CN114665086A - A kind of lithium-rich manganese-based cathode material and preparation method thereof - Google Patents

A kind of lithium-rich manganese-based cathode material and preparation method thereof Download PDF

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CN114665086A
CN114665086A CN202210152264.3A CN202210152264A CN114665086A CN 114665086 A CN114665086 A CN 114665086A CN 202210152264 A CN202210152264 A CN 202210152264A CN 114665086 A CN114665086 A CN 114665086A
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lithium
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rich manganese
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孙艳霞
海春喜
周园
董生德
申月
曾金波
任秀峰
李翔
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Qinghai Institute of Salt Lakes Research of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection 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
    • HELECTRICITY
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Abstract

本发明提供了一种富锂锰基正极材料及其制备方法,所述制备方法包括:将镍的乙酸盐、钴的乙酸盐和锰的乙酸盐,与预定量的沉淀剂一起加入到溶剂中,进行溶剂热反应,制备获得前驱体材料;将前驱体材料进行预烧,经冷却后获得预烧产物;将锂盐化合物和镁盐化合物与预烧产物混合均匀后进行煅烧,以获得所述富锂锰基正极材料。本发明所提供的制备方法,采用溶剂热法合成球形结构完整且分散性良好的富锂锰基前驱体材料,还通过以乙酸镁作为镁源进行掺杂改性,在提高材料的稳定性的同时使材料产生了多孔结构,该多孔结构可以缩短锂离子的迁移路径,为锂离子的传输提供更多的通道,从而有利于改善材料的电化学性能。

Figure 202210152264

The invention provides a lithium-rich manganese-based positive electrode material and a preparation method thereof. The preparation method comprises: adding nickel acetate, cobalt acetate and manganese acetate together with a predetermined amount of precipitant In a solvent, a solvothermal reaction is carried out to prepare a precursor material; the precursor material is pre-calcined, and a pre-calcined product is obtained after cooling; the lithium salt compound and the magnesium salt compound and the pre-calcined product are mixed uniformly and then calcined to obtain a The lithium-rich manganese-based cathode material is obtained. The preparation method provided by the invention adopts a solvothermal method to synthesize a lithium-rich manganese-based precursor material with a complete spherical structure and good dispersibility, and also uses magnesium acetate as a magnesium source for doping modification, thereby improving the stability of the material. At the same time, the material produces a porous structure, which can shorten the migration path of lithium ions and provide more channels for the transport of lithium ions, thereby helping to improve the electrochemical performance of the material.

Figure 202210152264

Description

一种富锂锰基正极材料及其制备方法A kind of lithium-rich manganese-based cathode material and preparation method thereof

技术领域technical field

本发明属于锂离子电池电极材料技术领域,具体涉及一种富锂锰基正极材料及其制备方法。The invention belongs to the technical field of lithium ion battery electrode materials, and particularly relates to a lithium-rich manganese-based positive electrode material and a preparation method thereof.

背景技术Background technique

锂离子电池由于具有电压高、比能量高、循环寿命长、安全性能好、工作温度范围宽、对环境友好等优点,被广泛应用于手机和笔记本等便携装置,医疗设备,电动工具等。近年来锂离子电池的应用范围也拓展至能源交通(电动车、混合动力汽车等),智能电网,新型能源储能(太阳能、风能)等一些新的领域,这些方面的应用对锂离子电池材料的性能提出了更高的要求。锂离子电池包括正负极材料,电解液,隔膜等重要组成部分,其中正极材料作为影响整个电池电化学性能、安全性、成本等的关键因素,其发展倍受科学界的广泛关注。目前常用的锂离子电池正极材料主要有层状结构的LiCoO2,LiMnO2,LiNiO2,LiNixCoyMn1-x-yO2,尖晶石结构的LiMn2O4以及橄榄石结构的LiFePO4等。遗憾的是,这些正极材料几乎都达到了它们可用比容量(120~200mAh·g–1)的极限,因此,高比容量正极材料的研发迫在眉睫。富锂锰基正极材料xLi2MnO3·(1-x)LiMO2(M=Ni,Co,Mn),或者可表示为Li1+xM1-xO2(M=Ni,Co,Mn),因具有在高电压下可发挥高容量的特性而备受广大科研工作者的广泛关注。然而,大量研究表明,该材料在高电压下充放电的过程中,首次过度脱锂会破坏材料的表面晶格结构,从而影响其电化学性能,如循环稳定性和倍率性能变差等。因此,提高富锂锰基材料xLi2MnO3·(1-x)LiMO2(M=Ni,Co,Mn)的结构稳定性,改善其电化学性能是当前要解决的关键问题。目前常用的改善富锂锰基正极材料结构稳定性的方法主要有掺杂,包覆,以及两种方法的结合等但这些改性方法并没有达到预期的改性效果,如包覆层虽然会保护正极材料颗粒受到来自电解液的侵蚀,但对材料内在的结构稳定性并没有贡献;掺杂会出现不均匀掺杂的情况,往往存在偏析,元素会聚集至表面,同时也不会产生孔道结构,对锂离子的迁移无贡献。在众多富锂锰基正极材料xLi2MnO3·(1-x)LiMO2(M=Ni,Co,Mn)的前驱体的合成方法中,利用氨水作为pH调节剂和过渡金属的螯合剂,并以水为溶剂的共沉淀法是目前材料合成界普遍采用的一种方法。而利用该方法在合成富锂锰基正极材料的过程中,氨水的挥发会造成环境污染,且严重危害人体的健康,此外,利用该方法合成的材料团聚严重,分散性差,首次库伦效率低,球形结构不完整且阻碍Li+的传输,结构稳定性差,从而导致其容量,循环稳定性等电化学性能劣化,影响材料电化学性能的发挥。Lithium-ion batteries are widely used in portable devices such as mobile phones and notebooks, medical equipment, power tools, etc. due to their high voltage, high specific energy, long cycle life, good safety performance, wide operating temperature range, and environmental friendliness. In recent years, the application scope of lithium-ion batteries has also expanded to energy transportation (electric vehicles, hybrid vehicles, etc.), smart grids, new energy storage (solar energy, wind energy) and other new fields. performance puts forward higher requirements. Lithium-ion batteries include positive and negative electrode materials, electrolytes, separators and other important components. As a key factor affecting the electrochemical performance, safety, and cost of the entire battery, the development of positive electrode materials has received extensive attention from the scientific community. At present, the commonly used cathode materials for lithium ion batteries mainly include layered LiCoO 2 , LiMnO 2 , LiNiO 2 , LiNixCoyMn1-x-yO 2 , spinel structure LiMn 2 O 4 and olivine structure LiFePO 4 . Unfortunately, these cathode materials almost all reach the limit of their usable specific capacity (120-200 mAh·g -1 ), so the research and development of cathode materials with high specific capacity is imminent. Lithium-rich manganese-based cathode material xLi 2 MnO 3 ·(1-x)LiMO 2 (M=Ni, Co, Mn), or can be expressed as Li 1+x M 1-x O 2 (M=Ni, Co, Mn) ), which has attracted extensive attention of scientific researchers because of its high capacity under high voltage. However, a large number of studies have shown that the first excessive delithiation of the material during the charge-discharge process at high voltage will destroy the surface lattice structure of the material, thereby affecting its electrochemical properties, such as poor cycle stability and rate performance. Therefore, improving the structural stability of the lithium-rich manganese-based material xLi 2 MnO 3 ·(1-x)LiMO 2 (M=Ni, Co, Mn) and improving its electrochemical performance are the key issues to be solved at present. At present, the commonly used methods to improve the structural stability of lithium-rich manganese-based cathode materials mainly include doping, coating, and the combination of the two methods, etc. However, these modification methods have not achieved the expected modification effect. Protects the positive electrode material particles from erosion from the electrolyte, but does not contribute to the inherent structural stability of the material; doping will cause uneven doping, often with segregation, elements will aggregate to the surface, and no pores will be generated. The structure does not contribute to the migration of lithium ions. In many synthesis methods of precursors of lithium-rich manganese-based cathode materials xLi 2 MnO 3 ·(1-x)LiMO 2 (M=Ni, Co, Mn), ammonia water is used as pH adjuster and transition metal chelator, The co-precipitation method with water as solvent is a commonly used method in the field of material synthesis. In the process of synthesizing lithium-rich manganese-based cathode materials using this method, the volatilization of ammonia water will cause environmental pollution and seriously endanger human health. In addition, the materials synthesized by this method have serious agglomeration, poor dispersibility, and low first coulomb efficiency. The spherical structure is incomplete and hinders the transport of Li + , and the structural stability is poor, which leads to the deterioration of its electrochemical properties such as capacity and cycle stability, and affects the electrochemical performance of the material.

