First-principles study of the reconstruction of MgM2O4 (M = Mn, Fe, Co) spinel surface

Tomoaki Kaneko; Yui Fujihara; Hiroaki Kobayashi; Keitaro Sodeyama

doi:10.1016/j.apsusc.2022.156065

First-principles study of the reconstruction of MgM₂O₄ (M = Mn, Fe, Co) spinel surface

Tomoaki Kaneko, Yui Fujihara, Hiroaki Kobayashi, Keitaro Sodeyama

Center for Mineral Processing and Metallurgy (CMPM)

Research output: Contribution to journal › Article › peer-review

Abstract

MgM₂O₄ (M = Mn, Fe, Co) spinels, which transform into rock-salt phases on Mg incorporation, are attractive cathode materials for future Mg battery applications. In this study, we investigated the energetics and reconstruction of MgM₂O₄ (M = Mn, Fe, Co) spinel surfaces using first-principles calculations. We found that the MgM₂O₄ spinels stabilized when the Mg atoms in the topmost layer occupied the rock-salt-like sites. With an increase in the number of Mg atoms, the rock salt phase preferentially grew on the spinel surface rather than in the bulk. These features agree well with the core–shell growth of the rock-salt phase observed by recent aberration-corrected scanning transmission electron microscopy measurements.

Original language	English
Article number	156065
Journal	Applied Surface Science
Volume	613
DOIs	https://doi.org/10.1016/j.apsusc.2022.156065
Publication status	Published - 2023 Mar 15

Keywords

Cathode
First-principles calculations
Mg-battery
Spinel surface
Surface reconstruction

ASJC Scopus subject areas

Chemistry(all)
Condensed Matter Physics
Physics and Astronomy(all)
Surfaces and Interfaces
Surfaces, Coatings and Films

Access to Document

10.1016/j.apsusc.2022.156065

Cite this

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title = "First-principles study of the reconstruction of MgM2O4 (M = Mn, Fe, Co) spinel surface",

abstract = "MgM2O4 (M = Mn, Fe, Co) spinels, which transform into rock-salt phases on Mg incorporation, are attractive cathode materials for future Mg battery applications. In this study, we investigated the energetics and reconstruction of MgM2O4 (M = Mn, Fe, Co) spinel surfaces using first-principles calculations. We found that the MgM2O4 spinels stabilized when the Mg atoms in the topmost layer occupied the rock-salt-like sites. With an increase in the number of Mg atoms, the rock salt phase preferentially grew on the spinel surface rather than in the bulk. These features agree well with the core–shell growth of the rock-salt phase observed by recent aberration-corrected scanning transmission electron microscopy measurements.",

keywords = "Cathode, First-principles calculations, Mg-battery, Spinel surface, Surface reconstruction",

author = "Tomoaki Kaneko and Yui Fujihara and Hiroaki Kobayashi and Keitaro Sodeyama",

note = "Funding Information: The authors would like to thank Yoshitaka Tateyama and Masanobu Nakayama for the fruitful discussions. The calculations were carried out on the Numerical Materials Simulator at NIMS and the ITO supercomputer at Research Institute for Information Technology, Kyushu University. This research was partially supported by JST, Japan ALCA-SPRING Grant Nos. JPMJAL1301 , Japan. Funding Information: The authors would like to thank Yoshitaka Tateyama and Masanobu Nakayama for the fruitful discussions. The calculations were carried out on the Numerical Materials Simulator at NIMS and the ITO supercomputer at Research Institute for Information Technology, Kyushu University. This research was partially supported by JST, Japan ALCA-SPRING Grant Nos. JPMJAL1301, Japan. Publisher Copyright: {\textcopyright} 2022 The Author(s)",

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AU - Sodeyama, Keitaro

N1 - Funding Information: The authors would like to thank Yoshitaka Tateyama and Masanobu Nakayama for the fruitful discussions. The calculations were carried out on the Numerical Materials Simulator at NIMS and the ITO supercomputer at Research Institute for Information Technology, Kyushu University. This research was partially supported by JST, Japan ALCA-SPRING Grant Nos. JPMJAL1301 , Japan. Funding Information: The authors would like to thank Yoshitaka Tateyama and Masanobu Nakayama for the fruitful discussions. The calculations were carried out on the Numerical Materials Simulator at NIMS and the ITO supercomputer at Research Institute for Information Technology, Kyushu University. This research was partially supported by JST, Japan ALCA-SPRING Grant Nos. JPMJAL1301, Japan. Publisher Copyright: © 2022 The Author(s)

PY - 2023/3/15

Y1 - 2023/3/15

N2 - MgM2O4 (M = Mn, Fe, Co) spinels, which transform into rock-salt phases on Mg incorporation, are attractive cathode materials for future Mg battery applications. In this study, we investigated the energetics and reconstruction of MgM2O4 (M = Mn, Fe, Co) spinel surfaces using first-principles calculations. We found that the MgM2O4 spinels stabilized when the Mg atoms in the topmost layer occupied the rock-salt-like sites. With an increase in the number of Mg atoms, the rock salt phase preferentially grew on the spinel surface rather than in the bulk. These features agree well with the core–shell growth of the rock-salt phase observed by recent aberration-corrected scanning transmission electron microscopy measurements.

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