Mössbauer studies of microscopic disorder in solid electrolytes

We implement for the first time Mössbauer Spectroscopy (MS) to investigate short-range properties of disorder in solid electrolytes. MS in¹²⁹I and¹¹⁹Sn was carried out in RbAg₄I₅ and as impurity in Ag₂Se, respectively. Measurements were performed both in the superionic and the normal phases. It is shown that localized cation hopping is an inherent feature of the α-AgI-type solid electrolytes. In RbAg₄I₅, at temperatures far belowT _c, a small fraction of Ag is still locally mobile and atT>T _c, its concentration increases exponentially. A strong linear temperature dependence of the point-charge electric field gradient is observed and explained in terms of local hopping. With¹¹⁹Sn in Ag₂Se we observe the onset of “local melting” of the Ag surrounding the SnSe₄ cluster at 50 K below the bulk superionic phase transition. The characteristic features of MS related to microscopic studies of solid electrolytes are fully described.