Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li3-xIn1-xZrxCl6 (0 ≤ X ≤ 0.5)

In recent years, ternary halides Li₃MX₆ (M = Y, Er, In; X = Cl, Br, I) have garnered attention as solid electrolytes due to their wide electrochemical stability window and favorable room-temperature conductivities. In this material class, the influences of iso- or aliovalent substitutions are so far rarely studied in-depth, despite this being a common tool for correlating structure and transport properties. In this work, we investigate the impact of Zr substitution on the structure and ionic conductivity of Li₃InCl₆ (Li_3-xIn_1-xZr_xCl₆ with 0 ≤ x ≤ 0.5) using a combination of neutron diffraction, nuclear magnetic resonance and impedance spectroscopy. Analysis of high-resolution diffraction data shows the presence of an additional tetrahedrally coordinated lithium position together with cation site-disorder, both of which have not been reported previously for Li₃InCl₆. This Li⁺ position and cation disorder lead to the formation of a three-dimensional lithium ion diffusion channel, instead of the expected two-dimensional diffusion. Upon Zr⁴⁺ substitution, the structure exhibits non-uniform volume changes along with an increasing number of vacancies, all of which lead to an increasing ionic conductivity in this series of solid solutions.