发明内容SUMMARY OF THE INVENTION

鉴于现有技术存在的不足,本发明提供了一种富锂锰基正极材料及其制备方法,以解决现有的富锂锰基正极材料合成方法在合成过程中产生的环境问题以及合成的富锂锰基正极材料存在球形结构不完整,分散性差,结构稳定性差以及电化学性能劣化等问题。In view of the deficiencies existing in the prior art, the present invention provides a lithium-rich manganese-based positive electrode material and a preparation method thereof, so as to solve the environmental problems generated in the synthesis process of the existing lithium-rich manganese-based positive electrode material synthesis method and the synthetic rich Lithium-manganese-based cathode materials have problems such as incomplete spherical structure, poor dispersion, poor structural stability, and deterioration of electrochemical performance.

为实现上述目的,本发明一方面提供了一种富锂锰基正极材料的制备方法,其包括:In order to achieve the above object, one aspect of the present invention provides a method for preparing a lithium-rich manganese-based positive electrode material, comprising:

S110、将镍的乙酸盐、钴的乙酸盐和锰的乙酸盐,与预定量的沉淀剂一起加入到溶剂中进行溶剂热反应,制备获得前驱体材料;S110, adding nickel acetate, cobalt acetate and manganese acetate together with a predetermined amount of precipitant into a solvent to carry out a solvothermal reaction to prepare a precursor material;

S120、将所述前驱体材料进行预烧,经冷却后获得预烧产物;S120, calcining the precursor material, and obtaining a calcined product after cooling;

S130、将锂盐化合物和镁盐化合物与所述预烧产物混合均匀后进行煅烧,以获得所述富锂锰基正极材料。S130 , mixing the lithium salt compound and the magnesium salt compound with the calcined product uniformly, and then calcining to obtain the lithium-rich manganese-based cathode material.

优选地,所述步骤S110,具体包括:Preferably, the step S110 specifically includes:

将镍的乙酸盐、钴的乙酸盐和锰的乙酸盐按照预定摩尔比溶解于溶剂中,搅拌至完全溶解后获得第一混合溶液;Dissolving nickel acetate, cobalt acetate and manganese acetate in a solvent according to a predetermined molar ratio, and stirring until completely dissolved to obtain a first mixed solution;

将预定量的沉淀剂加入到所述第一混合溶液中并溶解混合,以获得第二混合溶液;adding a predetermined amount of precipitant to the first mixed solution and dissolving and mixing to obtain a second mixed solution;

将所述第二混合溶液置于反应釜中进行溶剂热反应,反应结束后进行冷却以获得所述前驱体材料。The second mixed solution is placed in a reactor to perform a solvothermal reaction, and after the reaction is completed, cooling is performed to obtain the precursor material.

进一步优选地,所述预定摩尔比是根据所述前驱体材料的分子式为Mn0.54Ni0.13Co0.13(CO3)0.8的要求设定。Further preferably, the predetermined molar ratio is set according to the requirement that the molecular formula of the precursor material is Mn 0.54 Ni 0.13 Co 0.13 (CO 3 ) 0.8 .

进一步优选地,所述沉淀剂为尿素。Further preferably, the precipitating agent is urea.

