Journal
CHEMISTRY OF MATERIALS
Volume 24, Issue 4, Pages 720-725Publisher
AMER CHEMICAL SOC
DOI: 10.1021/cm2036794
Keywords
conversion; rechargeable batteries; spinel; electrode
Funding
- KISTI [KSC-2010-C2-0006]
- Converging Research Center through the Ministry of Education, Science and Technology [2011K000691]
- Human Resources Development of the Korea Institute of Energy Technology Evaluation and Planning (KETEP)
- Korea government Ministry of Knowledge Economy [20114010203120]
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The structural and electrochemical properties of the multicomponent oxide MnFeCoO4, which has a cubic spinel AB(2)O(4) structure, are studied experimentally and by using first principles calculations. A solid solution of the spinels Mn3O4, Fe3O4, and Co3O4 forms the spine! MnFeCoO4, with Co preferentially occupying tetrahedral sites (A site). First principles calculations predict that the valence states of each transition metal would shift from +8/3 for the single component oxide to +3, +3, and +2 for the Mn, Fe, and Co ions, respectively, in the mixed spinel. The charge ordering of the transition metals (Co2+ vs Mn3+, Fe3+) in the multicomponent oxide is speculated to be the reason for the strong preference of Co for the A site. As a result, the characteristic redox potential of each transition metal shifted, as demonstrated in an anode test of the multicomponent oxide in a lithium cell. This represents an example how the electrochemical performance could be tuned by multicomponent substitution.
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