中并转置到箱式炉中，升温速率为5℃/min，先在500℃保温4h，再在810℃保温12h，自然冷却至室温后，取出煅烧料做气流粉碎、过筛，得到烧料；
(3)取0.43g的Nb 2O 5与100g步骤(3)中的烧料依次分散到200.56g的醇水混合液中(水：乙醇＝1:5)，并转置到油浴锅中搅拌(转速为300rpm，温度90℃)，直至混合液蒸干，得到蒸干料；
(4)取出(3)中的蒸干料并放置于干净的匣钵中，转置到箱式炉，升温速率为5℃/min，600℃保温6h，室温下自然冷却，得到三元正极材料。
本实施例的三元正极材料的化学式为LiNi 0.8Co 0.1Mn 0.1O 2·LiNbO 3。
实施例3
本实施例的三元正极材料的制备方法，包括如下步骤：
(1)称取300g的Ni 0.8Co 0.1Mn 0.1(OH) 2、142.53g的LiOH·H 2O和442.53g的球磨珠放置于球磨罐中，球磨转速300rpm，时间1h，得到珠料混合物；
(2)取出步骤(1)中的珠料混合物并除去球磨珠后，放置于干净的匣钵中并转置到箱式炉中，升温速率为5℃/min，先在500℃保温4h，再在810℃保温12h，自然冷却至室温后，取出煅烧料做气流粉碎、过筛，得到烧料；
(3)取0.86g的Nb 2O 5与100g步骤(3)中的烧料依次分散到100.43g的醇水混合液中(水：乙醇＝1:5)，并转置到油浴锅中搅拌(转速为300rpm，温度90℃)，直至混合液蒸干，得到蒸干料；
(4)取出(3)中的蒸干料并放置于干净的匣钵中，转置到箱式炉，升温速率为5℃/min，550℃保温6h，室温下自然冷却，得到三元正极材料。
本实施例的三元正极材料的化学式为LiNi 0.8Co 0.1Mn 0.1O 2·LiNbO 3。
实施例4
本实施例的三元正极材料的制备方法，包括如下步骤：
(1)称取300g的Ni 0.8Co 0.1Mn 0.1(OH) 2、142.53g的LiOH·H 2O和442.53g的球磨珠放置于球磨罐中，球磨转速300rpm，时间1h，得到珠料混合物；
(2)取出步骤(1)中的珠料混合物并除去球磨珠后，放置于干净的匣钵中并转置到箱式炉中，升温速率为5℃/min，先在500℃保温4h，再在810℃保温12h，自然冷却至室温后，取出煅烧料做气流粉碎、过筛，得到烧料；
(3)取0.97g的B 2O 3与100g步骤(3)中的烧料依次分散到100.43g的醇水混合液中(水：乙醇＝1:5)，并转置到油浴锅中搅拌(转速为300rpm，温度90℃)，直至混合液蒸干，得到蒸干料；
(4)取出(3)中的蒸干料并放置于干净的匣钵中，转置到箱式炉，升温速率为5℃/min，300℃保温6h，室温下自然冷却，得到三元正极材料。
本实施例的三元正极材料的化学式为LiNi 0.8Co 0.1Mn 0.1O 2·Li 3BO 3。
实施例5
本实施例的三元正极材料的制备方法，包括如下步骤：
(1)称取300g的Ni 0.8Co 0.1Mn 0.1(OH) 2、142.53g的LiOH·H 2O和442.53g的球磨珠放置于球 磨罐中，球磨转速300rpm，时间1h，得到珠料混合物；
(2)取出步骤(1)中的珠料混合物并除去球磨珠后，放置于干净的匣钵中并转置到箱式炉中，升温速率为5℃/min，先在500℃保温4h，再在810℃保温12h，自然冷却至室温后，取出煅烧料做气流粉碎、过筛，得到烧料；
(3)取0.51g的TiO 2与100g步骤(3)中的烧料依次分散到100.43g的醇水混合液中(水：乙醇＝1:5)，并转置到油浴锅中搅拌(转速为300rpm，温度90℃)，直至混合液蒸干，得到蒸干料；
(4)取出(3)中的蒸干料并放置于干净的匣钵中，转置到箱式炉，升温速率为5℃/min，600℃保温6h，室温下自然冷却，得到三元正极材料。