进一步优选地,所述溶剂热反应的反应温度为160℃~180℃,反应时间为10h~24h。Further preferably, the reaction temperature of the solvothermal reaction is 160°C to 180°C, and the reaction time is 10h to 24h.

优选地,所述步骤S120中,所述预烧的温度为450℃~550℃,所述预烧的时间为6h~10h。Preferably, in the step S120, the temperature of the pre-burning is 450° C.˜550° C., and the time of the pre-burning is 6 h˜10 h.

优选地,所述步骤S130,具体包括:Preferably, the step S130 specifically includes:

将锂盐化合物和镁盐化合物与所述预烧产物按照预定反应比例混合均匀,以获得混合材料;Mixing the lithium salt compound and the magnesium salt compound with the calcined product uniformly according to a predetermined reaction ratio to obtain a mixed material;

将所述混合材料在空气气氛下升温至预定温度后进行煅烧,以获得所述多孔富锂锰基正极材料;The mixed material is heated to a predetermined temperature in an air atmosphere and then calcined to obtain the porous lithium-rich manganese-based cathode material;

进一步优选地,所述预定温度为850℃~950℃,所述煅烧的时间为10h~12h。Further preferably, the predetermined temperature is 850°C to 950°C, and the calcination time is 10h to 12h.

进一步优选地,所述锂盐化合物为碳酸锂,所述镁盐化合物为乙酸镁。Further preferably, the lithium salt compound is lithium carbonate, and the magnesium salt compound is magnesium acetate.

进一步优选地,所述富锂锰基正极材料的分子式为Li1.2[Mn0.54Ni0.13Co0.13]1- xMgxO2,其中,x=0.01~0.05;所述预定反应比例是根据所述富锂锰基正极材料的分子式为Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2的要求设定。Further preferably, the molecular formula of the lithium-rich manganese-based cathode material is Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1- x Mg x O 2 , wherein x=0.01-0.05; the predetermined reaction ratio is based on the The molecular formula of the lithium-rich manganese-based cathode material is set according to the requirements of Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1-x Mg x O 2 .

本发明的另一方面提供了一种如上所述的制备方法制备获得的富锂锰基正极材料。Another aspect of the present invention provides a lithium-rich manganese-based cathode material prepared by the above preparation method.

有益效果:本发明实施例提供的富锂锰基正极材料及其制备方法,通过使用具有分散性的溶剂,并采用溶剂热法合成球形结构完整且分散性良好的富锂锰基正极材料的前驱体材料,有利于改善合成过程中的团聚性问题;并且,本发明还通过以乙酸镁作为镁源对富锂锰基正极材料进行掺杂改性,在提高材料的稳定性的同时使富锂锰基正极材料产生了多孔结构,该多孔结构有利于锂离子的扩散,可以缩短锂离子的迁移路径,为锂离子的传输提供更多的通道,从而有利于改善材料的电化学性能;此外,该制备方法在制备过程中无有害物质生成,避免了造成环境污染以及危害人体健康。Beneficial effects: The lithium-rich manganese-based positive electrode material and the preparation method thereof provided in the embodiment of the present invention use a solvent with dispersibility and adopt a solvothermal method to synthesize the precursor of the lithium-rich manganese-based positive electrode material with complete spherical structure and good dispersibility It is beneficial to improve the agglomeration problem in the synthesis process; in addition, the present invention also uses magnesium acetate as a magnesium source to dope and modify the lithium-rich manganese-based positive electrode material, so as to improve the stability of the material and make the lithium-rich material more stable. The manganese-based cathode material produces a porous structure, which is conducive to the diffusion of lithium ions, which can shorten the migration path of lithium ions and provide more channels for the transport of lithium ions, which is beneficial to improve the electrochemical performance of the material; in addition, The preparation method does not generate harmful substances in the preparation process, thereby avoiding environmental pollution and endangering human health.

附图说明Description of drawings

通过结合附图进行的以下描述,本发明的实施例的上述和其它方面、特点和优点将变得更加清楚,附图中:The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

图1是本发明实施例提供的富锂锰基正极材料的制备方法的流程图;Fig. 1 is the flow chart of the preparation method of the lithium-rich manganese-based positive electrode material provided by the embodiment of the present invention;

图2为本发明实施例1提供的前驱体材料的扫描图;2 is a scanning diagram of the precursor material provided in Example 1 of the present invention;

图3为本发明实施例3提供的进行掺杂改性后的富锂锰基正极材料的扫描横截面图;3 is a scanning cross-sectional view of the lithium-rich manganese-based positive electrode material after doping modification provided in Example 3 of the present invention;

图4为本发明实施例2~4提供的添加不同含量的乙酸镁进行掺杂改性后对应获得的富锂锰基正极材料的循环性能图;Fig. 4 is the cycle performance diagram of correspondingly obtained lithium-rich manganese-based positive electrode materials obtained by adding different contents of magnesium acetate for doping modification provided in Examples 2-4 of the present invention;

图5为本发明对比例1提供的的未进行掺杂改性的富锂锰基正极材料的扫描横截面图;5 is a scanning cross-sectional view of the lithium-rich manganese-based positive electrode material provided by Comparative Example 1 of the present invention that is not subjected to doping modification;

图6(a)为本发明对比例1提供的未进行掺杂改性的富锂锰基正极材料的扫描图;Figure 6(a) is a scanning diagram of the lithium-rich manganese-based positive electrode material provided by Comparative Example 1 of the present invention without being modified by doping;

图6(b)为本发明实施例3提供的进行掺杂改性后的富锂锰基正极材料的扫描图。FIG. 6( b ) is a scanning diagram of the lithium-rich manganese-based cathode material after doping modification provided in Example 3 of the present invention.

具体实施方式Detailed ways

以下,将参照附图来详细描述本发明的具体实施例。然而,可以以许多不同的形式来实施本发明,并且本发明不应该被解释为限制于这里阐述的具体实施例。相反,提供这些实施例是为了解释本发明的原理及其实际应用,从而使本领域的其他技术人员能够理解本发明的各种实施例和适合于特定预期应用的各种修改。Hereinafter, specific embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application, to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular intended use.

