論文

査読有り
2016年

Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li2MnO3, studied by soft X-ray absorption spectroscopy

JOURNAL OF MATERIALS CHEMISTRY A
  • Masatsugu Oishi
  • ,
  • Keisuke Yamanaka
  • ,
  • Iwao Watanabe
  • ,
  • Keiji Shimoda
  • ,
  • Toshiyuki Matsunaga
  • ,
  • Hajime Arai
  • ,
  • Yoshio Ukyo
  • ,
  • Yoshiharu Uchimoto
  • ,
  • Zempachi Ogumi
  • ,
  • Toshiaki Ohta

4
23
開始ページ
9293
終了ページ
9302
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1039/c6ta00174b
出版者・発行元
ROYAL SOC CHEMISTRY

Li-rich layered oxides have attracted attention as promising positive electrode materials for next-generation lithium-ion secondary batteries because of their high energy storage capacity. The participation of the oxygen anion has been hypothesized to contribute to these oxides' high capacity. In the present study, we used O K-edge and Mn L-edge X-ray absorption spectroscopy (XAS) to study the reversible redox reactions that occur in single-phase Li-rich layered manganese oxide, Li2MnO3. We semiquantitatively analyzed the oxygen and manganese reactions by dividing the charge/discharge voltage region into two parts. The O K-edge XAS indicated that the electrons at the oxygen site reversibly contributed to the charge compensation throughout the charge/discharge processes at operating voltages between 2.0 and 4.8 V vs. Li+/Li-0. The Mn L-edge XAS spectra indicated that the Mn redox reaction occurred only in the lower-voltage region. Thus, at higher potentials, the electrons, mainly at the oxygen site, contributed to the charge compensation. Peaks whose energies were similar to peroxide appeared in and then disappeared from the O K-edge spectra obtained during the reversible redox cycles. These results indicate that the reorganization of the oxygen network in the crystal structure affects the redox components. By using two kinds of detection modes with different probing depths in XAS measurements, it was found that these redox reactions are bulk phenomena in the electrode.

リンク情報
DOI
https://doi.org/10.1039/c6ta00174b
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000378947200042&DestApp=WOS_CPL
URL
http://www.scopus.com/inward/record.url?eid=2-s2.0-84973874586&partnerID=MN8TOARS
URL
http://orcid.org/0000-0003-4600-3437
ID情報
  • DOI : 10.1039/c6ta00174b
  • ISSN : 2050-7488
  • eISSN : 2050-7496
  • ORCIDのPut Code : 30160802
  • SCOPUS ID : 84973874586
  • Web of Science ID : WOS:000378947200042

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