Journal article

Publication year: 2021

Pages: 4773-4782

Journal: Chemistry of Materials

Volume number: 33

Issue number: 12

ISSN: 0897-4756

eISSN: 1520-5002

DOI Link: https://doi.org/10.1021/acs.chemmater.1c01348

Publisher: American Chemical Society

Abstract: 
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 (Li3-xIn1-xZrxCl6 with 0 <= x <= 0.5) using a combination of neutron diffraction, nuclear magnetic resonance, and impedance spectroscopy. The analysis of high-resolution diffraction data shows the presence of an additional tetrahedrally coordinated lithium position together with a 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 nonuniform volume changes along with an increasing number of vacancies, all of which lead to increasing ionic conductivity in this series of solid solutions.

Harvard Citation style: Helm, B., Schlem, R., Wankmiller, B., Banik, A., Gautam, A., Ruhl, J., et al. (2021) Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li_3-xIn_1-x Zr_xCl₆ (0 ≤ x ≤ 0.5), Chemistry of Materials, 33(12), pp. 4773-4782. https://doi.org/10.1021/acs.chemmater.1c01348

APA Citation style: Helm, B., Schlem, R., Wankmiller, B., Banik, A., Gautam, A., Ruhl, J., Li, C., Hansen, M., & Zeier, W. (2021). Exploring Aliovalent Substitutions in the Lithium Halide Superionic Conductor Li_3-xIn_1-x Zr_xCl₆ (0 ≤ x ≤ 0.5). Chemistry of Materials. 33(12), 4773-4782. https://doi.org/10.1021/acs.chemmater.1c01348