WO2023124051A1 - 一种镍钴锰酸锂高镍单晶正极材料及其制备方法 - Google Patents

一种镍钴锰酸锂高镍单晶正极材料及其制备方法 Download PDF

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WO2023124051A1
WO2023124051A1 PCT/CN2022/108807 CN2022108807W WO2023124051A1 WO 2023124051 A1 WO2023124051 A1 WO 2023124051A1 CN 2022108807 W CN2022108807 W CN 2022108807W WO 2023124051 A1 WO2023124051 A1 WO 2023124051A1
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nickel
positive electrode
electrode material
cobalt
lithium
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PCT/CN2022/108807
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English (en)
French (fr)
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许开华
李伟
刘德宠
谢军
廖宁靖
施杨
周晓燕
陈玉君
徐世国
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格林美（无锡）能源材料有限公司
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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
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the technical field of lithium batteries, in particular to a nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material and a preparation method thereof.
  • LiNi x Co y Mn 1-xy O 2 ternary cathode material has been widely used in lithium-ion secondary batteries because of its high specific capacity and energy density, low cost and relatively environment-friendly features, especially Under the current background, it has a broad development space in the automotive power battery market. With the improvement of cruising range, the current cathode materials are gradually developing in the direction of high nickel and high voltage. Single crystal cathode materials have attracted much attention due to their advantages of relatively high plate compaction and less gas production.
  • the purpose of the present invention is to overcome the above-mentioned technical deficiencies, propose a nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material and its preparation method, and solve the problem that high-nickel single-crystal positive electrode materials in the prior art are difficult to balance high capacity, large size and high dispersion technical issues.
  • the first aspect of the present invention provides a method for preparing nickel-cobalt lithium manganate high-nickel single crystal positive electrode material, comprising the following steps:
  • nickel-cobalt-manganese hydroxide with lithium source, zirconium oxide, tungsten oxide, and sodium carbonate for ball milling, and then perform primary sintering to obtain nickel-cobalt lithium manganate high-nickel single crystal positive electrode material intermediate after crushing; wherein, the primary sintering temperature 50-150°C higher than the normal sintering temperature;
  • the nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material intermediate is uniformly mixed with the coating agent, and then secondary sintering is performed to obtain the nickel-cobalt lithium manganate high-nickel single-crystal positive electrode material.
  • the second aspect of the present invention provides a nickel-cobalt lithium manganese oxide high-nickel single crystal positive electrode material, the nickel-cobalt lithium manganate high-nickel single crystal positive electrode material provided by the first aspect of the present invention nickel-cobalt lithium manganate high-nickel single crystal The preparation method of the cathode material is obtained.
  • the beneficial effects of the present invention include:
  • the present invention introduces tungsten oxide and sodium carbonate in a sintering process. Due to the existence of oxygen vacancies inside the high-nickel material and some sodium ions occupying lithium sites, the W-O octahedron will be distorted in different ways such as inclination and rotation, which will affect the crystallinity of the material. Cell and electronic structure have varying degrees of influence, not only can enhance the conductivity of the material, but also can change the particle shape, so that the primary particles can be refined, using the characteristics of the combination of tungsten oxide and sodium carbonate, combined with zirconia doped , at a higher primary sintering temperature, a high-nickel single crystal cathode material with high capacity, high dispersion and excellent cycle performance is obtained.
  • Fig. 1 is the SEM picture of the nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material that the embodiment 1 of the present invention provides;
  • Fig. 2 is the SEM picture of the nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material that comparative example 1 of the present invention provides;
  • Fig. 3 is the SEM figure of the nickel-cobalt lithium manganate high-nickel single-crystal positive electrode material that comparative example 2 of the present invention provides;
  • Fig. 4 is the SEM picture of the nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material that comparative example 3 of the present invention provides;
  • Fig. 5 is the SEM picture of the nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material that comparative example 4 of the present invention provides;
  • Fig. 6 is the SEM figure of the nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material that comparative example 5 of the present invention provides;
  • Fig. 7 is an SEM image of the nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material provided in Comparative Example 6 of the present invention.
