Phase separation of a hexacyanoferrate-bridged coordination framework under electrochemical Na-ion insertion

Satoshi Kajiyama, Yoshifumi Mizuno, Masashi Okubo*, Ryosuke Kurono, Shin Ichi Nishimura, Atsuo Yamada

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

17 Citations (Scopus)

Abstract

Phase separation and transformation induced by electrochemical ion insertion are key processes in achieving efficient energy storage. Exploration of novel insertion electrode materials/reactions is particularly important to unravel the atomic/molecular-level mechanism and improve the electrochemical properties. Here, we report the unconventional phase separation of a cyanide-bridged coordination polymer, Eu[Fe(CN)6]·4H 2O, under electrochemical Na-ion insertion. Detailed structural analyses performed during the electrochemical reaction revealed that, in contrast to conventional electrochemical phase separation induced by the elastic interaction between nearest neighbors, the phase separation of Na xEu[Fe(CN)6]·4H2O is due to a long-range interaction, namely, cooperative rotation ordering of hexacyanoferrates. Kolmogorov-Johnson-Mehl-Avrami analysis showed that the activation energy for the phase boundary migration in NaxEu[Fe(CN)6] ·4H2O is lower than that in other conventional electrode materials such as Li1-xFePO4.

Original languageEnglish
Pages (from-to)3141-3147
Number of pages7
JournalInorganic Chemistry
Volume53
Issue number6
DOIs
Publication statusPublished - 2014 Mar 17
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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