物理化学学报 >> 2019, Vol. 35 >> Issue (7): 667-683.doi: 10.3866/PKU.WHXB201806062

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锂硒电池正极材料的研究进展

陈东,岳昕阳,李璕琭,吴晓京,周永宁*()   

  • 收稿日期:2018-06-28 发布日期:2018-12-21
  • 通讯作者: 周永宁 E-mail:ynzhou@fudan.edu.cn
  • 作者简介:周永宁,复旦大学青年研究员,出生于1982年。2010年在复旦大学材料科学系获得博士学位;2010-2011年复旦大学化学系从事博士后研究;2012-2015年在美国布鲁克海文国家实验室任助理研究员;2015年回国加入复旦大学材料科学系,任青年研究员。主要从事新型电池材料设计及机理研究
  • 基金资助:
    国家自然科学基金(51502039);中央组织部青年千人计划(D1210005)

Research Progress of Cathode Materials for Lithium-Selenium Batteries

Dong CHEN,Xinyang YUE,Xunlu LI,Xiaojing WU,Yongning ZHOU*()   

  • Received:2018-06-28 Published:2018-12-21
  • Contact: Yongning ZHOU E-mail:ynzhou@fudan.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(51502039);1000 Youth Talents Plan, China(D1210005)

摘要:

锂硒电池因其高体积比容量(3253 mAh·cm-3),以及硒的高电导率(1 × 10-3 S·m-1)等显著优点,在体积受限的储能系统中具有潜在的应用价值。引起了国内外研究学者的广泛关注。但是,目前锂硒电池的性能还不理想,仍然存在许多科学问题亟待解决,包括多硒化锂的穿梭效应,电解液的适配性,充放电过程中电极体积变化等。近年来,研究工作者针对这些关键科学问题开展了许多研究和探索,锂硒电池已成为储能领域的一个新的研究热点。本文综述了锂硒电池的研究现状,着重介绍了硒-碳复合正极材料的研究进展,论述了锂硒电池的优势及存在的问题,系统分析了硒基正极材料结构和性能之间的关系,总结了锂硒电池的反应机理及其与电解液的相关性,最后展望了锂硒电池的未来发展方向。

关键词: 锂硒电池, 正极材料, 硒-碳复合, 电解液, 穿梭效应

Abstract:

The global energy shortage has led to vigorous research for the development of new energy technologies in all countries to cope with the energy crisis and to meet the demand for green energy. In this regard, the development of new battery systems with high energy densities has become the current research hotspot. Lithium-sulfur battery is considered as a promising candidate due to its high energy density and low cost. However, it suffers from the insulating nature of sulfur and the shuttle effect of polysulfide, which hinder its practical application. Selenium (Se), as a congener element of sulfur, possesses electrochemical properties similar to sulfur. Lithium-selenium batteries have attracted considerable research attention due to the high electronic conductivity of selenium and high volumetric capacity. The conductivity of Se (1 × 10-3 S·m-1) is ~24 orders of magnitude higher than that of sulfur (5 × 10-28 S·m-1), providing much better electron transportation in cathode, leading to fast electrochemical reaction and high utilization of Se. Moreover, Se is compatible with cheap carbonate-based electrolytes, which could greatly reduce the cost. Lithium-selenium batteries also have much higher theoretical volumetric and gravimetric capacities (3253 mAh·cm-3 and 675 mAh·g-1, respectively) than those of commercial lithium-ion batteries such as LiCoO2/graphite and LiFePO4/graphite systems. Volumetric capacity is a more important requirement than gravimetric capacity for a battery, especially for applications in electric vehicles and portable electronic devices, because they have limited space for accommodating batteries. Thus, research on lithium-selenium batteries with high volumetric capacities is of great significance for these volume-sensitive applications. However, the electrochemical performance of current lithium-selenium batteries is not satisfactory. Several key problems must be solved, including shuttle effect, electrolyte compatibility, volume change during cycling, capacity fading, and low coulombic efficiency. In recent years, widespread research has been conducted to address these problems and considerable progress has been made. This review summarizes the status of research on lithium-selenium batteries, and focuses on the recent progress in the research of selenium-carbon cathode materials. The advantages and disadvantages of lithium-selenium batteries are discussed in detail. The performance-structure relationship is analyzed from the perspective of different dimensional structures, including one-dimensional nanofibers and nanowires, two-dimensional nanosheets, composite films and scaffolds, three-dimensional hollow structures, solid structures, and freestanding structures (spheres, nanobelts, nanotubes, microcubes etc.). Other types of selenium-based cathodes, including metal selenides and heterocyclic selenium-sulfur (SexSy), are also described. The compatible electrolytes and functional interlayers for lithium-selenium batteries are also discussed. The reaction mechanisms of lithium-selenium batteries and their relationship with various electrolytes are summarized. Finally, the future perspective of lithium-selenium batteries is proposed.

Key words: Lithium-selenium battery, Cathode material, Selenium-carbon composite, Electrolyte, Shuttle effect

MSC2000: 

  • O646