本实施例的三元正极材料的化学式为LiNi 0.8Co 0.1Mn 0.1O 2·Li 2TiO 3。
对比例1
本对比例的三元正极材料的制备方法，包括如下步骤：
(1)称取300g的Ni 0.8Co 0.1Mn 0.1(OH) 2、142.53g的LiOH·H 2O和442.53g的球磨珠放置于球磨罐中，球磨转速300rpm，时间1h，得到珠料混合物；
(2)取出步骤(1)中的珠料混合物并除去球磨珠后，放置于干净的匣钵中并转置到箱式炉中，升温速率为5℃/min，先在500℃保温4h，再在810℃保温12h，自然冷却至室温后，取出煅烧料做气流粉碎、过筛，得到烧料；
(3)取0.43g的Nb 2O 5与100g步骤(3)中的烧料依次分散到100.43g的醇水混合液中(水：乙醇＝10:1)，并转置到油浴锅中搅拌(转速为300rpm，温度90℃)，直至混合液蒸干，得到蒸干料；
(4)取出(3)中的蒸干料并放置于干净的匣钵中，转置到箱式炉，升温速率为5℃/min，600℃保温6h，室温下自然冷却，得到三元正极材料。
本实施例的三元正极材料的化学式为LiNi 0.8Co 0.1Mn 0.1O 2·LiNbO 3。
对比例2
本对比例的三元正极材料的制备方法，具体过程如下：
(1)称取300g的Ni 0.8Co 0.1Mn 0.1(OH) 2、142.53g的LiOH·H 2O和442.53g的球磨珠放置于球磨罐中，球磨转速300rpm，时间1h，得到珠料混合物；
(2)取出步骤(1)中的珠料混合物并除去球磨珠后，放置于干净的匣钵中并转置到 箱式炉中，升温速率为5℃/min，500℃保温4h，810℃保温12h，自然冷却至室温后，取出煅烧料做气流粉碎、过筛，得到烧料；
(3)取0.43g的Nb 2O 5与100g步骤(2)中的烧料混合，转置到箱式炉，升温速率为5℃/min，600℃保温6h，室温下自然冷却，得到三元正极材料。
实施例1-3和对比例1的粒度分布如表1所示：
表1实施例1-3和对比例1的粒度分布
名称 D10 D50 D90 D99
烧料 1.61 3.30 6.87 9.03
实施例1 2.51 4.61 8.15 11.72
实施例2 2.56 4.73 8.45 12.03
实施例3 2.43 4.58 8.22 11.82
对比例1 2.31 4.51 8.26 11.88
从表1中可知成品料的各粒度大小均大于烧料，结合图2的SEM可知微粉粘附到烧料缺陷位置，说明本公开实施例的制备方法可有效降低微粉含量并修复材料中的表面缺陷。
实施例1-3和对比例1的残余锂结果如表2所示：
表2实施例1-3和对比例1的残余锂
名称 LiOH Li 2CO 3 残余锂
烧料 0.4325 0.2398 0.1704
实施例1 0.2957 0.1961 0.1226
实施例2 0.3798 0.2404 0.1552
实施例3 0.3227 0.2075 0.1325
对比例1 0.1174 0.0780 0.0487
从表2可知实施例1-3的残余锂均比基材低，说明该制备方法可降低表面残余锂。对比例1的残余锂较低，与实施例1的区别为水醇比不同，说明水醇比对材料的残余锂和晶格锂有一定影响。
将实施例1-5和对比例1-2制备的三元正极材料与导电剂乙炔黑和粘结剂PVDF混合均匀，然后滴加适量的N-甲基吡咯烷酮(NMP)溶剂配制成浆料，将其均匀地涂布在处理好的铝箔基底上，干燥后冲压成圆形正极片并组装成纽扣电池用于扣电性能测试。测试结果如表3所示：
表3不同材料的测试性能
Figure PCTCN2021123409-appb-000001
