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The solid-solution regions in the Me Sm 2 S 4 -Me S and Me Sm 2 S 4 -Sm 2 S 3 ( Me = Ca, Ba) systems are revealed. The average ion, cation, and anion transport numbers of the synthesized solid electrolytes x Sm 2 S 3 [Ca(Ba)S] · (100 -x )Ca(Ba)Sm 2 S 4 ( x = 1-10 mol %) are determined by the electromotive force (emf) method with the use of concentration cells with and without transfer. In the phases under investigation, the ion transfer in the temperature range 673-723 K is provided by sulfide ions ( = 1.00 ± 0.02). The diffusion coefficients of S 2-ions in the solid electrolytes are determined by potentiostatic chronoamperometry. A vacancy mechanism of defect formation is proposed. It is demonstrated that the transport characteristics of the solid electrolytes based on the CaSm 2 S 4 compound are worse than those of the solid electrolytes based on the BaSm 2 S 4 compound.

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