  • the first aspect of the present invention provides a method for preparing nickel-cobalt lithium manganate high-nickel single crystal positive electrode material, comprising the following steps:
  • tungsten oxide and sodium carbonate are introduced as dopants in a sintering process. Due to the existence of oxygen vacancies inside the high-nickel material and some sodium ions occupying lithium sites, the W-O octahedron will be distorted in different ways such as tilt and rotation. It has different degrees of influence on the unit cell and electronic structure of the material, which can not only enhance the conductivity of the material, but also change the particle shape, so that the primary particles can be refined.
  • Using the characteristics of the combination of tungsten oxide and sodium carbonate, combined with Doped with zirconia, at a higher primary sintering temperature a high-nickel single crystal cathode material with high capacity, high dispersion and excellent cycle performance can be obtained.
  • the sintering temperature should not be too high. Too high will lead to excessive growth of single crystal, longer lithium ion transmission path, reduced ion conductivity, and reduced capacity and rate performance.
  • the chemical composition of nickel cobalt manganese hydroxide is: Ni x Co y Mn 1-xy (OH) 2 , 0.7 ⁇ x ⁇ 0.95, 0.02 ⁇ y ⁇ 0.25.
  • the chemical composition of the precursor of nickel-cobalt lithium manganate high-nickel single crystal positive electrode material is: Ni 0.80 Co 0.10 Mn 0.10 (OH) 2 .
  • the lithium source is at least one of lithium carbonate, lithium hydroxide, lithium nitrate, and lithium chloride; the molar ratio of nickel-cobalt-manganese hydroxide to lithium in the lithium source is 1: (1.01-1.1).
  • the molar ratio of nickel-cobalt-manganese hydroxide to zirconia, tungsten oxide and sodium carbonate is 1: (0.001-0.005): (0.001-0.005): (0.001-0.005), further 1: 0.002: 0.0016 : 0.002.
  • the primary sintering temperature is T 1
  • the normal sintering temperature is T 2
  • T 2 is a sintering DOE test of nickel-cobalt-manganese hydroxide and lithium source. After the nickel-cobalt-manganese single crystal positive electrode material-sintered material obtained by the above test is electrochemically tested, the discharge specific capacity The sintering temperature for maximum, best single crystal dispersion (ie, optimum sintering temperature).
  • the optimal sintering temperature is related to the molar ratio of transition metal elements and lithium ratio of nickel-cobalt-manganese hydroxide, and different nickel-cobalt-manganese hydroxides and different lithium ratios correspond to different optimal sintering temperatures. For example, when the lithium ratio of Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 to lithium hydroxide is 1.05, the optimum sintering temperature is 870°C.
  • the primary sintering time is 10-20 hours.
  • the type of coating agent is not limited, and those skilled in the art can select according to actual needs.
  • the coating agent can be an oxide or hydroxide of B, Al, Mg, V, Ti, P, Si, Y.
  • the coating agent is added in an amount of 0.05wt%-5wt% of the total amount of the nickel-cobalt lithium manganate high-nickel single-crystal cathode material intermediate.
  • the temperature of the secondary sintering is 200-600° C.
  • the time of the secondary sintering is 6-24 hours.
  • the present invention by forming a coating layer on the surface of the nickel-cobalt lithium manganese oxide high-nickel single crystal positive electrode material intermediate, the side reaction between the single crystal and the electrolyte can be reduced, and the service life of the battery can be further improved.
  • both the primary sintering process and the secondary sintering process are carried out under the condition of oxygen.
  • the second aspect of the present invention provides a nickel-cobalt lithium manganese oxide high-nickel single crystal positive electrode material, the nickel-cobalt lithium manganate high-nickel single crystal positive electrode material provided by the first aspect of the present invention nickel-cobalt lithium manganate high-nickel single crystal The preparation method of the cathode material is obtained.
  • Example 2 Compared with Example 1, the only difference is that the dopant is only zirconia.
  • Example 2 Compared with Example 1, the only difference is that no WO 3 is added to the dopant.
  • Example 2 Compared with Example 1, the difference is only that sodium carbonate is not added in the dopant.
  • Example 2 Compared with Example 1, the only difference is that zirconia is not added to the dopant.
