Journal
ADVANCED SCIENCE
Volume 2, Issue 8, Pages -Publisher
WILEY
DOI: 10.1002/advs.201500072
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Funding
- Advanced Low Carbon Technology Research and Development Program (ALCA)
- Special Coordination Funds for Promoting Science and Technology
- MEXT Elements Strategy Initiative to Form Core Research Center
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On the basis of the similarity between spinel and rocksalt structures, it is shown that some spinel oxides (e.g., MgCo2O4, etc) can be cathode materials for Mg rechargeable batteries around 150 degrees C. The Mg insertion into spinel lattices occurs via intercalation and push-out process to form a rocksalt phase in the spinel mother phase. For example, by utilizing the valence change from Co(III) to Co(II) in MgCo2O4, Mg insertion occurs at a considerably high potential of about 2.9 V vs. Mg2+/Mg, and similarly it occurs around 2.3 V vs. Mg2+/Mg with the valence change from Mn(III) to Mn(II) in MgMn2O4, being comparable to the ab initio calculation. The feasibility of Mg insertion would depend on the phase stability of the counterpart rocksalt XO of MgO in Mg2X2O4 or MgX3O4 (X = Co, Fe, Mn, and Cr). In addition, the normal spinel MgMn2O4 and MgCr2O4 can be demagnesiated to some extent owing to the robust host structure of Mg1-xX2O4, where the Mg extraction/insertion potentials for MgMn2O4 and MgCr2O4 are both about 3.4 V vs. Mg2+/Mg. Especially, the former intercalation and push-out process would provide a safe and stable design of cathode materials for polyvalent cations.
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