Atomic-scale observation of phase transition of MgMn2O4 cubic spinel upon the charging in Mg-ion battery

Quang Duc Truong; Hiroaki Kobayashi; Keiichiro Nayuki; Yoshikazu Sasaki; Itaru Honma

doi:10.1016/j.ssi.2019.115136

Atomic-scale observation of phase transition of MgMn₂O₄ cubic spinel upon the charging in Mg-ion battery

Quang Duc Truong, Hiroaki Kobayashi, Keiichiro Nayuki, Yoshikazu Sasaki, Itaru Honma

Center for Mineral Processing and Metallurgy (CMPM)

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

20 Citations (Scopus)

Abstract

Direct observation of demagnesiated structure of MgMn₂O₄ spinel oxides at atomic scale has been achieved using spherical aberration-corrected scanning transmission electron microscopy (STEM) with high-angle annular-dark-field (HAADF) and annular-bright-field (ABF) techniques. Upon the Mg ions extraction from MgMn₂O₄ spinel oxides, structural transition from cubic to tetragonal phases was observed. The phase transition is a result of Mn octahedral distortion due to cooperative Jahn–Teller distortion of six-coordinate Mn^III (t_2g ³–e_g ¹). On the basis of HAADF/ABF micrographs and electron energy-loss spectrometer (EELS), it is suggested that Mn³⁺/Mn⁴⁺ and/or Mn³⁺/Mn⁵⁺ redox couples play a crucial role in the first electrochemical Mg deintercalation. This is the first report on observation of cubic-tetragonal phase transition in charged spinel MgMn₂O₄ which shed new insight into the magnesium storage mechanism in this important cathode material for Mg-ion batteries.

Original language	English
Article number	115136
Journal	Solid State Ionics
Volume	344
DOIs	https://doi.org/10.1016/j.ssi.2019.115136
Publication status	Published - 2020 Jan

ASJC Scopus subject areas

Chemistry(all)
Materials Science(all)
Condensed Matter Physics

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10.1016/j.ssi.2019.115136

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@article{b2c5a116832d475ab4dc03f7c5ed8398,

title = "Atomic-scale observation of phase transition of MgMn2O4 cubic spinel upon the charging in Mg-ion battery",

abstract = "Direct observation of demagnesiated structure of MgMn2O4 spinel oxides at atomic scale has been achieved using spherical aberration-corrected scanning transmission electron microscopy (STEM) with high-angle annular-dark-field (HAADF) and annular-bright-field (ABF) techniques. Upon the Mg ions extraction from MgMn2O4 spinel oxides, structural transition from cubic to tetragonal phases was observed. The phase transition is a result of Mn octahedral distortion due to cooperative Jahn–Teller distortion of six-coordinate MnIII (t2g 3–eg 1). On the basis of HAADF/ABF micrographs and electron energy-loss spectrometer (EELS), it is suggested that Mn3+/Mn4+ and/or Mn3+/Mn5+ redox couples play a crucial role in the first electrochemical Mg deintercalation. This is the first report on observation of cubic-tetragonal phase transition in charged spinel MgMn2O4 which shed new insight into the magnesium storage mechanism in this important cathode material for Mg-ion batteries.",

author = "Truong, {Quang Duc} and Hiroaki Kobayashi and Keiichiro Nayuki and Yoshikazu Sasaki and Itaru Honma",

note = "Funding Information: This research work was financially supported by Japan Society for the Promotion of Science (JSPS, Grant No. PU15903 ), Japan. Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST) and Core Technology Consortium for Advanced Energy Devices, Tohoku University , Japan. This work was partially supported by ALCA - SPRING (ALCA-Specially Promoted Research for Innovative Next Generation Batteries) from Japan Science and Technology Agency (JST). Appendix A Funding Information: This research work was financially supported by Japan Society for the Promotion of Science (JSPS, Grant No. PU15903), Japan. Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST) and Core Technology Consortium for Advanced Energy Devices, Tohoku University, Japan. This work was partially supported by ALCA-SPRING (ALCA-Specially Promoted Research for Innovative Next Generation Batteries) from Japan Science and Technology Agency (JST). Publisher Copyright: {\textcopyright} 2019 Elsevier B.V.",

year = "2020",

month = jan,

doi = "10.1016/j.ssi.2019.115136",

language = "English",

volume = "344",

journal = "Solid State Ionics",

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T1 - Atomic-scale observation of phase transition of MgMn2O4 cubic spinel upon the charging in Mg-ion battery

AU - Truong, Quang Duc

AU - Kobayashi, Hiroaki

AU - Nayuki, Keiichiro

AU - Sasaki, Yoshikazu

AU - Honma, Itaru

N1 - Funding Information: This research work was financially supported by Japan Society for the Promotion of Science (JSPS, Grant No. PU15903 ), Japan. Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST) and Core Technology Consortium for Advanced Energy Devices, Tohoku University , Japan. This work was partially supported by ALCA - SPRING (ALCA-Specially Promoted Research for Innovative Next Generation Batteries) from Japan Science and Technology Agency (JST). Appendix A Funding Information: This research work was financially supported by Japan Society for the Promotion of Science (JSPS, Grant No. PU15903), Japan. Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST) and Core Technology Consortium for Advanced Energy Devices, Tohoku University, Japan. This work was partially supported by ALCA-SPRING (ALCA-Specially Promoted Research for Innovative Next Generation Batteries) from Japan Science and Technology Agency (JST). Publisher Copyright: © 2019 Elsevier B.V.

PY - 2020/1

Y1 - 2020/1

N2 - Direct observation of demagnesiated structure of MgMn2O4 spinel oxides at atomic scale has been achieved using spherical aberration-corrected scanning transmission electron microscopy (STEM) with high-angle annular-dark-field (HAADF) and annular-bright-field (ABF) techniques. Upon the Mg ions extraction from MgMn2O4 spinel oxides, structural transition from cubic to tetragonal phases was observed. The phase transition is a result of Mn octahedral distortion due to cooperative Jahn–Teller distortion of six-coordinate MnIII (t2g 3–eg 1). On the basis of HAADF/ABF micrographs and electron energy-loss spectrometer (EELS), it is suggested that Mn3+/Mn4+ and/or Mn3+/Mn5+ redox couples play a crucial role in the first electrochemical Mg deintercalation. This is the first report on observation of cubic-tetragonal phase transition in charged spinel MgMn2O4 which shed new insight into the magnesium storage mechanism in this important cathode material for Mg-ion batteries.

AB - Direct observation of demagnesiated structure of MgMn2O4 spinel oxides at atomic scale has been achieved using spherical aberration-corrected scanning transmission electron microscopy (STEM) with high-angle annular-dark-field (HAADF) and annular-bright-field (ABF) techniques. Upon the Mg ions extraction from MgMn2O4 spinel oxides, structural transition from cubic to tetragonal phases was observed. The phase transition is a result of Mn octahedral distortion due to cooperative Jahn–Teller distortion of six-coordinate MnIII (t2g 3–eg 1). On the basis of HAADF/ABF micrographs and electron energy-loss spectrometer (EELS), it is suggested that Mn3+/Mn4+ and/or Mn3+/Mn5+ redox couples play a crucial role in the first electrochemical Mg deintercalation. This is the first report on observation of cubic-tetragonal phase transition in charged spinel MgMn2O4 which shed new insight into the magnesium storage mechanism in this important cathode material for Mg-ion batteries.

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Atomic-scale observation of phase transition of MgMn₂O₄ cubic spinel upon the charging in Mg-ion battery

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