如本文中使用的,术语“包括”及其变型表示开放的术语,含义是“包括但不限于”。术语“基于”、“根据”等表示“至少部分地基于”、“至少部分地根据”。术语“一个实施例”和“一实施例”表示“至少一个实施例”。术语“另一个实施例”表示“至少一个其他实施例”。术语“第一”、“第二”等可以指代不同的或相同的对象。下面可以包括其他的定义,无论是明确的还是隐含的。除非上下文中明确地指明,否则一个术语的定义在整个说明书中是一致的。As used herein, the term "including" and variations thereof represent open-ended terms meaning "including but not limited to". The terms "based on", "depending on" and the like mean "based at least in part on", "based at least in part on". The terms "one embodiment" and "an embodiment" mean "at least one embodiment." The term "another embodiment" means "at least one other embodiment." The terms "first", "second", etc. may refer to different or the same objects. Other definitions, whether explicit or implicit, may be included below. The definition of a term is consistent throughout the specification unless the context clearly dictates otherwise.

如背景技术中所述,现有的富锂锰基正极材料的合成方法主要采取共沉淀法,在合成过程中易导致环境污染,此外,利用该方法合成的材料团聚严重,分散性差,球形结构不完整且阻碍锂离子的传输,结构稳定性差,从而导致其容量,循环稳定性等电化学性能劣化,影响材料电化学性能的发挥。因此,为了解决现有技术中所述富锂锰基正极材料存在的诸多技术问题,根据本发明的实施例提供了一种富锂锰基正极材料及其制备方法。As described in the background art, the existing method for synthesizing lithium-rich manganese-based cathode materials mainly adopts co-precipitation method, which easily leads to environmental pollution during the synthesis process. In addition, the materials synthesized by this method have serious agglomeration, poor dispersibility and spherical structure. It is incomplete and hinders the transport of lithium ions and has poor structural stability, which leads to the deterioration of its electrochemical properties such as capacity and cycle stability, and affects the electrochemical performance of the material. Therefore, in order to solve many technical problems existing in the lithium-rich manganese-based positive electrode material in the prior art, a lithium-rich manganese-based positive electrode material and a preparation method thereof are provided according to the embodiments of the present invention.

以下将结合附图来详细描述根据本发明的实施例的富锂锰基正极材料及其制备方法,图1是根据本发明的实施例的富锂锰基正极材料的制备方法的流程图。The lithium-rich manganese-based positive electrode material and the preparation method thereof according to the embodiments of the present invention will be described in detail below with reference to the accompanying drawings. FIG. 1 is a flowchart of the preparation method of the lithium-rich manganese-based positive electrode material according to the embodiment of the present invention.

参阅图1,在步骤S110中,将镍的乙酸盐、钴的乙酸盐和锰的乙酸盐,与预定量的沉淀剂一起加入到溶剂中进行溶剂热反应,制备获得前驱体材料。Referring to FIG. 1 , in step S110 , nickel acetate, cobalt acetate and manganese acetate are added to a solvent together with a predetermined amount of precipitant to perform a solvothermal reaction to prepare a precursor material.

优选地,所述步骤S110,具体包括:Preferably, the step S110 specifically includes:

将镍的乙酸盐、钴的乙酸盐和锰的乙酸盐按照预定摩尔比溶解于溶剂中,搅拌至完全溶解后获得第一混合溶液;Dissolving nickel acetate, cobalt acetate and manganese acetate in a solvent according to a predetermined molar ratio, and stirring until completely dissolved to obtain a first mixed solution;

将预定量的沉淀剂加入到所述第一混合溶液中并溶解混合,以获得第二混合溶液;adding a predetermined amount of precipitant to the first mixed solution and dissolving and mixing to obtain a second mixed solution;

将所述第二混合溶液置于含有聚四氟乙烯内胆的反应釜中进行溶剂热反应,反应结束后进行冷却以获得所述前驱体材料。The second mixed solution is placed in a reaction kettle containing a polytetrafluoroethylene liner to perform a solvothermal reaction, and after the reaction is completed, cooling is performed to obtain the precursor material.

进一步优选地,所述预定摩尔比是根据所述前驱体材料的分子式为Mn0.54Ni0.13Co0.13(CO3)0.8的要求设定;即所述镍的乙酸盐、所述钴的乙酸盐和所述锰的乙酸盐的摩尔比为0.13:0.13:0.54。Further preferably, the predetermined molar ratio is set according to the requirement that the molecular formula of the precursor material is Mn 0.54 Ni 0.13 Co 0.13 (CO 3 ) 0.8 ; that is, the nickel acetate, the cobalt acetic acid The molar ratio of the salt to the manganese acetate was 0.13:0.13:0.54.

进一步优选地,所述溶剂包括水、乙二醇和乙醇,所述溶剂应具有分散性,以起到分散溶解所述镍的乙酸盐、钴的乙酸盐和锰的乙酸盐的作用,并且不引入其他杂质离子;此外,所述溶剂的加入量为能够使所述第一混合溶液中所述镍金属离子、钴金属离子和锰金属离子的总浓度为0.5mol/L。Further preferably, the solvent includes water, ethylene glycol and ethanol, and the solvent should have dispersibility to disperse and dissolve the nickel acetate, cobalt acetate and manganese acetate, And no other impurity ions are introduced; in addition, the solvent is added in such an amount that the total concentration of the nickel metal ions, cobalt metal ions and manganese metal ions in the first mixed solution is 0.5 mol/L.

进一步优选地,所述沉淀剂为尿素,加入所述沉淀剂的物质的量等于所述第一混合溶液中所述镍金属离子、钴金属离子和锰金属离子的物质的量的总和。Further preferably, the precipitant is urea, and the amount of substances added to the precipitant is equal to the sum of the amounts of the nickel metal ions, cobalt metal ions and manganese metal ions in the first mixed solution.

进一步优选地,所述溶剂热反应的反应温度为160℃~180℃,反应时间为10h~24h。Further preferably, the reaction temperature of the solvothermal reaction is 160°C to 180°C, and the reaction time is 10h to 24h.