  • Example 2 Compared with Example 1, the only difference is that the temperature of primary sintering is 870°C.
  • Example 2 Compared with Example 1, the only difference is that the temperature of primary sintering is 1050°C.
  • Example 1 of the present invention The positive electrode materials prepared in Example 1 of the present invention and Comparative Examples 1-6 were tested by SEM, and the test results are shown in FIGS. 1-7 and Table 1.
  • Example 1 of the present invention Mix the positive electrode materials prepared in Example 1 of the present invention and Comparative Examples 1-6 with conductive agent acetylene carbon black and binder PVDF according to the mass ratio of 92:4:4, and add an appropriate amount of 1-methyl-2-pyrrolidone Ball milled for 1 hour to form a slurry evenly coated on the aluminum sheet, dried and pressed to make a positive electrode sheet.
  • the charge and discharge voltage is 3.0-4.3V.
  • the first cycle is charged and discharged at 0.2C/0.2C, and then 1C/1C for 200 cycles. circle, and the results are shown in Table 1.
  • the nickel-cobalt lithium manganese oxide high-nickel single-crystal positive electrode material prepared in Example 1 of the present invention has large single crystal size, good dispersion, and high discharge specific capacity, and has Good cycle stability.
  • the high-nickel single crystal positive electrode material obtained in Comparative Example 1 has a larger average particle size, but it still has poor discharge specific capacity and cycle performance. The reason is that only zirconia was added in Comparative Example 1 , without the action of tungsten oxide and sodium carbonate, the sintering temperature is relatively high, and the electrochemical performance is still poor.
  • the high-nickel single-crystal positive electrode material obtained in Comparative Example 2 has a larger average particle size, but it still has poor specific discharge capacity and cycle performance.
  • the reason is that in Comparative Example 2, no Tungsten oxide, which cannot play the role of tungsten oxide in enhancing the conductivity and refining the primary particles in the system, ultimately leads to the poor electrochemical performance of the high-nickel single crystal positive electrode material obtained in Comparative Example 2.
  • Example 3 Compared with Example 1, the average particle size of the high-nickel single crystal cathode material obtained in Comparative Example 3 significantly reduces, and has poor discharge specific capacity and cycle performance simultaneously. The reason is that sodium carbonate is not added in Comparative Example 3, and its It cannot cooperate with tungsten oxide to increase the single crystal size and improve the dispersion, which finally leads to the poor electrochemical performance of the high-nickel single crystal positive electrode material obtained in Comparative Example 3.
  • Comparative Example 4 Compared with Example 1, the high-nickel single crystal positive electrode material obtained in Comparative Example 4 has a large single crystal size, good dispersion, and discharge specific capacity, but the cycle performance is poor. The reason is that Comparative Example 4 does not incorporate zirconia, resulting in crystal The structural stability is lower than that of Example 1.
  • Example 1 Compared with Example 1, the average particle size and cycle performance of the high-nickel single crystal positive electrode material obtained in Comparative Example 5 were significantly reduced. Small, poor dispersion, significantly reduced cycle performance.
  • Example 1 Compared with Example 1, the average particle size of the high-nickel single crystal positive electrode material obtained in Comparative Example 6 is significantly increased, but its discharge specific capacity and cycle performance are significantly reduced. The reason is that the sintering temperature of Comparative Example 6 is too high. This leads to excessive growth of single crystal, longer lithium ion transport path, lower ion conductivity, and lower capacity and rate performance.

