Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
1331280 | Journal of Solid State Chemistry | 2016 | 9 Pages |
•Studied ion mobility, phase transitions, conductivity in K0.7M0.3SbF4 (M=Rb, NH4).•An analysis of 19F, 1H NMR spectra made it possible to identify types of ion mobility.•Phase transitions in the compounds studied are those into the superionic state.•The ionic conductivity of the compounds studied attains 10−2–10−4 S/cm at 450–500 K.•The structures of α– and β–K0.7Rb0.3SbF4 compound are monoclinic (space group P21/m).
Ion mobility, phase transitions, structure, and conductivity in the K0.7M0.3SbF4 (M=Rb, NH4) compounds were studied by NMR spectroscopy, DSC, X-ray, and conductivity measurements. The predominant form in the ion motions resulting from the phase transition of high modification was diffusion of fluoride and ammonium ions above 450 K. The high–temperature phases of K0.7M0.3SbF4 (M=Rb, NH4) are superionic, while their conductivity attains the values of ~10−2–10−4 S/cm at 450–500 K. The structures of α– and β–modifications of the K0.7Rb0.3SbF4 are monoclinic (space group P21/m). The main structural units in them are statistically substituting each other K+ and Rb+ cations and complex [SbF4]−∞1 anions linked into zigzag-like chains by bridge fluorine atoms. The nearest surrounding of each antimony atom contains five fluorine atoms, so that the antimony coordination polyhedron can be described, taking into account the lone electron pair, as a distorted SbF5E octahedron (ψ-octahedron).
Graphical abstractThe temperature dependence of the conductivity of the compounds studied. Figure optionsDownload full-size imageDownload as PowerPoint slide