Access to metastable complex ion conductors via mechanosynthesis: preparation, microstructure and conductivity of (Ba,Sr)LiF3 with inverse perovskite structure

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Abstract
Highly metastable Ba1−xSrxLiF3 (0 < x ≤ xmax ≈ 0.4) with an inverse perovskite structure analogous to that of BaLiF3 was synthesized by soft mechanical treatment of BaF2 and LiF together with SrF2 at ambient temperature. Ex as well as in situX-ray powder diffraction (XRPD) measurements show that heat treatment at 393 K initiates the decomposition of the mixed phase into BaLiF3, LiF and (Sr,Ba)F2. Structural details of the metastable compound (Ba,Sr)LiF3 were investigated by ultrafast 19F magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. Interestingly, five magnetically inequivalent F sites were identified which correspond to fluorine anions coordinated by a variable number of Ba and Sr cations, respectively. Details from XRPD and NMR spectroscopy are discussed with respect to the formation mechanisms and thermal stability of the as prepared fluorides. Impedance spectroscopy is used to characterize (long-range) ionic transport properties. Results are compared with those obtained recently on mechanosynthesized BaLiF3.

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