Fluorine Translational Anion Dynamics in Nanocrystalline Ceramics: SrF2-YF3 Solid Solutions

Abstract

Nanostructured materials have already become an integral part of our daily life. In many applications, ion mobility decisively affects the performance of, e.g., batteries and sensors. Nanocrystalline ceramics often exhibit enhanced transport properties due to their heterogeneous structure showing crystalline (defect-rich) grains and disordered interfacial regions. In particular, anion conductivity in nonstructural binary fluorides easily exceeds that of their coarse-grained counterparts. To further increase ion dynamics, aliovalent substitution is a practical method to influence the number of (i) defect sites and (ii) the charge carrier density. Here, we used high energy-ball milling to incorporate Y 3 + ions into the cubic structure of SrF 2 . As compared to pure nanocrystalline SrF 2 the ionic conductivity of Sr 1 − x Y x F 2 + x with x = 0.3 increased by 4 orders of magnitude reaching 0.8 × 10 − 5 S cm − 1 at 450 K. We discuss the effect of YF 3 incorporation on conductivities isotherms determined by both activation energies and Arrhenius pre-factors. The enhancement seen is explained by size mismatch of the cations involved, which are forced to form a cubic crystal structure with extra F anions if x is kept smaller than 0.5.

Keywords

• nanocrystalline ceramics
• binary fluorides, ionic conductivity
• ball milling
• cation mixing
• aliovalent substitution