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293-K conductivity optimization for single crystals of solid electrolytes with tysonite structure (LaF3): I. Nonstoichiometric phases R 1−yCayF3−y (R = La-Lu, Y)

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Abstract

The systematic optimization of single-crystal fluoride-conducting solid electrolytes R 1 − y Ca y F3 − y with a tysonite type structure (LaF3) with respect to the conductivity at room temperature, σ(293 K), is based on high-temperature measurements of σ(T) of stoichiometric fluorides of rare earth elements, RF3 (R = La-Nd), in dependence of the radius \(R^{3 + } (r_{R^{3 + } } )\); two-component stoichiometric La1 − y R y F3 phases (R = Pr, Nd) in dependence on the average cation radius (r cat ); and two-component nonstoichiometric phases R 1 − y Ca y F3 − y (R = La-Lu, Y) in dependence of the CaF2 content. The optimization of the composition with respect to thermal stability is based on studying the phase diagrams of CaF2-RF3 systems and the behavior of R 1 − y Ca y F3 − y crystals upon heating when measuring temperature dependences σ(T). Singlecrystal samples of a number of investigated R 1 − y Ca y F3 − y compounds has σ(293 K) values high enough to be applied in solid-state electrochemical devices operating at room temperature (chemical sensors, fluorine-ion batteries, and accumulators) and in devices subjected to thermal cycling.

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Authors and Affiliations

  1. Shubnikov Institute of Crystallography, Russian Academy of Sciences, Leninskii pr. 59, Moscow, 119333, Russia

    B. P. Sobolev, N. I. Sorokin, E. A. Krivandina & Z. I. Zhmurova

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  1. B. P. Sobolev
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  2. N. I. Sorokin
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Correspondence to B. P. Sobolev.

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Original Russian Text © B.P. Sobolev, N.I. Sorokin, E.A. Krivandina, Z.I. Zhmurova, 2014, published in Kristallografiya, 2014, Vol. 59, No. 4, pp. 609–622.

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Sobolev, B.P., Sorokin, N.I., Krivandina, E.A. et al. 293-K conductivity optimization for single crystals of solid electrolytes with tysonite structure (LaF3): I. Nonstoichiometric phases R 1−yCayF3−y (R = La-Lu, Y). Crystallogr. Rep. 59, 550–562 (2014). https://doi.org/10.1134/S1063774514040191

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