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

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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

Published: 22 April 2021

CLC number:

TM912

Fund:National Natural Science Foundation of China (22002054, 52064028, 51504111, 51564029), China Postdoctoral Science Foundation (2018M633418), and Analysis and Testing Foundation of Kunming University of Science and Technology (2018T20172015).

About author:: Xinhua Zhaireceived his B.E. degree in engineering from Liaoning Institute of Science and Technology in 2018. He is currently pursuing his master at College of Metallurgy and Energy Engineering, Kunming University of Science and Technology under the supervision of Prof. Hui Huang. His research is focused on lithium-rich manganese cathode materials in lithium-ion batte-ries.
Hui Huang received her B.E. degree in polymer scie-nce from Sichuan University, M.S. degree in inorganic material in Yunnan University, and obtained her PhD degree in metallurgical physical chemistry from Kunming University of Science and Technology. She was as a visiting scholar in Florida University from 2014 to 2015 and she is currently a full professor in Kunming University of Science and Technology. Her current research interests include energy-saving conductive polymer electrode materials, energy storage materials, special functional powder materials, metallurgical electrochemistry and novel materials in hydrometallurgy. At present, she has published 48 research papers, including 36 SCI and EI papers.

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	ZHAI Xinhua
	ZHANG Panpan
	ZHOU Jianfeng
	HE Yapeng
	HUANG Hui
	GUO Zhongcheng

Cite this article:

ZHAI Xinhua,ZHANG Panpan,ZHOU Jianfeng, et al. Research Progress on Doping Modification of Li-rich Manganese-based Cathode Materials for Lithium-ion Batteries[J]. Materials Reports, 2021, 35(7): 7056-7062.

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

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