| INORGANIC MATERIALS AND CERAMIC MATRIX COMPOSITES |
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| Research Progress in High Performance Lithium Manganese Phosphate Cathode Materials |
| LI Junhao1, FENG Sitong1, ZHANG Shengjie1, ZHENG Yuying1, XU Jianbo2, DANG Dai1, LIU Quanbing1
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1 School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006
2 Department of Mechanical and Aerospace Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong SAR, China |
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Abstract Lithium-ion batteries have many advantages such as high energy density, good cycle performance, no memory effectand so on. They are widely used in many fields such as electronic products, electric traffic, and energy storage system, which have greatly improved the modern human's life. Lithium iron phosphate (LiFePO4), as a cathode electrode material, possesses high safety, excellent cycle performance and thermal stability, and it is widely used in lithium-ion power battery. However, its energy density is low, which restricts its further development and application. Lithium manganese phosphate (LiMnPO4) has high safety and stability similar to LiFePO4, and its theoretical energy density is 21% higher than that of the latter, so it is considered to be the most promising cathode material for next-generation power lithium-ion power battery.
However, the olivine-structured LiMnPO4 still has some inherent defects that restrict its development and application: (1) the ionic conductivity and electronic conductivity of the material are very low, which make it's difficult to make full use of the material capacity; (2) LiMnPO4 reacts with the electrolyte to produce the product Li4P2O7, etc. which will result in the activity will gradually lose as charge and discharge process;(3) the manganese phosphate (MnPO4) formed after delithiation will be affected by the Jahn-Teller effect, the crystal structure will change from octahedron to cubic phase, and the channel of lithium-ion decompression is compressed, causing structural irreversible changes; (4) part of manganese ions are dissolved in the disproportionation reaction that occurs in the electrolyte causes the material to cycle poorly. A lot of work has been done to overcome these problems.
In order to improve the electrochemical performance of LiMnPO4, the researchers have made continuous attempts in the preparation and modification of materials:(1) nanocrystallization, shortening the solid-state diffusion path of lithium-ion, and increasing the reaction area of the electrode, thereby increasing the ionic conductivity of the material in macro; (2) selection control of planes, increasing the area of the crystal plane for rapid migration of lithium ions, thereby increasing the ionic conductivity of the material in micro; (3) body doping, in-situ substitution of heteroatoms or formation of solid solution to stabilize the crystal structure and improve ionic/electronic conductivity, thereby improving the cyclic and rate performance of the material;(4) surface coating, by coating conductive carbon, metal oxide layer, etc. on the surface of the material to improve the ionic/electronic conductivity of the material and prevent LiMnPO4 from directly contacting the electrolyte. Since now, LiMnPO4 has been developed from the original almost playno specific capacity, and developed to a theoretical value at a low rate.
In this paper, the research progress on the preparation and modification of high performance LiMnPO4 is summarized. The approaches to improve the material properties are analyzed from the aspects of material structure, surface interface properties and electrode reaction kinetics. Finally, we believe that the crystal surface control and surface coating modification on the basis of element doping and nanocrystallization is the most effective way to maximize the material properties, thus promoting its commercialization process.
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Published: 23 July 2019
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| Fund:This work was financially supported by the National Natural Science Foundation of China (21606050), Zhujiang Science and Technology New Star Project (201806010039), and Characteristic Innovation Projects of Collegesin Guangdong Province (2017KTSCX055). |
About author:: Junhao Li received his B.E. degree in Guangzhou University in 2017. He is a postgraduate student of Guangdong University of Technology under the supervision of associate professor Quanbing Liu. At present, his main research direction is manganese lithium phosphate cathode material and transition metal oxide cathode material inlithium-ion battery.
Quanbing Liu received his B.E. degree in chemistry from Wuhan Institute of Technology in 2007 and received his Ph.D. degree in applied chemistry from the South China University of Technology in 2012. He had worked on the research and design of lithium-ion batte-ries in the Tianjin Institute of Power Source and Zhuhai Coslight Battery Co., Ltd. He was introduced to Guangdong University of Technology as one of the “100 Youth” talents in 2016/11. He was selected into the fifth batch of “Outstanding Young Talents” in Zhuhai and the eighth batch of “Pearl River Science and Technology Stars” in Guangzhou. At present, he is mainly engaged in research on new energy materials and devices, including lithium ion batteries, lithium sulfur batteries, super capacitors, fuel cells.In recent years, more than 20 SCI papers have been published in the field, such as Advanced Energy Materials, Small, Journal of Materials Chemistry A, Journal of Power Source, and so on. |
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2019, Vol. 33 
