Bulk and surface properties of ionic salt CsH 5(PO 4) 2

Abstract

We report a comparative study of transport and thermodynamic properties of single-crystal and polycrystalline samples of the ionic salt CsH 5(PO 4) 2 possessing a peculiar three-dimensional hydrogen-bond network. The observed potential of electrolyte decomposition ≈ 1.3 V indicates that the main charge carriers in this salt are protons. However, in spite of the high proton concentration, the conductivity appears to be rather low with a high apparent activation energy E a ≈ 2 eV, implying that protons are strongly bound. The transport anisotropy though is not large, correlates with the crystal structure: the highest conductivity is found in the [001] direction ( σ 130 °C ∼ 5.6 × 10 − 6 S cm − 1 ) while the minimal conductivity is in the [100] direction ( σ 130 °C ∼ 10 −6 S cm − 1 ). The conductivity of polycrystalline samples appears to exceed the bulk one by 1–3 orders of magnitude with a concomitant decrease of the activation energy ( E a ≈ 1.05 eV), which indicates that a pseudo-liquid layer with a high proton mobility is formed at the surface of grains. Infrared and Raman spectroscopy used to study the dynamics of the hydrogen-bond system in single-crystal and polycrystalline samples have confirmed the formation of such a modified surface layer in the latter. However, no bulk phase transition into the superionic disordered phase is observed in CsH 5(PO 4) 2 up to the melting point T melt ∼ 151.6 °C, in contrast to its closest relative compound CsH 2PO 4.