Ion mobility, phase transitions, and conductivity of crystal phases in KF-CsF-SbF3-H2O system according to data of NMR and impedance spectroscopy

Abstract

The methods of NMR, thermogravimetric analysis, and impedance spectroscopy were used to study ion mobility, phase transitions, and ion conductivity in crystal phases in the KF-CsF-SbF3-H2O system. Analysis of 19F NMR spectra allowed tracing the dynamics of ion movement in the fluoride sublattice under temperature variations, determining their types and temperature ranges, in which they are implemented. The observed phase transitions in potassium-cesium fluoroantimonates(III) are phase transitions to the superionic state. It is found that the predominant form of ion movement in the high-temperature modifications formed as a result of phase transitions becomes diffusion of fluoride ions. According to the results of electrophysical studies the K1 − xCsxSbF4 (x ≤ 0.2) high-temperature phases are superionic. Their conductivity reaches the values of ∼10−2 to 10−3 S/cm at 463–483 K. The high-temperature phases are stabilized under cooling, which results in a significant increase in conductivity at the room temperature.