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Abstract

本发明公开了一种镍钴锰酸锂高镍单晶正极材料及其制备方法。该制备方法，包括以下步骤：将镍钴锰氢氧化物与锂源、氧化锆、氧化钨、碳酸钠混合球磨，随后进行一次烧结，经粉碎后得到镍钴锰酸锂高镍单晶正极材料中间体；其中，一次烧结温度高出正常烧结温度50～150℃；将镍钴锰酸锂高镍单晶正极材料中间体与包覆剂混合均匀，随后进行二次烧结，得到镍钴锰酸锂高镍单晶正极材料。本发明通过在一次烧结过程中引入氧化钨和碳酸钠，不仅能够增强材料的导电性，还可以改变颗粒形貌，使得一次粒子得以细化，利用氧化钨和碳酸钠结合的这一特点，再结合氧化锆掺杂，在较高的一次烧结温度下，得到高容量、高分散性且循环性能优异的高镍单晶正极材料。

Description

一种镍钴锰酸锂高镍单晶正极材料及其制备方法 技术领域
本发明涉及锂电池技术领域，尤其是涉及一种镍钴锰酸锂高镍单晶正极材料及其制备方法。
背景技术
LiNi xCo yMn 1-x-yO 2三元正极材料因其较高的比容量和能量密度，较低的成本及相对环境友好的特点，在锂离子二次电池中得到了广泛的应用，特别是当下背景下，其在汽车动力电池市场具有广阔的发展空间。随着续航里程的提高，当下的正极材料正在逐步向高镍化、高电压方向发展。单晶正极材料因为相对高的极片压实和产气少的优势而备受关注。但是高镍单晶材料烧结过程中存在两个问题：一是当烧结温度略低时，尽管放电比容量高，但是单晶团聚，分散性差，导致循环性能下降，产气增加；二是当烧结温度偏高时，单晶尺寸大，分散性好，但放电比容量显著下降。
因此，如何制备具有高容量、大尺寸以及高分散性的高镍单晶正极材料仍是一个巨大的挑战。
发明内容
本发明的目的在于克服上述技术不足，提出一种镍钴锰酸锂高镍单晶 正极材料及其制备方法，解决现有技术中高镍单晶正极材料难以兼顾高容量、大尺寸以及高分散性的技术问题。
本发明的第一方面提供一种镍钴锰酸锂高镍单晶正极材料的制备方法，包括以下步骤：
将镍钴锰氢氧化物与锂源、氧化锆、氧化钨、碳酸钠混合球磨，随后进行一次烧结，经粉碎后得到镍钴锰酸锂高镍单晶正极材料中间体；其中，一次烧结温度高出正常烧结温度50～150℃；
将镍钴锰酸锂高镍单晶正极材料中间体与包覆剂混合均匀，随后进行二次烧结，得到镍钴锰酸锂高镍单晶正极材料。
本发明的第二方面提供一种镍钴锰酸锂高镍单晶正极材料，该镍钴锰酸锂高镍单晶正极材料通过本发明第一方面提供的镍钴锰酸锂高镍单晶正极材料的制备方法得到。
与现有技术相比，本发明的有益效果包括：
本发明通过在一次烧结过程中引入氧化钨和碳酸钠，由于高镍材料内部氧空位的存在和部分钠离子占据锂位，W-O八面体会发生倾斜、旋转等不同方式的畸变，对材料的晶胞及电子结构产生不同程度的影响，不仅能够增强材料的导电性，还可以改变颗粒形貌，使得一次粒子得以细化，利用氧化钨和碳酸钠结合的这一特点，再结合氧化锆掺杂，在较高的一次烧结温度下，得到高容量、高分散性且循环性能优异的高镍单晶正极材料。
附图说明
图1是本发明实施例1提供的镍钴锰酸锂高镍单晶正极材料的SEM图；
图2是本发明对比例1提供的镍钴锰酸锂高镍单晶正极材料的SEM图；
图3是本发明对比例2提供的镍钴锰酸锂高镍单晶正极材料的SEM图；
图4是本发明对比例3提供的镍钴锰酸锂高镍单晶正极材料的SEM图；
图5是本发明对比例4提供的镍钴锰酸锂高镍单晶正极材料的SEM图；
图6是本发明对比例5提供的镍钴锰酸锂高镍单晶正极材料的SEM图；
