Electrochemical Properties and Crystal and Electronic Structures of Spinel αMgCo<sub>2−</sub><i><sub>x</sub></i>Mn<i><sub>x</sub></i>O<sub>4</sub>-(1 − α)Mg(Mg<sub>0.33</sub>V<sub>1.67−</sub><i><sub>y</sub></i>Ni<i><sub>y</sub></i>)O<sub>4</sub> for Magnesium Secondary Batteries (Supporting Information)
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In the present study, αMgCo1.5Mn0.5O4-(1 − α)Mg1.33V1.57Ni0.1O4 was synthesized by a reverse co-precipitation method. The products were assigned to a spinel structure with a space group Fd3m based on powder X-ray diffraction analysis. Inductively coupled plasma-atomic emission spectroscopy revealed that the composition was not close to the target composition; the Mg content was higher and the V content was lower than expected. Charge/discharge cyclic tests showed that the discharge capacity exceeded 180 mAh g−1 and that the cyclability was reversible up to 60 cycles at 90 °C with a cut-off voltage of 0.945 to −1.055 V vs. Ag/Ag+ (3.545–1.545 V vs. Mg/Mg2+) for α = 0.3. The electronic structure was analyzed using the maximum-entropy method based on a Rietveld analysis, and it was found that Mg insertion was easier for α = 0.3, 0.5, 0.9 than for MgCo1.5Mn0.5O4 and Mg1.33V1.57Ni0.1O4. The strain in MO6 octahedra for α = 0.1, 0.3, 0.5, 0.7 was smaller than that for MgCo1.5Mn0.5O4 and Mg1.33V1.57Ni0.1O4, which suggests that the host structure was stabilized by forming a solid solution. A Rietveld analysis after the first discharge and second charge confirmed a partly reversible phase transition from the spinel phase to a rock-salt phase. The valence of the transition metals was examined by X-ray absorption fine structure (XAFS) measurements, and the Co and Mn K-edge spectra revealed that Co and Mn were present as Co2.67+ to Co2+ and Mn4+ to Mn3+ species for α = 0.3. Both Co and Mn redox processes are considered to contribute to Mg intercalation. Extended XAFS (EXAFS) Co K-edge and Mn K-edge spectra for the powder specimens and after the first discharge and second charge showed that bonds between Co, V atoms and nearest-neighbor O atoms were distorted after the first discharge, and that this distortion was relaxed after the second charge.