所述沉淀剂既具有N元素又具有C元素,在进行溶剂热反应的过程中,在高温高压的反应条件下,所述沉淀剂能够将镍、钴和锰三种元素络合在一起进行共沉淀,从而形成所述前驱体材料。The precipitating agent has both N element and C element. During the solvothermal reaction process, under the reaction conditions of high temperature and high pressure, the precipitating agent can complex the three elements of nickel, cobalt and manganese together for co-coagulation. precipitation, thereby forming the precursor material.

本发明使用具有分散性的溶剂,并采用溶剂热法合成富锂锰基正极材料的前驱体材料,获得的所述前驱体材料球形结构完整且分散性良好,有利于改善富锂锰基正极材料在合成过程中的团聚性问题。The present invention uses a solvent with dispersibility, and adopts a solvothermal method to synthesize the precursor material of the lithium-rich manganese-based positive electrode material. The obtained precursor material has a complete spherical structure and good dispersibility, which is beneficial to improving the lithium-rich manganese-based positive electrode material. Agglomeration problems during synthesis.

在步骤S120中,将所述前驱体材料进行预烧,经冷却后获得预烧产物。In step S120, the precursor material is calcined, and a calcined product is obtained after cooling.

优选地,所述预烧的温度为450℃~550℃,所述预烧的时间为6h~10h。Preferably, the temperature of the pre-sintering is 450° C.˜550° C., and the time of the pre-sintering is 6 h˜10 h.

在步骤S130中,将锂盐化合物和镁盐化合物与所述预烧产物混合均匀后进行煅烧,以获得所述富锂锰基正极材料。In step S130, the lithium salt compound and the magnesium salt compound are uniformly mixed with the calcined product and then calcined to obtain the lithium-rich manganese-based cathode material.

优选地,所述步骤S130,具体包括:Preferably, the step S130 specifically includes:

将锂盐化合物和镁盐化合物与所述预烧产物按照预定反应比例混合均匀,以获得混合材料;Mixing the lithium salt compound and the magnesium salt compound with the calcined product uniformly according to a predetermined reaction ratio to obtain a mixed material;

将所述混合材料在空气气氛下升温至预定温度后进行煅烧,以获得所述多孔富锂锰基正极材料。The mixed material is heated to a predetermined temperature in an air atmosphere and then calcined to obtain the porous lithium-rich manganese-based positive electrode material.

进一步优选地,所述预定温度为850℃~950℃,所述煅烧的时间为10h~12h。Further preferably, the predetermined temperature is 850°C to 950°C, and the calcination time is 10h to 12h.

进一步优选地,所述锂盐化合物为碳酸锂,所述镁盐化合物为乙酸镁。Further preferably, the lithium salt compound is lithium carbonate, and the magnesium salt compound is magnesium acetate.

优选地,所述富锂锰基正极材料的分子式为Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2,其中,x=0.01~0.05;所述预定反应比例是根据所述富锂锰基正极材料的分子式为Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2的要求设定。Preferably, the molecular formula of the lithium-rich manganese-based cathode material is Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1-x Mg x O 2 , where x=0.01-0.05; the predetermined reaction ratio is based on the rich The molecular formula of the lithium-manganese-based cathode material is set according to the requirements of Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1-x Mg x O 2 .

进一步优选地,x的值为0.01,或0.03,或0.05。Further preferably, the value of x is 0.01, or 0.03, or 0.05.

其中,由于在高温煅烧的过程中会造成锂离子的挥发,导致锂离子损失,因此,所述碳酸锂的加入量应过量5%摩尔量。Wherein, since the volatilization of lithium ions will result in the loss of lithium ions in the process of high temperature calcination, the addition amount of the lithium carbonate should be in excess of 5% by mole.

本发明以乙酸镁作为镁源,在制备过程中对富锂锰基正极材料进行掺杂改性,由于乙酸镁中含有较多的C、H元素,与经过预烧的所述前驱体材料以及碳酸锂化合物混合后在空气气氛下进行高温煅烧的过程中会释放出二氧化碳、水蒸气等,导致富锂锰基材料产生了多孔结构,该多孔结构有利于锂离子的扩散,缩短锂离子的迁移路径,为锂离子的传输提供更多的通道,且随着镁掺杂量的增加,多孔结构越明显,此外,通过掺杂镁离子可以改善材料的结构稳定性,从而改善了材料的电化学性能。In the present invention, magnesium acetate is used as the magnesium source, and the lithium-rich manganese-based positive electrode material is doped and modified during the preparation process. Because magnesium acetate contains more elements of C and H, it is different from the pre-fired precursor material and the Carbon dioxide, water vapor, etc. will be released in the process of high temperature calcination in air atmosphere after the lithium carbonate compound is mixed, resulting in a porous structure of the lithium-rich manganese-based material, which is conducive to the diffusion of lithium ions and shortens the migration of lithium ions. It provides more channels for the transport of lithium ions, and with the increase of magnesium doping amount, the porous structure becomes more obvious. In addition, the structural stability of the material can be improved by doping magnesium ions, thereby improving the electrochemical performance of the material. performance.

根据本发明的实施例还提供了一种由上述的制备方法制备形成的富锂锰基正极材料。所述富锂锰基正极材料利用镁离子进行掺杂改性,在提高了材料结构稳定性的同时还产生了多孔结构,该多孔结构缩短锂离子的迁移路径,为锂离子的传输提供更多的通道,从而改善了材料的电化学性能。According to an embodiment of the present invention, there is also provided a lithium-rich manganese-based cathode material prepared by the above preparation method. The lithium-rich manganese-based positive electrode material is modified by doping with magnesium ions, which not only improves the stability of the material structure, but also produces a porous structure, which shortens the migration path of lithium ions and provides more transportation for lithium ions. channels, thereby improving the electrochemical performance of the material.