图7是本发明对比例6提供的镍钴锰酸锂高镍单晶正极材料的SEM图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明的第一方面提供一种镍钴锰酸锂高镍单晶正极材料的制备方法，包括以下步骤：
S1、将镍钴锰氢氧化物与锂源、氧化锆、氧化钨、碳酸钠混合球磨，随后进行一次烧结，经粉碎后得到镍钴锰酸锂高镍单晶正极材料中间体；其中，一次烧结温度高出正常烧结温度50～150℃；
S2、将镍钴锰酸锂高镍单晶正极材料中间体与包覆剂混合均匀，随后进行二次烧结，得到镍钴锰酸锂高镍单晶正极材料。
本发明通过在一次烧结过程中引入氧化钨和碳酸钠作为掺杂剂，由于高镍材料内部氧空位的存在和部分钠离子占据锂位，W-O八面体会发生倾斜、旋转等不同方式的畸变，对材料的晶胞及电子结构产生不同程度的影响，不仅能够增强材料的导电性，还可以改变颗粒形貌，使得一次粒子得以细化，利用氧化钨和碳酸钠结合的这一特点，再结合氧化锆掺杂，在较高的一次烧结温度下，得到高容量、高分散性且循环性能优异的高镍单晶正极材料。但是烧结的温度也不宜过高，过高将导致单晶过度生长，锂离 子传输路径较长，离子导电性降低，导致容量及倍率性能下降。
本发明中，镍钴锰氢氧化物的化学组成为：Ni xCo yMn 1-x-y(OH) 2，0.7≤x≤0.95,0.02≤y≤0.25。在本发明的一些具体实施方式中，镍钴锰酸锂高镍单晶正极材料前驱体的化学组成为：Ni 0.80Co 0.10Mn 0.10(OH) 2。
本发明中，锂源为碳酸锂、氢氧化锂、硝酸锂、氯化锂中的至少一种；镍钴锰氢氧化物与锂源中锂的摩尔比为1：(1.01～1.1)。
本发明中，镍钴锰氢氧化物与氧化锆、氧化钨、碳酸钠的摩尔比为1：(0.001～0.005)：(0.001～0.005)：(0.001～0.005)，进一步为1：0.002：0.0016：0.002。通过向体系中掺杂引入氧化钨、碳酸钠和氧化锆，得到分散性良好、放电比容量及循环性能优异的单晶材料。但引入的碳酸钠含量不宜过高，若加入量过多将会导致体系残碱量增加，不利于提高电池性能。
本发明中，一次烧结温度为T 1，正常烧结温度为T 2，且△T＝T 1-T 2＝50～150℃，进一步为60～100℃，更进一步为70～80℃。需要说明的是，正常烧结温度T 2为镍钴锰氢氧化物与锂源进行一次烧结DOE试验，由上述试验得到的镍钴锰单晶正极材料一烧料经过电化学测试后，放电比容量最大、单晶分散性最好的烧结温度(即，最佳烧结温度)。最佳烧结温度与镍钴锰氢氧化物的过渡金属元素摩尔比以及锂配比有关，不同的镍钴锰氢氧化物以及不同的锂配比均对应有不同的最佳烧结温度。例如，Ni 0.8Co 0.1Mn 0.1(OH) 2与氢氧化锂的锂配比为1.05时，最佳烧结温度为870℃。
本发明中，一次烧结的时间为10～20h。
本发明中，对包覆剂的种类不作限制，本领域技术人员可以根据实际需要进行选择。例如，包覆剂可以为B、Al、Mg、V、Ti、P、Si、Y的氧化物或氢氧化物。包覆剂的加入量为镍钴锰酸锂高镍单晶正极材料中间体总量的0.05wt％～5wt％。该过程中，二次烧结的温度为200～600℃，二次烧结时间为6～24h。本发明中，通过在镍钴锰酸锂高镍单晶正极材料中间体表面形成包覆层，能够减少单晶与电解液的副反应，进一步提高电池的使用 寿命。
本发明中，一次烧结过程和二次烧结过程均在氧气的条件下进行。
本发明的第二方面提供一种镍钴锰酸锂高镍单晶正极材料，该镍钴锰酸锂高镍单晶正极材料通过本发明第一方面提供的镍钴锰酸锂高镍单晶正极材料的制备方法得到。
实施例1
