Evidence for reversible formation of metallic Cu in Cu0.1V2O5 xerogel cathodes during intercalation cycling of Li+ ions as detected by X-ray absorption spectroscopy

被引:50
作者
Giorgetti, M
Mukerjee, S
Passerini, S
McBreen, J
Smyrl, WH
机构
[1] Univ Minnesota, Dept Chem Engn & Mat Sci, Corros Res Ctr, Minneapolis, MN 55455 USA
[2] Northeastern Univ, Dept Chem, Boston, MA 02115 USA
[3] ENEA, CR Casaccia, I-00060 Rome, Italy
[4] Brookhaven Natl Lab, Div Mat Sci, Dept Appl Sci, Upton, NY 11973 USA
关键词
D O I
10.1149/1.1379029
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Vanadium pentoxide materials prepared through sol-gel processes (xerogel. aerogel. and aerogel-like) act as excellent intercalation hosts for lithium as well as polyvalent cations. The large lithium insertion capacity of these materials makes them attractive for use as cathodes in high-capacity lithium batteries. Copper-doped V2O5-based cathodes have excellent properties in terms of high intercalation rate and very good reversibility upon cycling with no capacity hiding after more than 450 cycles. This paper reports in situ X-ray absorption spectroscopy (XAS) investigations of copper-doped V2O5 xerogel. The K-edge X-ray adsorption thresholds of V and Cu were studied. The local structure around copper is found to change dramatically during individual insertion/ release cycles for Li+ ions. The XAS analysis indicates that the lithiation of the Cu0.1V2O5 xerogel cathode proceeds with concurrent formation of copper metal. However. the starting compound is regenerated upon releasing the inserted lithium (charging the cathode), thus revealing the foundation for excellent structural and electronic reversibility of the material. (C) 2001 The Electrochemical Society.
引用
收藏
页码:A768 / A774
页数:7
相关论文
共 42 条
[1]  
ABRUNA HD, 1991, ELECTROCHEMICAL INTE, P1
[2]  
ALLEN PG, 1992, SYNCHROTRON RAD NEWS, V5, P16
[3]   ABINITIO STUDIES OF X-RAY ABSORPTION-EDGE IN COPPER-COMPLEXES .1. ATOMIC CU2+ AND CU(II)CL2 [J].
BAIR, RA ;
GODDARD, WA .
PHYSICAL REVIEW B, 1980, 22 (06) :2767-2776
[4]   STUDY OF UNDERPOTENTIALLY DEPOSITED COPPER ON GOLD BY FLUORESCENCE DETECTED SURFACE EXAFS [J].
BLUM, L ;
ABRUNA, HD ;
WHITE, J ;
GORDON, JG ;
BORGES, GL ;
SAMANT, MG ;
MELROY, OR .
JOURNAL OF CHEMICAL PHYSICS, 1986, 85 (11) :6732-6738
[5]   Hydrothermal synthesis of vanadium oxides [J].
Chirayil, T ;
Zavalij, PY ;
Whittingham, MS .
CHEMISTRY OF MATERIALS, 1998, 10 (10) :2629-2640
[6]   Doped vanadium oxides as host materials for lithium intercalation [J].
Coustier, F ;
Hill, J ;
Owens, BB ;
Passerini, S ;
Smyrl, WH .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (04) :1355-1360
[7]   A 400 mAh/g aerogel-like V2O5 cathode for rechargeable lithium batteries [J].
Coustier, F ;
Passerini, S ;
Smyrl, WH .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1998, 145 (05) :L73-L74
[8]   V2O5 aerogel-like lithium intercalation host [J].
Coustier, F ;
Lee, JM ;
Passerini, S ;
Smyrl, WH .
SOLID STATE IONICS, 1999, 116 (3-4) :279-291
[9]   Performance of copper-doped V2O5 xerogel in coin cell assembly [J].
Coustier, F ;
Jarero, G ;
Passerini, S ;
Smyrl, WH .
JOURNAL OF POWER SOURCES, 1999, 83 (1-2) :9-14
[10]   AN EXTENDED X-RAY-ABSORPTION FINE-STRUCTURE STUDY OF AQUEOUS-SOLUTIONS BY EMPLOYING MOLECULAR-DYNAMICS SIMULATIONS [J].
DANGELO, P ;
DINOLA, A ;
FILIPPONI, A ;
PAVEL, NV ;
ROCCATANO, D .
JOURNAL OF CHEMICAL PHYSICS, 1994, 100 (02) :985-994