锂离子电池用富锂锰基正极材料掺杂改性研究进展

doi:10.11896/cldb.19090064

材料导报

2021, Vol. 35

Issue (7): 7056-7062 https://doi.org/10.11896/cldb.19090064

无机非金属及其复合材料

锂离子电池用富锂锰基正极材料掺杂改性研究进展

翟鑫华^1,2, 张盼盼^1,2, 周建峰^2,3, 何亚鹏^1,2, 黄惠^1,2,3, 郭忠诚^1,2,3

1 昆明理工大学冶金与能源工程学院,昆明 650093
2 云南省冶金电极材料工程技术研究中心,昆明 650106
3 昆明理工恒达科技股份有限公司,昆明 650106

Research Progress on Doping Modification of Li-rich Manganese-based Cathode Materials for Lithium-ion Batteries

ZHAI Xinhua^1,2, ZHANG Panpan^1,2, ZHOU Jianfeng^2,3, HE Yapeng^1,2, HUANG Hui^1,2,3, GUO Zhongcheng^1,2,3

1 College of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
2 Research Center of Metallurgical Electrode Materials Engineering Technology,Kunming 650106, China
3 Kunming Hendera Science and Technology Co., Ltd., Kunming 650106, China

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摘要锂离子电池因具有能量密度高、循环寿命长、自放电率小和环境污染小等优点,目前成为能源设备领域使用占比最多的一类电化学储能电池。正极材料作为锂离子电池中Li⁺的主要提供者,其研发始终受到科技工作者的广泛关注。其中,富锂锰基正极材料具有高比容量、高电压和优异的高温性能等优点,被视为极具潜力的正极材料。然而,富锂锰基正极材料在工作中存在稳定性不好的问题,例如富锂锰材料在充放电循环过程中容易发生锂镍混排,导致层状结构坍塌,影响材料性能,进而使得此类正极材料的应用前景受限。因此,近些年研究者对富锂锰基正极材料进行大量改性研究,并获得优异的成果。在所有的改性方法中,离子掺杂改性由于其特殊的机理,成为改性方法中较佳的选择。目前,富锂锰基正极材料离子掺杂的主要形式包括阳离子掺杂、阴离子掺杂、聚阴离子掺杂和共掺杂。阳离子掺杂是现阶段最为常见的掺杂形式,其主要是在过渡金属位置进行掺杂,少部分在Li位进行掺杂。阳离子掺杂能够抑制过渡金属离子向锂层迁移,减缓尖晶石相生成,提高富锂锰基正极材料结构的稳定性。阴离子掺杂主要是弥补和替换充电过程中形成的氧空位,该方法能够抑制氧空位形成,提高正极材料的安全性和库伦效率。聚阴离子掺杂与阴离子掺杂相似,同样是在正极材料的氧位进行掺杂,由于聚阴离子与过渡金属的结合能更强,过渡金属迁移被抑制,层状结构更加稳固,材料性能显著提升。共掺杂是将阳离子和阴离子同时掺杂到正极材料中,该方法具备阴、阳离子单独掺杂时的效果,可以稳定层状结构,并能显著提高正极材料的循环稳定性,提高电池的循环能力。本文总结了富锂锰基正极材料的结构组成、反应机理以及自身存在的缺陷,重点讨论了阳离子掺杂、阴离子掺杂、聚阴离子掺杂和共掺杂等掺杂方法对富锂锰基正极材料性能的影响,分析了现阶段掺杂改性仍存在的问题并展望其未来研究方向,以期为制备稳定和高性能的富锂锰基正极材料提供参考。

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关键词: 锂离子电池富锂锰基正极材料离子掺杂掺杂改性电化学性能

