化学学报 ›› 2013, Vol. 71 ›› Issue (07): 1011-1016.DOI: 10.6023/A13030268 上一篇    下一篇

研究通讯

锂离子电池Sn30Co30C40三元合金负极材料的制备与性能研究

刘欣a, 解晶莹b, 赵海雷a,c, 王可b, 汤卫平b, 潘延林b, 丰震河b, 吕鹏鹏a   

  1. a 北京科技大学材料科学与工程学院 北京 100083;
    b 上海空间电源研究所 上海 200245;
    c 新能源材料与技术北京市重点实验室 北京 100083
  • 投稿日期:2013-03-12 发布日期:2013-05-02
  • 通讯作者: 解晶莹, E-mail: xiejingying2007@126.com;赵海雷, hlzhao@ustb.edu.cn. E-mail:xiejingying2007@126.com; hlzhao@ustb.edu.cn.
  • 基金资助:

    项目受国家基础研究(973, No. 2013CB934003);国家自然科学基金(21273019);上海市科技人才计划(No. 12XD1421900)和上海市科委科技创新项目(Nos. 10dz2250900, 12dz1200503)资助.

Synthesis and Properties of Sn30Co30C40 Ternary Alloy Anode Material for Lithium Ion Battery

Liu Xina, Xie Jingyingb, Zhao Haileia,c, Wang Keb, Tang Weipingb, Pan Yanlinb, Feng Zhenheb, Lv Pengpenga   

  1. a School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083;
    b Shanghai Institute of Space Power Sources, Shanghai 200245;
    c Beijing Key Lab of New Energy Materials and Technology, Beijing 100083
  • Received:2013-03-12 Published:2013-05-02
  • Supported by:

    Project supported by the National Key Basic Research Development Program of China (973 special preliminary study plan, No. 2013CB934003), the National Natural Science Foundation of China (No. 21273019), Shanghai Science and Technology Talent Project Funds (No. 12XD1421900) and Shanghai Science and Technology Development Funds (Nos. 10dz2250900, 12dz1200503).

随着人们对高比能量锂离子电池需求的逐步增加, Sn基合金成为目前高比容量负极材料的研究热点. 以低成本的金属氧化物、活性炭为原料经碳热还原法首先合成出中间产物CoSn2, 再将Co、石墨引入, 经高能球磨制备了Sn30Co30C40三元合金负极材料. 材料呈现微米级颗粒形貌, 其内部是由均匀分散于无定形碳中10 nm左右CoSn晶粒所组成. 材料的比容量为550 mAh/g左右, 首次效率为80%左右, 循环稳定性好、倍率性能优越, 是一种非常有发展前景的高比容量锂离子电池负极材料.

关键词: Sn30Co30C40, 碳热还原-高能球磨, 电化学性能, 合金负极, 锂离子电池

With the development of advanced lithium ion batteries, electrode materials with higher capacity are urgently in demand. With respect to the anode materials, Sn-based alloy materials with high theoretical capacity (990 mAh/g) have the potential to replace the traditional, low capacity carbon-based materials. However, the practical application of Sn-based anode materials is severely retarded due to the poor cycling stability of electrode, which is believed to be caused by the pulverization of active particles resulting from the large volume of Sn during lithiation/delithiation process. The Sn-Co-C ternary alloy with amorphous or nano microstructure can overcome this problem and therefore display attractive electrochemical performance, including high capacity and good cycle stability. In the present work, amorphous Sn30Co30C40 alloy material was synthesized through a simple and scalable two-step method (carbothermal reduction-high energy ball milling method). CoSn2 alloy was firstly prepared by the carbothermal reduction route from low cost metal oxide and activated carbon. Then the prepared CoSn2 were mixed with metal cobalt and graphite in a molar ratio of 3:3:8 via a high energy ball milling process to synthesize the final Sn30Co30C40 material. The preferential synthesis of CoSn2 alloy was important to get Sn30Co30C40 material with much smaller CoSn grain dispersed in carbon matrix and thus critical to the better electrochemical performance. XRD, SEM, TEM, HR-TEM, S-TEM and electrochemical tests were used to evaluate the structure and electrochemical performance of the CoSn2 and Sn30Co30C40 materials. The synthesized Sn30Co30C40 material displayed micro-sized particle morphology, which in fact was composed of 10 nm CoSn grains distributed well in amorphous carbon matrix. The Sn30Co30C40 material showed high specific capacity of 550 mAh/g with an initial coulombic efficiency of 80%, good cycling stability and excellent rate-capability. The specific capacity of 430, 380, 280 mAh/g could be achieved at the rate of 1 C, 2 C and 5 C, respectively.

Key words: Sn30Co30C40, carbothermal reduction-high energy ball milling, electrochemical performance, alloy anode, lithium ion battery