Structural and electrochemical effects of cobalt doping on lithium manganese oxide spinel |
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Authors: | A. Butz M. Wohlfahrt-Mehrens R. Oesten R. A. Huggins |
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Affiliation: | (1) Center for Solar Energy and Hydrogen Research, D-89081 Ulm, Germany;(2) University of Kiel, Technical Faculty, D-24143 Kiel, Germany |
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Abstract: | Pure LiMn2O4 and lithium manganese oxide spinels with partial replacement of manganese by cobalt up to 20 mole%, LiCoxMn2−xO4, were prepared. The effect of extended cycling on the crystal structure was investigated. A capacity decrease with increasing cobalt content was observed in the potential range about 4100 mV vs. Li/Li+. Cycling behavior is significantly improved, compared to LiMn2O4. LiCoxMn2−xO4 is discharged in a single phase reaction in the upper potential range around 4100 mV vs. Li/Li+, whereas pure LiMn2O4 shows a two phase behavior. LiMn2O4 shows a significant broadening of peaks in plots of differential capacity and change in shape of the voltage profile upon extended cycling. LiCoxMn2−xO4 shows neither broadening nor change. Voltage profiles and plots of the differential capacity differ significantly compared to spinels with lithium substitution, Li1+xMn2−xO4. In contrast to Li1+xMn2-xO4, LiCoxMn2-xO4 is discharged in a two step process in the range of 0 ≤ × ≤ 0,5. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996 |
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