以下将结合具体的实施例来说明上述富锂锰基正极材料及其制备方法,本领域技术人员所理解的是,下述实施例仅是本发明上述富锂锰基正极材料及其制备方法的具体示例,而不用于限制其全部。The above-mentioned lithium-rich manganese-based positive electrode materials and their preparation methods will be described below with reference to specific examples. Those skilled in the art will understand that the following embodiments are only examples of the above-mentioned lithium-rich manganese-based positive electrode materials and their preparation methods of the present invention. Specific examples are not intended to limit them all.

实施例1:前驱体材料的制备Example 1: Preparation of Precursor Materials

将镍的乙酸盐、钴的乙酸盐和锰的乙酸盐按照0.13:0.13:0.54的摩尔比溶解于乙二醇溶剂中,搅拌至完全溶解后获得第一混合溶液;将沉淀剂尿素加入到所述第一混合溶液中并溶解混合,以获得第二混合溶液;将所述第二混合溶液倒入含有聚四氟乙烯内胆的反应釜中,在160℃下进行溶剂热反应,反应时间为24h,反应结束后进行冷却,然后经过洗涤、干燥,以获得所述前驱体材料,其中,所述前驱体材料的分子式为Mn0.54Ni0.13Co0.13(CO3)0.8The acetate of nickel, the acetate of cobalt and the acetate of manganese are dissolved in the ethylene glycol solvent according to the molar ratio of 0.13:0.13:0.54, and the first mixed solution is obtained after stirring to complete dissolution; adding into the first mixed solution and dissolving and mixing to obtain a second mixed solution; pouring the second mixed solution into a reaction kettle containing a polytetrafluoroethylene liner, and performing a solvothermal reaction at 160°C, The reaction time is 24h, and after the reaction is completed, cooling, washing and drying are performed to obtain the precursor material, wherein the molecular formula of the precursor material is Mn 0.54 Ni 0.13 Co 0.13 (CO 3 ) 0.8 .

图2为本发明实施例1制备获得的前驱体材料的扫描图,如图2所示,采用溶剂热法制备获得的前驱体材料的球形结构完整且分散性良好。FIG. 2 is a scanning diagram of the precursor material prepared in Example 1 of the present invention. As shown in FIG. 2 , the precursor material prepared by the solvothermal method has a complete spherical structure and good dispersibility.

实施例2~4:经镁离子掺杂改性的富锂锰基正极材料的制备Examples 2-4: Preparation of Li-rich Manganese-Based Cathode Materials Modified by Doping with Magnesium Ions

将实施例1制备获得的所述前驱体材料在500℃下进行预烧6h,获得预烧产物;The precursor material prepared in Example 1 was calcined at 500° C. for 6 h to obtain a calcined product;

将锂盐化合物和镁盐化合物与所述预烧产物按照预定反应比例混合均匀,以获得混合材料;所述预定反应比例是根据所述富锂锰基正极材料的分子式为Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2的要求设定,其中,所述碳酸锂的添加量应过量5%摩尔量;Mixing the lithium salt compound and the magnesium salt compound with the calcined product uniformly according to a predetermined reaction ratio to obtain a mixed material; the predetermined reaction ratio is Li 1.2 [Mn 0.54 Ni according to the molecular formula of the lithium-rich manganese-based positive electrode material 0.13 Co 0.13 ] 1-x Mg x O 2 the requirement setting, wherein, the addition amount of the lithium carbonate should be 5% molar excess;

将所述混合材料在空气气氛下升温至900℃进行煅烧12h,以获得所述经镁离子掺杂改性的富锂锰基正极材料。The mixed material was heated to 900° C. in an air atmosphere for calcination for 12 h, so as to obtain the lithium-rich manganese-based cathode material modified by magnesium ion doping.

实施例2~4中,区别在于所述富锂锰基正极材料Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2中x的值分别为0.01、0.03和0.05,其余均相同。In Examples 2 to 4, the difference is that the value of x in the lithium-rich manganese-based cathode material Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1-x Mg x O 2 is 0.01, 0.03 and 0.05, respectively, and the rest are the same.

图3为本发明实施例3(富锂锰基正极材料Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2中x的值为0.03)制备获得的进行掺杂改性后的富锂锰基正极材料的扫描横截面图,如图3所示,经过镁离子掺杂改性后的富锂锰基正极材料呈多孔结构,该多孔结构有利于锂离子的扩散,缩短锂离子的扩散路径,进而有利于改善材料的电化学性能。Fig. 3 is the rich-rich doping modified prepared in Example 3 of the present invention (the lithium-rich manganese-based cathode material Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1-x Mg x O 2 in which the value of x is 0.03) The scanning cross-sectional view of the lithium-manganese-based cathode material, as shown in Figure 3, the lithium-rich manganese-based cathode material modified by magnesium ion doping has a porous structure, which is conducive to the diffusion of lithium ions and shortens the lithium ion. Diffusion path, which in turn is beneficial to improve the electrochemical performance of the material.

图4为本发明实施例2~4中添加不同含量的乙酸镁进行掺杂改性后对应获得的富锂锰基正极材料的循环性能图,如图4所示,当富锂锰基正极材料Li1.2[Mn0.54Ni0.13Co0.13]1- xMgxO2中x的值为0.03时,所述富锂锰基正极材料的循环性能最佳,经过300次循环后容量保持率为94.04%。FIG. 4 is a graph showing the cycle performance of the lithium-rich manganese-based positive electrode materials obtained by adding different contents of magnesium acetate for doping modification in Examples 2 to 4 of the present invention. As shown in FIG. 4 , when the lithium-rich manganese-based positive electrode materials are When the value of x in Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1- x Mg x O 2 is 0.03, the cycle performance of the lithium-rich manganese-based cathode material is the best, and the capacity retention rate is 94.04% after 300 cycles .

