Anhydrous proton conductive xCHS-(1-x)WSiA composites prepared via liquid-phase shaking.

High proton conductive x CsHSO 4 -(1- x)H 4 SiW 12 O 40 (CHS-WSiA) composites were successfully prepared via a new liquid-phase shaking method. N,N ‑Dimethylacetamide (DMAc) and zirconium balls were used as a solvent/dispersing medium and a collision medium, respectively. X-ray diffraction characterization confirmed that the liquid-phase shaking treatment induced an ion-exchange reaction between Cs+ ions in CHS and H+ ions in WSiA to form new composite materials. The proton conductivities of these composites were significantly improved over their precursor materials, especially at low temperatures, below the superprotic phase-transition temperature of CHS. The 0.9CHS-0.1WSiA (in mole ratio) composite, for instance, showed the highest proton conductivities of 1.38 × 10−4 to 2.42 × 10−3 S cm−1 from 50 °C to 170 °C under dry conditions of nitrogen atmosphere. The enhanced anhydrous proton conductivities of the Cs-substituted WSiA composites were also corroborated with shortening of the hydrogen bonding distance in these composites for fast proton hopping transport mechanism via 1H NMR evaluation. • Superprotic xCsHSO 4 ·(1-x)H 4 SiW 12 O 40 composites prepared via liquid-phase shaking. • High Cs substitution into WSiA induced shorter H-bonds and lower E A. • Anhydrous proton conductivities due to new hydrogen bonds formation. [ABSTRACT FROM AUTHOR]