In situ X-ray absorption spectroscopic study on LiNi0.5Mn0.5O2 cathode material during electrochemical cycling

被引:209
作者
Yoon, WS
Grey, CP
Balasubramanian, M
Yang, XQ
McBreen, J [1 ]
机构
[1] SUNY Stony Brook, Dept Chem, Stony Brook, NY 11794 USA
[2] Brookhaven Natl Lab, Upton, NY 11973 USA
关键词
D O I
10.1021/cm030220m
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
We have investigated the local electronic and atomic structure of the LiMn0.5Ni0.5O2 electrode during the first charge and discharge process using in situ X-ray absorption spectroscopy (XAS) of the Mn and Ni K-edges. The Ni K-edge structure in the XANES spectrum shifts to higher energy during charge and shifts back reversibly during discharge in the higher voltage region of similar to4 V, whereas the Mn K-edge structure does not appear to exhibit a rigid edge shift. Further Li-ion intercalation during extended discharge in the 1-V plateau leads to the reduction of Mn4+ ions suggesting that the charge compensation in this region is achieved via the reduction of Mn4+ ions to Mn2+. Mn K-edge EXAFS results indicate that a small amount of Li is found in the Ni2+/Mn4+ layers. These Li ions in the transition metal layers are primarily present in the second coordination shell of Mn and not around Ni. Ni K-edge EXAFS fitting results suggest that the oxidation process upon Li deintercalation takes place in two steps: Ni2+ to Ni3+ first, and then Ni3+ to Ni4+.
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页码:3161 / 3169
页数:9
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