Directed Dehydration as Synthetic Tool for Generation of a New Na4 SnS4 Polymorph: Crystal Structure, Na+ Conductivity, and Influence of Sb-Substitution.

Abstract

We present the convenient synthesis and characterization of the new ternary thiostannate Na4SnS4 (space group I41/acd ) by directed removal of crystal water molecules from Na4SnS4⋅14 H2O. The compound represents a new kinetically stable polymorph of Na4SnS4, which is transformed into the known, thermodynamically stable form (space group P4‾21c ) at elevated temperatures. Thermal co‐decomposition of mixtures with Na3SbS4⋅9 H2O generates solid solution products Na4−x Sn1−x Sb x S4 (x=0.01, 0.10) isostructural to the new polymorph (x=0). Incorporation of Sb5+ affects the bonding and local structural situation noticeably evidenced by X‐ray diffraction, 119Sn and 23Na NMR, and 119Sn Mössbauer spectroscopy. Electrochemical impedance spectroscopy demonstrates an enormous improvement of the ionic conductivity with increasing Sb content for the solid solution (σ 25°C=2×10−3, 2×10−2, and 0.1 mS cm−1 for x=0, 0.01, and 0.10), being several orders of magnitude higher than for the known Na4SnS4 polymorph.