Oxidation process of polysulfides in charge process for lithium-sulfur batteries

被引:30
作者
Xiong, Shizhao [1 ]
Xie, Kai [1 ]
Diao, Yan [1 ]
Hong, Xiaobin [1 ]
机构
[1] Natl Univ Def Technol, Sch Aerosp & Mat Engn, Dept Mat Engn & Appl Chem, Changsha 410073, Hunan, Peoples R China
关键词
Polysulfides; Oxidation process; Solution thermodynamic analysis; Lithium-sulfur batteries; Carbon disulfide; CATHODE MATERIAL; HIGH-CAPACITY; COMPOSITE; MECHANISMS; DISCHARGE; CELLS;
D O I
10.1007/s11581-012-0697-9
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The oxidation of polysulfides to element sulfur in charge process was studied by solution thermodynamic analysis and means of cyclic voltammetry (CV), X-ray diffraction (XRD), and charge-discharge test. Basing on the solution thermodynamic analysis, the oxidation process of polysulfides to element sulfur would arise only if the charge voltage exceeds 3.36 V in a lithium-sulfur cell employing 1.0 M LiN(CF3SO2)(2) in 1,2-dimethoxy ethane. Furthermore, the minimum of charge voltage which can push the oxidation would fall down with the increasing solubility of elemental sulfur in electrolyte solution. These analyses were confirmed by practical measurements. One new anodic peak corresponding to the oxidation process of polysulfides to solid sulfur was observed by CV. Both XRD patterns and charge-discharge test showed that the element sulfur appeared in the cathode after the battery was charged over 3.4 V. Hence, the lithium-sulfur cell charged over 3.4 V exhibited an improved cycle life since the capacity degradation between the first cycle and the second was depressed. In order to improve the energy efficiency, carbon disulfide was added in the electrolyte solution of lithium-sulfur cell to increase the solubility of sulfur.
引用
收藏
页码:867 / 872
页数:6
相关论文
共 33 条
[1]   Building better batteries [J].
Armand, M. ;
Tarascon, J. -M. .
NATURE, 2008, 451 (7179) :652-657
[2]   Ordered mesoporous carbon/sulfur nanocomposite of high performances as cathode for lithium-sulfur battery [J].
Chen, Shu-Ru ;
Zhai, Yun-Pu ;
Xu, Gui-Liang ;
Jiang, Yan-Xia ;
Zhao, Dong-Yuan ;
Li, Jun-Tao ;
Huang, Ling ;
Sun, Shi-Gang .
ELECTROCHIMICA ACTA, 2011, 56 (26) :9549-9555
[3]   Capacity fading mechanisms on cycling a high-capacity secondary sulfur cathode [J].
Cheon, SE ;
Choi, SS ;
Han, JS ;
Choi, YS ;
Jung, BH ;
Lim, HS .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2004, 151 (12) :A2067-A2073
[4]   Rechargeable lithium sulfur battery - I. Structural change of sulfur cathode during discharge and charge [J].
Cheon, SE ;
Ko, KS ;
Cho, JH ;
Kim, SW ;
Chin, EY ;
Kim, HT .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2003, 150 (06) :A796-A799
[5]   Rechargeable lithium sulfur battery - II. Rate capability and cycle characteristics [J].
Cheon, SE ;
Ko, KS ;
Cho, JH ;
Kim, SW ;
Chin, EY ;
Kim, HT .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2003, 150 (06) :A800-A805
[6]   Analytical detection of soluble polysulphides in a modified Swagelok cell [J].
Dominko, Robert ;
Demir-Cakan, Rezan ;
Morcrette, Mathieu ;
Tarascon, Jean-Marie .
ELECTROCHEMISTRY COMMUNICATIONS, 2011, 13 (02) :117-120
[7]   Morphological and Structural Studies of Composite Sulfur Electrodes upon Cycling by HRTEM, AFM and Raman Spectroscopy [J].
Elazari, Ran ;
Salitra, Gregory ;
Talyosef, Yossi ;
Grinblat, Judith ;
Scordilis-Kelley, Charislea ;
Xiao, Ang ;
Affinito, John ;
Aurbach, Doron .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2010, 157 (10) :A1131-A1138
[8]  
Enghag P., 2004, ENCY ELEMENTS
[9]  
Hwang DC, 2005, US Patent, Patent No. 6852450
[10]  
Ji X, 2009, NAT MATER, V2460, P500