Abstract: Lithium-ion batteries have the advantages of high energy density, long cycle life, low self-discharge rate, and low environmental pollution, which have become the typical electrochemical energy storage batteries with the largest proportion of energy equipment. As the main supp-lier of Li⁺ in lithium-ion batteries, the research and development of cathode materials has always attracted widespread attention of scientific and technological workers. Lithium-rich manganese-based cathode materials possess the merits of high specific capacity, high voltage, and excellent high-temperature performance, and are considered to be potential cathode materials. However, lithium-rich manganese-based cathode materials commonly suffer from the stability problems. For example, the lithium-nickel mixing during the charge and discharge cycle of the lithium-manganese-rich materials leads to the collapse of the layered structure and affects the mate-rial performance, further obstructing the application of such cathode materials. Therefore, a large number of modification approaches have been performed on lithium-rich manganese-based cathode materials in recent years, and excellent results have been achieved. In all modification met-hods, the ion doping modification has been regarded an excellent choice in the modification methods. Commonly, the ion doping approaches mainly contain cation doping, anion doping, polyanion doping and co-doping. Cation doping is the most common doping option at this stage. It is mainly doped at the transition metal position, and a small part is doped with Li site. Cation doping can inhibit the migration of excessive metal ions to the lithium layer, slow the spinel phase formation, and increase the structural stability of lithium manganese-based cathode materials. Anion doping mainly compensates and replaces the oxygen vacancies formed during the charging process. This method can suppress the formation of oxygen vacancies, improve the safety and the coulomb efficiency of the cathode electrode material. Polyanion doping is similar to anion doping, and is also doped at the oxygen position of the cathode electrode material. As the strong binding energy of the polyanion and the transition metals, the migration of the transition metals is suppressed, resulting into the stable layered structure and significantly improved electrochemical performances. Co-doping is the simultaneous doping of cations and anions into the cathode electrode material. This method combines the synergistic effect of the cations and cations simultaneously, which can stabilize the layered structure, significantly improve its stability, and improve the cycling ability of the battery. This article summarizes the structural composition, reaction mechanism, and intrinsic defects of lithium-rich manganese-based cathode mate-rials. We emphatically focus on the doping methods of cation doping, anion doping, polyanion doping, and co-doping and analyze their effects on the material properties. Besides, the existing problems of the doping modification at this stage are also elaborated, and future research directions are prospected in order to provide a reference for the preparation of stable and high-performance lithium-manganese-based cathode materials.

Key words: lithium-ion batteries lithium-rich manganese-based cathode materials ion doping doping modification electrochemical properties

出版日期: 2021-04-10 发布日期: 2021-04-22

ZTFLH:

TM912

基金资助: 国家自然科学基金(22002054;52064028;51504111;51564029);中国博士后科学基金 (2018M633418);昆明理工大学分析测试基金 (2018T20172015)

作者简介: 翟鑫华,2018年6月毕业于辽宁科技学院,获工学学士学位。现为昆明理工大学冶金与能源工程学院硕士研究生,师从黄惠教授。目前主要研究方向为锂离子电池用富锂锰基正极材料。
黄慧,昆明理工大学教授,博士研究生导师。获得四川大学高分子科学学士学位,云南大学无机材料硕士学位,昆明理工大学冶金物理化学博士学位,2014年—2015年在佛罗里达大学任访问学者。主要从事导电节能聚合物电极材料、储能材料、特种功能粉末材料、冶金电化学和湿法冶金新材料等领域的研究。目前已发表48篇研究论文,其中包括36篇SCI和EI论文。

引用本文:

翟鑫华, 张盼盼, 周建峰, 何亚鹏, 黄惠, 郭忠诚. 锂离子电池用富锂锰基正极材料掺杂改性研究进展[J]. 材料导报, 2021, 35(7): 7056-7062.
ZHAI Xinhua, ZHANG Panpan, ZHOU Jianfeng, HE Yapeng, HUANG Hui, GUO Zhongcheng. Research Progress on Doping Modification of Li-rich Manganese-based Cathode Materials for Lithium-ion Batteries. Materials Reports, 2021, 35(7): 7056-7062.

链接本文:

http://www.mater-rep.com/CN/10.11896/cldb.19090064 或 http://www.mater-rep.com/CN/Y2021/V35/I7/7056

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