从表3可知，实施例1-3的初始容量、容量保持率等均优于对比例1、2。其中，实施例1的I (003)/I (104)强度最高，证明Li +/Ni 2+混排最少，层状结构较完整，初始容量也最高，容量保持率最好。相反，对比例1的I (003)/I (104)强度最低，初始容量也最低，容量保持率最差，说明有机溶剂和水的比例对其扣电性能产生一定影响。
以上对本公开提供的一种三元正极材料及其制备方法和应用进行了详细的介绍，本文中应用了具体实施例对本公开的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本公开的方法及其核心思想，包括若干实施方式，并且也使得本领域的任何技术人员都能够实践本公开，包括制造和使用任何装置或系统，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开原理的前提下，还可以对本公开进行若干改进和修饰，这些改进和修饰也落入本公开权利要求的保护范围内。本公开专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。

Claims (10)

  1. 一种三元正极材料，其中，所述三元正极材料的化学式为LiNi xCo yMn (1-x-y)MO 2，其中0.5≤x≤1，y≥0，M含有的元素选自铌、硼或钛中的至少一种。
  2. 权利要求1所述的一种三元正极材料的制备方法，包括如下步骤：
    (1)将锂源、镍钴锰的前驱体混合，进行球磨，得到混合物；
    (2)将所述混合物进行第一次烧结、粉碎、过筛，得到烧料；
    (3)将所述烧料和化合物加入有机溶剂和水的混合液中混合，搅拌，蒸干，得到蒸干料；
    (4)将所述蒸干料进行第二次烧结，冷却，即得所述三元正极材料；
    其中，步骤(3)中，所述化合物为铌化合物、硼化合物或钛化合物中的至少一种。
  3. 根据权利要求2所述的制备方法，其中，步骤(1)中，所述镍钴锰的前驱体的化学式为Ni xCo yMn (1-x-y)(OH) 2，其中0.5≤x≤1，y≥0，且1-x-y＞0。
  4. 根据权利要求2所述的制备方法，其中，步骤(1)中，所述锂源为LiOH或Li 2CO 3中的至少一种。
  5. 根据权利要求2所述的制备方法，其中，步骤(2)中，所述第一次烧结分为两段烧结：第一段烧结的升温速率为1～10℃/min，第一段烧结的温度为400℃～800℃，时间为2～8h，第二段烧结的温度为650℃～1100℃，煅烧时间为8～16h。
  6. 根据权利要求2所述的制备方法，其中，步骤(3)中，所述铌化合物为Nb 2O 5、NbS 2、C 10H 25NbO 5、C 4H 4NNbO 9和LiNbO 3中至少一种；所述硼化合物为B 2O 3、H 3BO 3、LiBO 2和Li 2B 4O 7中至少一种；所述钛化合物为TiO 2、Li 2TiO 3和钛酸酯中至少一种。
  7. 根据权利要求2所述的制备方法，其中，步骤(3)中，所述烧料和所述化合物的质量比为(0.28-1):100；所述烧料和所述混合液的质量比为(0.1-5)：1；所述混合液中，所述有机溶剂和水的质量比为(0.2-100):1。
  8. 根据权利要求2所述的制备方法，其中，步骤(3)中，所述有机溶剂为乙醇、丙醇、异丙醇中至少一种。
  9. 根据权利要求2所述的制备方法，其中，步骤(4)中，所述第二次烧结的升温速率为1～10℃/min，第二次烧结的温度为400℃～700℃，第二次烧结的时间为2～10h；所述第二次烧结的气氛为空气或氧气。
  10. 一种电池，包括权利要求1所述的三元正极材料。
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