Superprotonic CsH2PO4-CsHSO4 solid solutions

We have performed partial HSO 4 − substitution in CsH2PO4 and studied the associated structural changes and the proton conductivity of the resultant (CsH2PO4)1 − x (CsHSO4) x solid solutions in the range x = 0.01–0.3. The results indicate that, at room temperature, the solid solutions are disordered. In the range x = 0.01–0.1, they are isostructural with the low-temperature phase of CsH2PO4 (sp. gr. P21/m), and their unit-cell parameters increase with x, whereas in the range x = 0.15–0.3 the solid solutions are isostructural with the high-temperature, cubic phase of CsH2PO4 (Pm3m), and their unit-cell parameter decreases. The conductivity of the (CsH2PO4)1 − x (CsHSO4) x solid solutions with x ≤ 0.3 depends significantly on their composition and increases at low temperatures by up to four orders of magnitude, approaching that of the superionic phase of CsH2PO4 in the range x = 0.15–0.3 because of the hydrogen bond weakening and increased proton mobility. The conductivity of the superionic phase decreases with increasing x by no more than a factor of 1.5–2, and the superionic phase transition, which occurs at 231°C in CsH2PO4, shifts to lower temperatures and disappears for x ≥ 0.15. The activation energy for low-temperature conduction decreases with increasing x: from 0.9 eV in CsH2PO4 to 0.48 eV at x = 0.1.