锂硫电池石墨烯/硫复合正极材料的制备及其电化学性能

doi:10.3724/SP.J.1077.2014.13485

无机材料学报 ›› 2014, Vol. 29 ›› Issue (6): 627-632.DOI: 10.3724/SP.J.1077.2014.13485 CSTR: 32189.14.SP.J.1077.2014.13485

锂硫电池石墨烯/硫复合正极材料的制备及其电化学性能

陈飞彪¹, 王英男¹, 吴伯荣^1,2, 熊云奎³, 廖维林³, 吴锋^1,2, 孙喆²

(1. 北京理工大学化工与环境学院, 北京100081; 2. 动力电池及化学能源材料北京市高等学校工程研究中心, 北京100081; 3. 江西师范大学精细化工重点实验室, 南昌 330027)

收稿日期:2013-09-24 修回日期:2013-11-25 出版日期:2014-06-20 网络出版日期:2014-05-27
作者简介:陈飞彪(1983-), 男, 博士研究生. E-mail: chengfeibiao@163.com
基金资助:
国家863计划(2013AA050903) 863 Program(2013AA050903)

Preparation and Electrochemical Performance of Activation Graphene/Sulfur Complex Cathode Material for Lithium-sulfur Batteries

CHEN Fei-Biao¹, WANG Ying-Nan¹, WU Bo-Rong^{1, 2}, XIONG Yun-Kui³, LIAO Wei-Ling³, WU Feng^{1, 2}, SUN Zhe²

(1. School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081, China; 2. Beijing Higher Institution Engineering Research Center of Power Battery and Chemical Energy Materials, Beijing 100081, China; 3. Jiangxi Fine Chemical Key Laboratory , Jiangxi Normal University, Jiangxi 330027, China)

Received:2013-09-24 Revised:2013-11-25 Published:2014-06-20 Online:2014-05-27
About author:CHEN Fei-Biao. E-mail: chengfeibiao@163.com

摘要/Abstract

摘要：

以经活化处理的石墨烯(AG)为主体材料, 通过化学还原法制备了石墨烯负载硫的复合正极材料AG/S。SEM、EDX和TEM测试结果表明经活化处理后形成手风琴结构的AG, 有利于电解液的浸润; 活性物质硫均匀地负载在AG表面, 同时沉积在AG的层间。电化学测试表明: 在400 mA/g电流密度下, AG/S复合正极材料首次放电比容量为1452.9 mAh/g, 经过200次循环之后, 放电比容量仍保持在909.7 mAh/g; 在1000 mA/g电流密度下, AG/S复合材料首次放电比容量为1309.9 mAh/g, 经过200次循环之后, 放电比容量仍保持在717.1 mAh/g。AG/S复合正极材料的倍率性能、库仑效率和循环性能优异, 这得益于小尺寸的硫在材料中均匀分布, 活化石墨烯优良的导电性以及其结构对硫的固化作用。

关键词: 锂硫电池, 石墨烯, 复合正极材料, 循环性能

Abstract:

Novel accordion structure activation graphene/sulfur (AG/S) complex cathode materials were prepared by solution-based reaction-deposition method using activation graphene (AG) as precursors. SEM, EDX and TEM measurement were conducted. The result indicated that the AG/S had accordion structure with a uniform S coating on accordion structure AG. At the same time, sulfur was also found to be deposited on the interlayer of AG. Constant current charge-discharge tests showed that the AG/S complex cathode material with 65wt% sulfur delivered a high initial discharge speciﬁc capacity of 1452.9 mAh/g at the current density of 400 mA/g, with 909.7 mAh/g remained after 200 cycles. Meanwhile, an initial discharge speciﬁc capacity of 1309.9 mAh/g could be obtained for the material at the larger current density of 1000 mA/g, keeping 717.1 mAh/g after 200 cycles at the same current density. The rate performance, coulombic efficiency and cycling stability of the AG/S complex cathode materials were confirmed to be excellent, which may be originated from the homogeneous distribution of the sulfur with small powder size in the composites, the excellent electrical conductivity of AG and the fixation effect of the functional groups on the surface of AG for S.

Key words: lithium-sulfur battery, graphene, complex cathode material, cycling performance

中图分类号:

O646

陈飞彪, 王英男, 吴伯荣, 熊云奎, 廖维林, 吴锋, 孙喆. 锂硫电池石墨烯/硫复合正极材料的制备及其电化学性能[J]. 无机材料学报, 2014, 29(6): 627-632.

CHEN Fei-Biao, WANG Ying-Nan, WU Bo-Rong, XIONG Yun-Kui, LIAO Wei-Ling, WU Feng, SUN Zhe. Preparation and Electrochemical Performance of Activation Graphene/Sulfur Complex Cathode Material for Lithium-sulfur Batteries[J]. Journal of Inorganic Materials, 2014, 29(6): 627-632.

图/表 8

图1 MCMB和AG (a)及AG、AG/S和S (b)的XRD图谱

Fig. 1 XRD patterns of MCMB and AG (a) and AG, AG/S and S (b)

图2 AG(a)和AG/S(b)的SEM照片, AG/S的能谱分析(c), C元素图(d)和S元素图(e)

Fig. 2 SEM images of AG (a) and AG/S (b), EDX analysis of AG/S (c), elemental maps of C (d) and S (e)

图3 AG (a, b)和AG/S (c, d)的TEM照片

Fig. 3 TEM images of AG (a, b) and AG/S (c, d)

图4 AG/S复合正极材料的TGA曲线

Fig. 4 Thermo gravimetric analysis (TGA) curves of AG/S complex cathode materials

图5 AG/S复合正极材料的CV曲线

Fig. 5 Cyclic voltammogram curves of AG/S complex cathode materials

图6 AG/S复合正极材料的充放电平台曲线(a)和循环性能(b)

Fig. 6 Charge-discharge profiles of the AG/S composite after different cycles at 400 mA/g rate (a) and cycling performance of the AG/S composite (b)

图7 AG/S复合正极材料的倍率性能

Fig.7 Rate capabilities of the AG/S composite cathodes

图8 单质S及AG/S复合正极材料的交流阻抗曲线

Fig. 8 Impedance spectra for electrodes of the pure S and AG/S composite

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锂硫电池石墨烯/硫复合正极材料的制备及其电化学性能

Preparation and Electrochemical Performance of Activation Graphene/Sulfur Complex Cathode Material for Lithium-sulfur Batteries

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