J. Phys. Soc. Jpn. 92, 014702 (2023) [7 Pages]
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Effect of Oxygen Hole in Li2MnO3 Revealed by Hard X-ray Photoemission Spectroscopy and Band Structure Calculations

Keisuke Morita1, Mitoki Itoda1, Eiji Hosono2 , Daisuke Asakura2 , Masashi Okubo3 , Yasumasa Takagi4 , Akira Yasui4 , Naurang L. Saini5 , and Takashi Mizokawa1
+ Affiliations
1Department of Applied Physics, Waseda University, Shinjuku, Tokyo 169-8555, Japan2National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki 305-8568, Japan3Department of Electrical Engineering and Bioscience, School of Advanced Science and Engineering, Waseda University, Shinjuku, Tokyo 169-8555, Japan4Japan Synchrotron Radiation Research Institute, Sayo, Hyogo 679-5198, Japan5Department of Physics, University of Roma “La Sapienza”, Piazzale Aldo Moro 2, 00185 Roma, Italy
Received June 21, 2022; Accepted November 15, 2022; Published December 16, 2022

We have studied the electronic structure of Li2MnO3 which has been attracting interest as a promising oxygen redox type cathode material for Li ion battery. Hard x-ray photoemission spectroscopy and subsequent cluster model analysis show that the Mn valence is 4+ and that the charge transfer energy Δ is close to 0 eV. Δ of Li2MnO3 is smaller than the typical Δ values of tetravalent Mn oxides. The small Δ value suggests that the delithiation process of Li2MnO3 is dominated by electron removal from the O 2p orbitals. In addition to the ground state properties of Li2MnO3, effect of Li or oxygen vacancy on the electronic structure is examined by means of band structure calculations. The Li vacancy drives the system metallic due to itinerant O 2p holes while the system with oxygen vacancy remains an insulator.

©2023 The Physical Society of Japan
https://doi.org/10.7566/JPSJ.92.014702

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