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Superionic Conduction in Co-Vacant P2-Nax CoO2 Created by Hydrogen Reductive Elimination
Kenichi Kato1,2, Hidetaka Kasai3,4,5, Akihiro Hori3,6
1RIKEN SPring-8 Center, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5148, Japan. katok@spring8.or.jp.
Abstract:
The layered P2-Nax MO2 (M: transition metal) system has been widely recognized as electronic or mixed conductor. Here, we demonstrate that Co vacancies in P2-Nax CoO2 created by hydrogen reductive elimination lead to an ionic conductivity of 0.045 S cm(-1) at 25 °C. Using in situ synchrotron X-ray powder diffraction and Raman spectroscopy, the composition of the superionic conduction phase is evaluated to be Na0.61 (H3 O)0.18 Co0.93 O2 . Electromotive force measurements as well as molecular dynamics simulations indicate that the ion conducting species is proton rather than hydroxide ion. The fact that the Co-stoichiometric compound Nax (H3 O)y CoO2 does not exhibit any significant ionic conductivity proves that Co vacancies are essential for the occurrence of superionic conductivity.
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