%0 Journal Article %A Helm, Bianca %A Schlem, Roman %A Wankmiller, Björn %A Banik, Ananya %A Gautam, Ajay %A Ruhl, Justine %A Li, Cheng %A Hansen, Michael Ryan %A Zeier, Wolfgang %T Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li<sub>3– x</sub>In<sub>1– x</sub>Zr<sub>x</sub>Cl<sub>6</sub> (0 ≤ x ≤ 0.5) %J Chemistry of materials %V 33 %N 12 %@ 0897-4756 %C Washington, DC %I American Chemical Society %M FZJ-2021-05019 %P 4773 - 4782 %D 2021 %X In recent years, ternary halides Li<sub>3</sub>MX<sub>6</sub> (M = Y, Er, In; X = Cl, Br, I) have garnered attention assolid electrolytes due to their wide electrochemical stability window and favorable roomtemperatureconductivities. In this material class, the influences of iso- or aliovalentsubstitutions are so far rarely studied in-depth, despite this being a common tool for correlatingstructure and transport properties. In this work, we investigate the impact of Zr substitution onthe structure and ionic conductivity of Li<sub>3</sub>InCl<sub>6</sub> (Li<sub>3-x</sub>In<sub>1-x</sub>Zr<sub>x</sub>Cl<sub>6</sub> with 0 ≤ x ≤ 0.5) using acombination of neutron diffraction, nuclear magnetic resonance and impedance spectroscopy.Analysis of high-resolution diffraction data shows the presence of an additional tetrahedrallycoordinated lithium position together with cation site-disorder, both of which have not beenreported previously for Li<sub>3</sub>InCl<sub>6</sub>. This Li<sup>+</sup> position and cation disorder lead to the formation ofa three-dimensional lithium ion diffusion channel, instead of the expected two-dimensionaldiffusion. Upon Zr<sup>4+</sup> substitution, the structure exhibits non-uniform volume changes alongwith an increasing number of vacancies, all of which lead to an increasing ionic conductivity inthis series of solid solutions %F PUB:(DE-HGF)16 %9 Journal Article %U <Go to ISI:>//WOS:000665651400048 %R 10.1021/acs.chemmater.1c01348 %U https://juser.fz-juelich.de/record/903325