Electron delocalization in cyanide-bridged coordination polymer electrodes for Li-ion batteries studied by soft x-ray absorption spectroscopy

Daisuke Asakura, Masashi Okubo, Yoshifumi Mizuno, Tetsuichi Kudo, Haoshen Zhou, Kenta Amemiya, Frank M.F. De Groot, Jeng Lung Chen, Wei Cheng Wang, Per Anders Glans, Chinglin Chang, Jinghua Guo, Itaru Honma

Research output: Contribution to journalArticlepeer-review

32 Citations (Scopus)

Abstract

The electronic structure change during the reversible Li-ion storage reaction in a bimetallic MnFe-Prussian blue analogue (LixK 0.14Mn1.43[Fe(CN)6]•6H2O) was investigated by soft x-ray absorption spectroscopy. The Mn L2,3-edge spectra revealed the unchanged Mn2+ high-spin state regardless of Li-ion concentration (x). On the other hand, the Fe L2,3-edge spectra clearly revealed a reversible redox behavior as Fe3+Fe2+ states with Li-ion insertion/extraction. Experimental findings suggested strong metal-to-ligand charge transfer in conjunction with the ligand-to-metal one. The resulting charge delocalization between the Fe and CN is considered to contribute to the high reversibility of the Li-ion storage process.

Original languageEnglish
Article number045117
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume84
Issue number4
DOIs
Publication statusPublished - 2011 Jul 14
Externally publishedYes

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics

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