对比例1:未进行掺杂改性的富锂锰基正极材料的制备Comparative Example 1: Preparation of Li-rich Manganese-Based Cathode Material without Doping Modification

将实施例1制备获得的所述前驱体材料在500℃下进行预烧6h,获得预烧产物;The precursor material prepared in Example 1 was calcined at 500° C. for 6 h to obtain a calcined product;

将所述预烧产物与过量5%摩尔量的碳酸锂化合物混合均匀,以获得混合材料;Mixing the calcined product with an excess 5% molar lithium carbonate compound to obtain a mixed material;

将所述混合材料在空气气氛下升温至900℃进行煅烧12h,以获得未进行掺杂改性的富锂锰基正极材料。The mixed material was heated to 900° C. in an air atmosphere for calcination for 12 hours, so as to obtain a lithium-rich manganese-based cathode material without doping modification.

其中,对比例1与实施例2~4的区别仅在于在制备过程中不添加任何乙酸镁。Wherein, the difference between Comparative Example 1 and Examples 2 to 4 is only that no magnesium acetate is added in the preparation process.

图5为本发明对比例1制备获得的未进行掺杂改性的富锂锰基正极材料的扫描横截面图,如图5所示,未进行掺杂改性的富锂锰基正极材料无多孔结构,但元素分布均匀,进一步表明采用溶剂热法有利于制备获得分散性良好的富锂锰基正极材料,且导致富锂锰基正极材料产生多孔结构的原因是由于添加了乙酸镁进行掺杂改性。FIG. 5 is a scanning cross-sectional view of the lithium-rich manganese-based positive electrode material without doping and modification prepared in Comparative Example 1 of the present invention. As shown in FIG. 5 , the lithium-rich manganese-based positive electrode material without doping and modification has no Porous structure, but uniform distribution of elements, which further shows that the solvothermal method is beneficial to the preparation of lithium-rich manganese-based cathode materials with good dispersibility, and the reason for the porous structure of lithium-rich manganese-based cathode materials is the addition of magnesium acetate for doping. Heterogeneous modification.

图6(a)为本发明对比例1制备获得的未进行掺杂改性的富锂锰基正极材料的扫描图;图6(b)为本发明实施例3(富锂锰基正极材料Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2中x的值为0.03)制备获得的进行掺杂改性后的富锂锰基正极材料的扫描图。由图6可知,不论是否加入乙酸镁进行掺杂改性,获得的富锂锰基正极材料的球形结构依然保持完整,且球形颗粒尺寸大约为4微米。Figure 6(a) is a scanning diagram of the lithium-rich manganese-based positive electrode material without doping modification prepared in Comparative Example 1 of the present invention; Figure 6(b) is Example 3 of the present invention (lithium-rich manganese-based positive electrode material Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1-x Mg x O 2 in which the value of x is 0.03) The scanning diagram of the lithium-rich manganese-based cathode material after doping and modification. It can be seen from Fig. 6 that the spherical structure of the obtained lithium-rich manganese-based cathode material remains intact regardless of whether magnesium acetate is added for doping modification, and the spherical particle size is about 4 microns.

综上所述,本发明实施例提供的富锂锰基正极材料及其制备方法,该制备方法使用具有分散性的溶剂,并采用溶剂热法合成富锂锰基正极材料的前驱体材料,获得的所述前驱体材料球形结构完整且分散性良好,有利于改善富锂锰基正极材料在合成过程中的团聚性问题;并且,所述制备方法还以乙酸镁作为镁源,在制备过程中对富锂锰基正极材料进行掺杂改性,在提高了材料结构稳定性的同时还产生了多孔结构,该多孔结构有利于锂离子的扩散,缩短锂离子的迁移路径,为锂离子的传输提供更多的通道,且随着镁掺杂量的增加,多孔结构越明显,从而改善了材料的电化学性能;此外,在制备过程中无任有害物质生成,避免了造成环境污染以及危害人体健康。To sum up, the lithium-rich manganese-based positive electrode material and the preparation method thereof provided in the embodiments of the present invention use a solvent with dispersibility, and the precursor material of the lithium-rich manganese-based positive electrode material is synthesized by solvothermal method to obtain The precursor material has a complete spherical structure and good dispersibility, which is conducive to improving the agglomeration problem of the lithium-rich manganese-based cathode material during the synthesis process; and the preparation method also uses magnesium acetate as the magnesium source. Doping and modifying the lithium-rich manganese-based cathode material not only improves the structural stability of the material, but also produces a porous structure, which is conducive to the diffusion of lithium ions, shortens the migration path of lithium ions, and facilitates the transport of lithium ions. More channels are provided, and as the amount of magnesium doping increases, the porous structure becomes more obvious, thereby improving the electrochemical performance of the material; in addition, no harmful substances are generated during the preparation process, which avoids environmental pollution and harms the human body. healthy.

上述对本发明的特定实施例进行了描述。其它实施例在所附权利要求书的范围内。The foregoing describes specific embodiments of the invention. Other embodiments are within the scope of the appended claims.

在整个本说明书中使用的术语“示例性”、“示例”等意味着“用作示例、实例或例示”,并不意味着比其它实施例“优选”或“具有优势”。出于提供对所描述技术的理解的目的,具体实施方式包括具体细节。然而,可以在没有这些具体细节的情况下实施这些技术。在一些实例中,为了避免对所描述的实施例的概念造成难以理解,公知的结构和装置以框图形式示出。The terms "exemplary", "example" and the like used throughout this specification mean "serving as an example, instance or illustration" and do not mean "preferred" or "advantage" over other embodiments. The detailed description includes specific details for the purpose of providing an understanding of the described technology. However, these techniques may be practiced without these specific details. In some instances, well-known structures and devices are shown in block diagram form in order to avoid obscuring the concepts of the described embodiments.

以上结合附图详细描述了本发明的实施例的可选实施方式,但是,本发明的实施例并不限于上述实施方式中的具体细节,在本发明的实施例的技术构思范围内,可以对本发明的实施例的技术方案进行多种简单变型,这些简单变型均属于本发明的实施例的保护范围。The optional embodiments of the embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the embodiments of the present invention are not limited to the specific details of the above-mentioned embodiments. Within the scope of the technical concept of the embodiments of the present invention, the The technical solutions of the embodiments of the present invention undergo various simple modifications, and these simple modifications all belong to the protection scope of the embodiments of the present invention.

