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化学进展 2015, Vol. 27 Issue (4): 336-348 DOI: 10.7536/PC141010 前一篇   后一篇

所属专题： 锂离子电池

• 综述与评价 •

锂离子电池SiOx(0<x≤2)基负极材料

刘欣1, 赵海雷*1,3, 解晶莹*2,4, 吕鹏鹏1, 王可2, 崔佳佳4   

  1. 1. 北京科技大学材料科学与工程学院 北京 100083;
    2. 上海空间电源研究所 上海 200245;
    3. 新能源材料与技术北京市重点实验室 北京 100083;
    4. 上海动力与储能电池系统工程中心 上海 200245
  • 收稿日期:2014-10-01 修回日期:2014-12-01 出版日期:2015-04-15 发布日期:2015-02-04
  • 通讯作者: 赵海雷, 解晶莹 E-mail:hlzhao@ustb.edu.cn;xiejingying2007@126.com
  • 基金资助:
    国家重点基础研究发展计划(973)项目(No. 2013CB934003),国家自然科学基金项目(No. 21273019),国家高技术研究发展计划(863)项目(No. 2013AA050902),上海市科技人才计划项目(No. 12XD1421900)和上海市科委科技创新项目(No.12dz1200503, 13dz2280200)资助
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SiOx(0<x≤2) Based Anode Materials for Lithium-Ion Batteries

Liu Xin1, Zhao Hailei*1,3, Xie Jingying*2,4, Lv Pengpeng1, Wang Ke2, Cui Jiajia4   

  1. 1. School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China;
    2. Shanghai Institute of Space Power Sources, Shanghai 200245, China;
    3. Beijing Key Lab of New Energy Materials and Technology, Beijing 100083, China;
    4. Shanghai Engineering Center for Power and Energy Storage Systems, Shanghai 200245, China
  • Received:2014-10-01 Revised:2014-12-01 Online:2015-04-15 Published:2015-02-04
  • Supported by:
    The work was supported by the National Key Basic Research Program of China (973 Program)(No. 2013CB934003), the National Natural Science Foundation of China (No. 21273019), the National High Technology Research and Development Program of China (863 Program)(No. 2013AA050902) , the Shanghai Science and Technology Talent Project Funds (No.12XD1421900), and the Shanghai Science and Technology Development Funds (No. 12dz1200503,13dz2280200).
随着锂离子电池向电动汽车、可再生能源储能系统等大型应用领域发展,锂离子电池的能量密度、功率密度等性能指标需要进一步提高。在负极材料方面,传统的石墨碳负极材料的比容量有限,已经难以满足高能量密度电池的需求。以Si基材料为代表的新型高比容量负极材料受到了人们的广泛关注。其中,SiOx材料在发挥高比容量的同时,具有相比纯Si更小的体积变化,因而在循环寿命方面更具实用潜力。本文对目前报道的SiOx基负极材料的研究工作进行总结,系统阐述了SiOx材料的基本电化学性能、结构模型、电化学机理及合成方法,分类介绍了改进SiOx材料电化学性能的各类措施,并对其中SiO及无定形SiO2材料进行了重点论述。研究表明,氧含量、歧化程度、表面状态等对SiOx材料的电化学性能具有重要影响;界面团簇混合(ICM)结构模型可更好地对其电化学机理进行理解;通过与第二相(碳、金属、金属氧化物等)复合,造孔,表面改性(包覆、刻蚀等)及其他手段(改变粘结剂及电解液)可有效提升SiOx基材料的首次库仑效率和循环性能;部分使用SiOx基材料的全电池具有循环600次后容量保持率达90%的优秀循环性能。SiOx基材料已成为一种在高比能量锂离子电池中极具应用潜力的负极材料。
关键词： SiOx, 无定形态, 复合物, 负极材料, 锂离子电池
With rapidly growing application of lithium-ion batteries in electric vehicles and renewable energy storage, there is an increasing demand on high performance batteries in terms of energy density and power density. For anode materials, the traditional graphitized carbon materials cannot meet these requirements, novel high-capacity anode materials are being widely investigated, including Si-based materials. Among them, SiOx is considered to be a promising anode material for the practical use because it can deliver a high capacity and at the same time produce relatively lower volume change upon cycling compared to pure silicon. This paper summarizes the published works on SiOx-based anode materials. The basic electrochemical performance, structure model, electrochemical reaction mechanism and synthesis methods of SiOx powders are systematically reviewed. Methods used to improve electrochemical performance are classified and introduced, emphasized on those of SiO and amorphous SiO2. These works suggested that the oxygen content, disproportionation level and surface state of SiOx have significant influence on the electrochemical performance of SiOx. The interface clusters mixture (ICM) structural model can be used to better understand the nature of the electrochemical reaction processes of SiOx. Introduction of second phase (carbon, metals, metal oxides, etc.), preparation of porous structure, surface modification and optimization of binder and electrolyte are proved to be effective methods to improve the coulombic efficiency and cycling performance of SiOx electrode. Batteries with optimized SiOx-based material showed good cycling stability with 90% capacity retention after 600 cycles. SiOx-based composite is one of the best promising anode materials for lithium-ion batteries with high energy density.

Contents
1 Introduction
2 Properties of SiOx material
2.1 Basic electrochemical performance
2.2 Structure
2.3 Mechanism of the electrochemical process
2.4 Synthesis methods
3 SiOx-based materials
3.1 Compositing with second phase
3.2 Porous structured SiOx
3.3 Surface modification
3.4 Other factors and issues
4 Conclusion and outlook

Key words: SiOx, amorphous phase, composites, anode materials, lithium-ion batteries

中图分类号: 

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摘要

锂离子电池SiOx(0<x≤2)基负极材料