锂离子电池的明星材料磷酸铁锂:基本性能、优化改性及未来展望

doi:10.11896/cldb.18090309

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Abstract  LiFePO₄ (LFP), an important member of the olivine-type lithium transition metal phosphate family, is currently regarded as one of the most successful commercialized cathode materials for lithium-ion batteries due to its prominent merits, including low cost, high safety, environmental friendliness, abundant resource, stable crystal structure, flat voltage profile, etc. However, its stable crystal structure leads to low electronic conductivity (10^-9—10^-10 S·cm^-1) and lithium ions mobility (10^-13—10^-16 cm²·s^-1), which severely limit its electrochemical perfor-mance. In this regard, overcoming the intrinsic bottlenecks of material and elevating its reversible capacity as well as rate capability, have become one of the hot topics in the field of energy storage devices. On the one hand, continuous efforts devoted in fundamental researches have made us a more clear understanding over LFP and analogous materials, and provided a theoretical basis for further optimization and modification of LFP. On the other hand, the electrochemical performance of commercial production of LFP prepared via solid phase methods, the most commonly used ones at present, still has tremendous potential for enhancement. Consequently, improving the production process or developing new industrialized preparation technologies are of significant concern both in academic and in industry.
    In recent years,researchers have achieved fruitful results in the modification and optimization of LFP by adopting a variety of optimization strategies:Ⅰ. structural nanosizing; Ⅱ. coating with advanced carbon materials, Ⅲ. crystal orientation engineering; Ⅳ. in-situ carbon coating, Ⅴ. suppressing or eliminating defects, Ⅵ. ions doping and Ⅶ. quantum dots modification, etc. Indeed, achieving superior electrochemical performance of LFP-based composites requires affective combination of multiple methodologies, and it is unadvisable to expect to make breakthrough with a single approach. Moreover, for lithium ions migrate with single diffusion channels along the b-axis in LFP bulk phase, preparing LFP with (010) crystal planes preferred orientation is beneficial to shorten the transmission distance of lithium ions, thus increasing de-intercalation/intercalation sites and in turns enhancing reaction kinetics. In this respect, the crystal orientation engineering has been a crucial strategy for further improving the performances of LFP. Besides, with the deepening of the basic research of LFP, a series of significant progresses have been made in the dynamic processes, such as lithium ions delithiation/relithiation, transportation, reaction mechanism and material structure evolution.
    Based on the research exploring of crystal structure of olivine lithium iron phosphate (Pnma), this paper provides a systematical summary over the lithium ions diffusion in LFP crystal, the characteristic of (010) crystal plane and its influence on electrochemical performances, as well as a thorough review of the seven aspects. Furthermore, it also points out the research directions and perspectives of LFP in the near future, involving mechanism research and applied research.

Key words： LiFePO₄ lithium ions diffusion anti-site defects (010) planes cathode materials lithium-ion batteries

Published: 12 September 2019

CLC number:

TM914

About author:: Liuwen Tian graduated from Sichuan University with a major of advanced energy materials and devices, whose research direction is LiFePO₄ based lithium-ion batte-ries. He received his Bachelor degree in 2017. In the same year, he entered the Institute of Photovoltaics, Southwest Petroleum University to pursue Master degree under supervision of Prof. Yuelong Huang and Prof. Hua Yu. His current research interests lie in high-efficiency and flexible perovskite solar cells, energy storage materials and technology.
Hua Yu is currently a full professor in the Institute of Photovoltaics, Southwest Petroleum University. He received his Ph.D. degree in Griffith University in 2010. And received his Bachelor and Master degrees in Harbin Institute of Technology and Guangzhou Institute of Energy Conversion, Chinese Academy of Science in 2003 and 2006, respectively. He did his postdoctoral study at the University of Queensland from 2011 to 2015. He worked as a Research Fellow at Advanced Materials Processing Center in Australia from 2015 to 2018. After that he joined the Southwest Petroleum University. His present research interests are the applied research about the application of smart film materials in advanced energy devices, including solar cells, lithium-ion batteries, and smart glass.
Yuelong Huang is currently the dean of the Institute of Photovoltaics, Southwest Petroleum University. He received his Bachelor and Master degrees in Physics Department from Lanzhou University in 1998 and 2001, respectively. And he received his Ph.D. degree from Hagen University in German with the support of German DAAD scholarship from 2001 to 2005. After that, he did his postdoctoral study at the JUELICH National Research Centre, German. His research is focused on silicon material, silicon electronic devices and photovoltaic technology (e.g., high efficiency silicon film and silicon heterojunction solar cell technology). Dr. Yuelong Huang has been engaging in the research and industrialization promotion of the photovoltaic solar cells for many years. He is experienced in promoting the transformation of scientific and technological achievements, the innovation of technology enterprises and starting up business for technical ta-lents. He holds the posts in several equity investment funds as member of the investment decision committee and repeatedly served as the jury member of the Thousand Talents Plan of the Central Organization Department of China.

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Cite this article:

TIAN Liuwen,YU Hua,ZHANG Wenfeng, et al. The Star Material of Lithium Ion Batteries, LiFePO₄: Basic Properties,Optimized Modification and Future Prospects[J]. Materials Reports, 2019, 33(21): 3561-3579.

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http://www.mater-rep.com/EN/10.11896/cldb.18090309 OR http://www.mater-rep.com/EN/Y2019/V33/I21/3561

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