(1)称取2.0kg Ni 0.80Co 0.10Mn 0.10(OH) 2粉末、0.93kg LiOH·H 2O、5.78g纳米ZrO 2、8.10gWO 3和4.95g碳酸钠在球磨混合机混合均匀后，将混合料放在氧气气氛炉中进行煅烧，煅烧温度为950℃，烧结时间为15h，待反应结束后，经冷却、粉碎、过筛得到镍钴锰酸锂高镍单晶正极材料中间体；
(2)将4.65gY 2O 3与镍钴锰酸锂高镍单晶正极材料中间体混合均匀后于高氧气气氛中在500℃热处理10h，得到钇包覆的镍钴锰酸锂高镍单晶正极材料。
实施例2
(1)称取2.0kg Ni 0.80Co 0.10Mn 0.10(OH) 2粉末、0.93kg LiOH·H 2O、5.78g纳米ZrO 2、8.10gWO 3和4.95g碳酸钠在球磨混合机混合均匀后，将混合料放在氧气气氛炉中进行煅烧，煅烧温度为930℃，烧结时间为20h，待反应结束后，经冷却、粉碎、过筛得到镍钴锰酸锂高镍单晶正极材料中间体；
(2)将4.65gY 2O 3与镍钴锰酸锂高镍单晶正极材料中间体混合均匀后于高氧气气氛中在500℃热处理10h，得到钇包覆的镍钴锰酸锂高镍单晶正极材料。
实施例3
(1)称取2.0kg Ni 0.80Co 0.10Mn 0.10(OH) 2粉末、0.93kg LiOH·H 2O、5.78g纳米ZrO 2、8.10gWO 3和4.95g碳酸钠在球磨混合机混合均匀后，将混合料放在氧气气氛炉中进行煅烧，煅烧温度为970℃，烧结时间为10h，待反应结束后，经冷却、粉碎、过筛得到镍钴锰酸锂高镍单晶正极材料中间体；
(2)将4.65gY 2O 3与镍钴锰酸锂高镍单晶正极材料中间体混合均匀后于高氧气气氛中在500℃热处理10h，得到钇包覆的镍钴锰酸锂高镍单晶正极材料。
对比例1
与实施例1相比，区别仅在于，掺杂剂仅为氧化锆。
对比例2
与实施例1相比，区别仅在于，掺杂剂中未加入WO 3。
对比例3
与实施例1相比，区别仅在于，掺杂剂中未加入碳酸钠。
对比例4
与实施例1相比，区别仅在于，掺杂剂中未加入氧化锆。
对比例5
与实施例1相比，区别仅在于，一次烧结的温度为870℃。
对比例6
与实施例1相比，区别仅在于，一次烧结的温度为1050℃。
试验组
将本发明实施例1和对比例1～6制备的正极材料进行SEM测试，测试结果见图1～7和表1。
将本发明实施例1和对比例1～6制备的正极材料分别与导电剂乙炔炭黑、粘结剂PVDF按照质量比92：4：4比例混合均匀，加入适量的1-甲基-2吡咯烷酮球磨1小时配成浆料均匀涂在铝片上，烘干、压片制成正极片。以金属锂片为负极组装成2032扣式电池，采用蓝电测试系统进行电性能测试，充放电电压为3.0～4.3V，首圈以0.2C/0.2C充放电，再以1C/1C循环200圈，结果见表1。
表1
Figure PCTCN2022108807-appb-000001
通过表1可以看出，与对比例1～6相比，本发明实施例1制备的镍钴锰酸锂高镍单晶正极材料单晶尺寸大、分散性好、放电比容量高，同时具有良好的循环稳定性。
与实施例1相比，对比例1所得高镍单晶正极材料具有较大的平均粒径，但其仍然具有较差的放电比容量和循环性能，其原因在于，对比例1仅加入氧化锆，在没有氧化钨和碳酸钠的作用下，导致其烧结温度偏高，电化学性能仍然较差。
与实施例1相比，对比例2所得高镍单晶正极材料具有较大的平均粒径，但其也仍然具有较差的放电比容量和循环性能，其原因在于，对比例2中未加入氧化钨，其无法发挥氧化钨在体系中增强导电性、细化一次粒子的作用，最终导致对比例2所得高镍单晶正极材料具有较差的电化学性能。
与实施例1相比，对比例3所得高镍单晶正极材料的平均粒径显著降低，同时具有较差的放电比容量和循环性能，其原因在于，对比例3中未 加入碳酸钠，其无法与氧化钨配合作用以增大单晶尺寸、提高分散性，并最终导致对比例3所得高镍单晶正极材料具有较差的电化学性能。
