High anion conductivity in a ternary non-equilibrium phase of BaF(2) and CaF(2) with mixed cations.

A highly conductive ternary fluoride with mixed cations is prepared by joint high-energy ball milling of cubic BaF(2) and CaF(2) in the ratio 0.4 : 0.6. The sample produced at room temperature consists of a nanocrystalline, defect-rich mixed (Ba,Ca)F(2) phase with retained cubic symmetry as well as of single-phase CaF(2) particles. The anion conductivity of the mixed phase, which decomposes at higher temperature (770 K) into BaF(2) and CaF(2), exceeds that of single-phase nanocrystalline BaF(2) by two and that of CaF(2) by four orders of magnitude. In turn, these conductivities are each greater by about two orders than those of the respective microcrystalline counterparts. Structural features of the samples are characterized by X-ray diffraction, TEM and (19)F MAS NMR spectroscopy. Static (19)F NMR spectra confirm the unexpectedly high anion conductivity probed by impedance spectroscopy.