Effect of cation substitution in Cs_1–2x Ba _x H₂PO₄ on structural properties and proton conductivity

Abstract

We synthesized compounds with partial substitution of Cs⁺ cations in CsH₂PO₄ by Ba²⁺ cations. The structural, electron transport and thermodynamic properties of Cs_1–2x Ba _x H₂PO₄ (x = 0–0.15) were studied for the first time with the help of a set of physicochemical methods: infrared and impedance spectroscopy, X-ray diffraction and synchronous thermal analysis. The proton conductivity of Cs_1–2x Ba _x H₂PO₄ at 50–230°C was investigated in detail by impedance measurements. The formation of solid substitution solutions isostructural with CsH₂PO₄ (P2₁/m) is observed in the range of substitution degrees of x = 0–0.1, with a slight decrease in the unit cell parameters and some salt amorphization. The conductivity of disordered Cs_1–2x Ba _x H₂PO₄ in the low-temperature region increases by two orders of magnitude at x = 0.02 and increases with an increasing fraction of barium cations by three or four orders of magnitude at x = 0.05–0.1; the superionic phase transition practically disappears. At x = 0.15, heterophase systems based on salts are formed, showing high conductivity and a further decrease in the activation energy of conductivity to 0.63 eV. The conductivity of the high-temperature phase of Cs_1–2x Ba _x H₂PO₄ does not change with increasing fraction of the substituent.