Formation of Amorphous H3Zr2Si2PO12 by Electrochemical Substitution of Sodium Ions in Na3Zr2Si2PO12 with Protons

Satoshi Tsukuda, Keigo Miyake, Takuya Yamaguchi, Masao Kita, Tomohiro Ishiyama, Junji Nishii, Toshiharu Yamashita, Hiroshi Kawazoe, Takahisa Omata

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1 Citation (Scopus)


The sodium ions in Na3Zr2Si2PO12 (NASICON) were substituted with protons using an electrochemical alkali-proton substitution (APS) technique at 400 °C under a 5% H2/95% N2 atmosphere. The sodium ions in NASICON were successfully substituted with protons to a depth of <400 μm from the anode. Completely protonated NASICON, i.e., H3Zr2Si2PO12, was obtained to a depth <40 μm from the anode, although complete protonation of NASICON cannot be achieved by ion exchange in aqueous acid. H3Zr2Si2PO12 was amorphous, whereas the partially protonated NASICON was crystalline, and its unit cell volume decreased with an increase in the extent of substitution. Amorphous H3Zr2Si2PO12 was prepared by pressure-induced amorphization of the NASICON framework, in which an internal pressure of -3.5 GPa was induced by the substitution of large sodium ions with small protons during APS at 400 °C.

Original languageEnglish
Pages (from-to)13949-13954
Number of pages6
JournalInorganic chemistry
Issue number22
Publication statusPublished - 2017 Nov 20

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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