Electrochemical behavior of Ge and GeX2 (X = O, S) glasses:: Improved reversibility of the reaction of Li with Ge in a sulfide medium

被引:96
作者
Kim, Youngsik [1 ]
Hwang, Haesuk [2 ]
Lawler, Katherine [1 ]
Martin, Steve W. [1 ]
Cho, Jaephil [2 ]
机构
[1] Iowa State Univ, Dept Mat Sci & Engn, Ames, IA 50011 USA
[2] Kumoh Natl Inst Technol, Dept Appl Chem, Gumi 730701, South Korea
关键词
germanium; sulfide glasses; anode materials; cycle life; lithium-ion batteries;
D O I
10.1016/j.electacta.2007.12.015
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Sulfide glasses have been considered as new anode materials for lithium-ion batteries because their high ionic conductivity (approximately >= 10(-4) S/cm) (more than one order of magnitude higher than oxide glasses (approximately <= 10(-6) S/cm)) was expected to accelerate Li+ ion insertion into and extraction from anode materials during charge and discharge reactions. This intrinsic property can yield the reversible lithium-alloying reaction by minimizing the aggregation of lithium-alloy phases leading to the improvement of cycling behavior. To examine sulfide glasses as new anode materials, GeS2 glass was chosen for study in this work due to its stability in air-atmospheres. The electrochemical properties of the GeS2 glass were compared with those of the Ge metal and GeO2 glass. The initial insertion of lithium into the GeX2 (X = O, S) glasses leads to the formation of Li2X (X = O, S) phases associated with the irreversible capacity on the first cycle. The improved reversibility of the reaction of lithium with Ge was observed in the Li2S medium rather than Li2O one, which leads to the improvement of cycle performance in the GeS2 glass anode. (C) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码:5058 / 5064
页数:7
相关论文
共 28 条
[1]  
Anderson O.L., 1954, J AM CERAM SOC, V37, P573, DOI [DOI 10.1111/J.1151-2916.1954.TB13991.X, 10.1111/j.1151-2916.1954.tb13991.x]
[2]   On the aggregation of tin in SnO composite glasses caused by the reversible reaction with lithium [J].
Courtney, IA ;
McKinnon, WR ;
Dahn, JR .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (01) :59-68
[3]   Electrochemical and in situ x-ray diffraction studies of the reaction of lithium with tin oxide composites [J].
Courtney, IA ;
Dahn, JR .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1997, 144 (06) :2045-2052
[4]   Key factors controlling the reversibility of the reaction of lithium with SnO2 and Sn2BPO6 glass [J].
Courtney, IA ;
Dahn, JR .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1997, 144 (09) :2943-2948
[5]   Combinatorial study of Sn1-xCox (0 &lt; x &lt; 0.6) and [Sn0.55Co0.45]1-yCy (0 &lt; y &lt; 0.5) alloy negative electrode materials for Li-ion batteries [J].
Dahn, JR ;
Mar, RE ;
Abouzeid, A .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2006, 153 (02) :A361-A365
[6]   On the nature of Li insertion in tin composite oxide glasses [J].
Goward, GR ;
Leroux, F ;
Power, WP ;
Ouvrard, G ;
Dmowski, W ;
Egami, T ;
Nazar, LF .
ELECTROCHEMICAL AND SOLID STATE LETTERS, 1999, 2 (08) :367-370
[7]   Electrochemical and multinuclear solid-state NMR studies of tin composite oxide glasses as anodes for Li ion batteries [J].
Goward, GR ;
Nazar, LF ;
Power, WP .
JOURNAL OF MATERIALS CHEMISTRY, 2000, 10 (05) :1241-1249
[8]  
HIGGINS RA, 1998, HDB BATTERY MAT, P359
[9]   Tin-based amorphous oxide: A high-capacity lithium-ion-storage material [J].
Idota, Y ;
Kubota, T ;
Matsufuji, A ;
Maekawa, Y ;
Miyasaka, T .
SCIENCE, 1997, 276 (5317) :1395-1397
[10]  
IDOTA Y, 1994, Patent No. 2134053