Formation of Amorphous H3 Zr2 Si2 PO12 by Electrochemical Substitution of Sodium Ions in Na3 Zr2 Si2 PO12 with Protons

Inorganic Chemistry
Satoshi TsukudaTakahisa Omata

Abstract

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.

References

Jul 14, 2009·Inorganic Chemistry·Alodia OreraUlises Amador
Feb 22, 2014·Journal of the American Chemical Society·Takahisa OmataNaoki Ohashi
May 6, 2015·Physical Chemistry Chemical Physics : PCCP·Tomohiro IshiyamaTakahisa Omata
Mar 10, 2016·The Journal of Physical Chemistry. a·Kamali Kesavan, T Ravindran Thoguluva

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