本说明书内容的上述描述被提供来使得本领域任何普通技术人员能够实现或者使用本说明书内容。对于本领域普通技术人员来说,对本说明书内容进行的各种修改是显而易见的,并且,也可以在不脱离本说明书内容的保护范围的情况下,将本文所定义的一般性原理应用于其它变型。因此,本说明书内容并不限于本文所描述的示例和设计,而是与符合本文公开的原理和新颖性特征的最广范围相一致。The above description of the present specification is provided to enable any person of ordinary skill in the art to make or use the present specification. Various modifications to this specification will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other variations without departing from the scope of this specification . Thus, this disclosure is not intended to be limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1.一种富锂锰基正极材料的制备方法,其特征在于,所述制备方法包括:1. a preparation method of lithium-rich manganese-based positive electrode material, is characterized in that, described preparation method comprises: S110、将镍的乙酸盐、钴的乙酸盐和锰的乙酸盐,与预定量的沉淀剂一起加入到溶剂中进行溶剂热反应,制备获得前驱体材料;S110, adding nickel acetate, cobalt acetate and manganese acetate together with a predetermined amount of precipitant into a solvent to carry out a solvothermal reaction to prepare a precursor material; S120、将所述前驱体材料进行预烧,经冷却后获得预烧产物;S120, calcining the precursor material, and obtaining a calcined product after cooling; S130、将锂盐化合物和镁盐化合物与所述预烧产物混合均匀后进行煅烧,以获得所述富锂锰基正极材料。S130 , mixing the lithium salt compound and the magnesium salt compound with the calcined product uniformly, and then calcining to obtain the lithium-rich manganese-based cathode material. 2.根据权利要求1所述的制备方法,其特征在于,所述步骤S110,具体包括:2. The preparation method according to claim 1, wherein the step S110 specifically comprises: 将镍的乙酸盐、钴的乙酸盐和锰的乙酸盐按照预定摩尔比溶解于溶剂中,搅拌至完全溶解后获得第一混合溶液;Dissolving nickel acetate, cobalt acetate and manganese acetate in a solvent according to a predetermined molar ratio, and stirring until completely dissolved to obtain a first mixed solution; 将预定量的沉淀剂加入到所述第一混合溶液中并溶解混合,以获得第二混合溶液;adding a predetermined amount of precipitant to the first mixed solution and dissolving and mixing to obtain a second mixed solution; 将所述第二混合溶液置于反应釜中进行溶剂热反应,反应结束后进行冷却以获得所述前驱体材料。The second mixed solution is placed in a reactor to perform a solvothermal reaction, and after the reaction is completed, cooling is performed to obtain the precursor material. 3.根据权利要求2所述的制备方法,其特征在于,所述预定摩尔比是根据所述前驱体材料的分子式为Mn0.54Ni0.13Co0.13(CO3)0.8的要求设定。3 . The preparation method according to claim 2 , wherein the predetermined molar ratio is set according to the requirement that the molecular formula of the precursor material is Mn 0.54 Ni 0.13 Co 0.13 (CO 3 ) 0.8 . 4 . 4.根据权利要求2所述的制备方法,其特征在于,所述沉淀剂为尿素。4. The preparation method according to claim 2, wherein the precipitating agent is urea. 5.根据权利要求2所述的制备方法,其特征在于,所述溶剂热反应的反应温度为160℃~180℃,反应时间为10h~24h。5 . The preparation method according to claim 2 , wherein the reaction temperature of the solvothermal reaction is 160° C. to 180° C., and the reaction time is 10 h to 24 h. 6 . 6.根据权利要求1所述的制备方法,其特征在于,所述步骤S120中,所述预烧的温度为450℃~550℃,所述预烧的时间为6h~10h。6 . The preparation method according to claim 1 , wherein in the step S120 , the temperature of the calcination is 450° C.˜550° C., and the time of the calcination is 6 h˜10 h. 7 . 7.根据权利要求1~6任一所述的制备方法,其特征在于,所述步骤S130,具体包括:7. The preparation method according to any one of claims 1 to 6, wherein the step S130 specifically comprises: 将锂盐化合物和镁盐化合物与所述预烧产物按照预定反应比例混合均匀,以获得混合材料;Mixing the lithium salt compound and the magnesium salt compound with the calcined product uniformly according to a predetermined reaction ratio to obtain a mixed material; 将所述混合材料在空气气氛下升温至预定温度后进行煅烧,以获得所述多孔富锂锰基正极材料;The mixed material is heated to a predetermined temperature in an air atmosphere and then calcined to obtain the porous lithium-rich manganese-based cathode material; 其中,所述预定温度为850℃~950℃,所述煅烧的时间为10h~12h。Wherein, the predetermined temperature is 850°C to 950°C, and the calcination time is 10h to 12h. 8.根据权利要求7所述的制备方法,其特征在于,所述锂盐化合物为碳酸锂,所述镁盐化合物为乙酸镁。8 . The preparation method according to claim 7 , wherein the lithium salt compound is lithium carbonate, and the magnesium salt compound is magnesium acetate. 9 . 9.根据权利要求8所述的制备方法,其特征在于,所述富锂锰基正极材料的分子式为Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2,其中,x=0.01~0.05;所述预定反应比例是根据所述富锂锰基正极材料的分子式为Li1.2[Mn0.54Ni0.13Co0.13]1-xMgxO2的要求设定。The preparation method according to claim 8, wherein the molecular formula of the lithium-rich manganese-based cathode material is Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1-x Mg x O 2 , wherein x=0.01 ~0.05; the predetermined reaction ratio is set according to the requirement that the molecular formula of the lithium-rich manganese-based cathode material is Li 1.2 [Mn 0.54 Ni 0.13 Co 0.13 ] 1-x Mg x O 2 . 10.根据权利要求1~9任一所述的制备方法制备获得的富锂锰基正极材料。10. The lithium-rich manganese-based cathode material prepared according to the preparation method of any one of claims 1 to 9.
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