与实施例1相比，对比例4所得高镍单晶正极材料具有单晶尺寸大、分散性好、放电比容量，但循环性能较差，原因在于对比例4未掺入氧化锆，导致晶体的结构稳定性较实施例1下降。
与实施例1相比，对比例5所得高镍单晶正极材料的平均粒径和循环性能均显著降低，其原因在于，对比例5并未提高烧结温度，从而导致所得正极材料的单晶尺寸小，分散性差，循环性能显著下降。
与实施例1相比，对比例6所得高镍单晶正极材料的平均粒径显著增大，但是其放电比容量和循环性能均显著下降，其原因在于，对比例6的烧结温度过高，导致单晶过度生长，锂离子传输路径较长，离子导电性降低，导致容量及倍率性能下降。
以上所述本发明的具体实施方式，并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形，均应包含在本发明权利要求的保护范围内。

Claims (10)

  1. 一种镍钴锰酸锂高镍单晶正极材料的制备方法，其特征在于，包括以下步骤：
    将镍钴锰氢氧化物与锂源、氧化锆、氧化钨、碳酸钠混合球磨，随后进行一次烧结，经粉碎后得到镍钴锰酸锂高镍单晶正极材料中间体；其中，一次烧结温度高出正常烧结温度50～150℃；
    将所述镍钴锰酸锂高镍单晶正极材料中间体与包覆剂混合均匀，随后进行二次烧结，得到镍钴锰酸锂高镍单晶正极材料。
  2. 根据权利要求1所述镍钴锰酸锂高镍单晶正极材料的制备方法，其特征在于，所述正常烧结温度为镍钴锰氢氧化物与锂源进行一次烧结DOE试验，由上述试验得到的镍钴锰单晶正极材料一烧料经过电化学测试后，放电比容量最大、单晶分散性最好的烧结温度。
  3. 根据权利要求1所述镍钴锰酸锂高镍单晶正极材料的制备方法，其特征在于，所述一次烧结温度高出正常烧结温度70～80℃。
  4. 根据权利要求1所述镍钴锰酸锂高镍单晶正极材料的制备方法，其特征在于，所述镍钴锰氢氧化物的化学组成为：Ni xCo yMn 1-x-y(OH) 2，0.7≤x≤0.95,0.02≤y≤0.25；所述锂源为碳酸锂、氢氧化锂、硝酸锂、氯化锂中的至少一种；所述镍钴锰氢氧化物与锂源中锂的摩尔比为1：(1.01～1.1)。
  5. 根据权利要求1所述镍钴锰酸锂高镍单晶正极材料的制备方法，其特征在于，所述镍钴锰氢氧化物与氧化锆、氧化钨、碳酸钠的摩尔比为1：(0.001～0.005)：(0.001～0.005)：(0.001～0.005)。
  6. 根据权利要求5所述镍钴锰酸锂高镍单晶正极材料的制备方法，其特征在于，所述镍钴锰氢氧化物与氧化锆、氧化钨、碳酸钠的摩尔比为1：0.002：0.0016：0.002。
  7. 根据权利要求1所述镍钴锰酸锂高镍单晶正极材料的制备方法，其 特征在于，所述一次烧结的时间为10～20h。
  8. 根据权利要求1所述镍钴锰酸锂高镍单晶正极材料的制备方法，其特征在于，所述包覆剂为B、Al、Mg、V、Ti、P、Si、Y的氧化物或氢氧化物中的至少一种；包覆剂的加入量为所述镍钴锰酸锂高镍单晶正极材料中间体总量的0.05wt％～5wt％；所述二次烧结的温度为200～600℃，所述二次烧结的时间为6～24h。
  9. 根据权利要求1所述镍钴锰酸锂高镍单晶正极材料的制备方法，其特征在于，一次烧结过程和二次烧结过程均在氧气的条件下进行。
  10. 一种镍钴锰酸锂高镍单晶正极材料，其特征在于，所述镍钴锰酸锂高镍单晶正极材料通过权利要求1～9中任一项所述镍钴锰酸锂高镍单晶正极材料的制备方法得到。
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