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First-principles calculations of stable local structures and electronic structures of magnesium secondary battery cathode materials, MgCo2−xMnxO4 (x = 0, 0.5), in second charged state after first discharge

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Abstract

The stable structures associated with the second charge of MgCo2−xMnxO4 (x = 0, 0.5), where Mg is removed from the stable first-discharge models, are investigated using first-principles calculations. If spinel structures remain in the stable structures after the first discharge process, the stable structures during the second charge process change to spinel structures very similar to the pristine (uncycled material). Structural change of the Mg/Co mixed-cation-spinel-based model is more difficult than that of the normal-spinel-based model because Co atoms at 16c sites encounter more difficulty than Mg atoms at 16c sites in migrating to 8a sites. However, if the Mg/Co mixed-cation-spinel-based models after the first discharge have Co atoms at the 8a sites, the models are expected to change to the fully spinel structure during the second charge. These theoretical results are in good agreement with the experimental measurements; furthermore, the desorption mechanism and diffusion process for Mg2+ in MgCo2−xMnxO4 (x = 0, 0.5) crystals during the charging process, which have not been determined in previous experimental studies, are revealed.

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Acknowledgements

This research was financially supported by JST, ALCA-SPRING Grant Number JPMJAC1301, Japan. This work was also supported in part by JSPS KAKENHI Grant Number 20K15382, Japan. We are deeply grateful for the cooperation of Dr. Keiichi Osaka of the Japan Synchrotron Radiation Research Institute (JASRI) for cooperation with the synchrotron radiation synchrotron X-ray diffraction measurements (BL19B2, SPring-8, Proposal No. 2019A1760) and Dr. Koji Ohara of JASRI (Japan Synchrotron Radiation Research Institute) for assistance with synchrotron X-ray total scattering measurements (BL04B2, SPring-8, Proposal Nos. 2019A1137 and 2018A1040).

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  1. Faculty of Science & Technology, Tokyo University of Science, 2641 Yamazaki, Noda-shi, Chiba, 278-8510, Japan

    Chiaki Ishibashi, Mai Ichiyama, Naoya Ishida, Naoto Kitamura & Yasushi Idemoto

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  1. Chiaki Ishibashi
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  2. Mai Ichiyama
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Correspondence to Yasushi Idemoto.

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Ishibashi, C., Ichiyama, M., Ishida, N. et al. First-principles calculations of stable local structures and electronic structures of magnesium secondary battery cathode materials, MgCo2−xMnxO4 (x = 0, 0.5), in second charged state after first discharge. J Solid State Electrochem 26, 663–682 (2022). https://doi.org/10.1007/s10008-021-05098-3

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