Stability of the superprotonic conduction of (1-x)CsH 2 PO 4 /xSiO 2 (0 ≤ x ≤ 0.3) composites under dry and humid environments

2018 
Abstract We have used temperature- and time-resolved electrochemical impedance spectroscopy, x-ray diffraction, and thermal analysis methods to investigate the effect of mixing CsH 2 PO 4 with nano-silica on the superprotonic conduction of this solid acid. We collected data on (1-x)CsH 2 PO 4 /xSiO 2 (0 ≤ x ≤ 0.3) composites in dry (air) and humid (P H2O  ∼ 0.38 atm) environments at temperatures below and above the superprotonic transition of CsH 2 PO 4 (T SP  ∼ 234 °C). We first observed that a three-order-of-magnitude proton conductivity jump occurred in the unmixed sample (x = 0) at T SP , even under dry conditions and despite chemical changes (dehydration). We also found that the proton conductivity of the x = 0.1, 0.2 and 0.3 composites measured at T = 260 °C in air is nearly one order of magnitude greater than that of the unmixed phosphate (x = 0). Even more significantly, we found that humid sample environments have no effect on the stability of the proton conductivity of the x = 0.2 composite measured over a 10 h timespan at temperatures above T SP . This is contrary to the behavior of the x = 0 sample, which is known [31] to be stable under humid conditions, but undergoes a three-order-of-magnitude proton conductivity drop in air.
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