Anhydrous Silicophosphoric Acid Glass: Thermal Properties and Proton Conductivity.

ABSTRACT

Anhydrous silicophosphoric acid glass with an approximate composition of H5 Si2 P9 O29 was synthesized and its thermal and proton-conducting properties were characterized. Despite exhibiting a glass transition at 192 °C, the supercooled liquid could be handled as a solid up to 280 °C owing to its high viscosity. The glass and its melt exhibited proton conduction with a proton transport number of ∼1. Although covalent O-H bonds were weakened by relatively strong hydrogen bonding, the proton conductivity (4×10-4  S cm-1 at 276 °C) was considerably lower than that of phosphoric acid. The high viscosity of the melt was due to the tight cross-linking of phosphate ion chains by six-fold-coordinated Si atoms. The low proton conductivity was attributed to the trapping of positively charged proton carriers around anionic SiO6 units (expressed as (SiO6/2 )2- ) to compensate for the negative charges.