Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li3MCl6(M = Y, Er) Superionic Conductors
Name
aenm.201903719.pdf
Description
Published version
Size
2.53 MB
Format
Adobe PDF
Checksum (MD5)
33101fa73e08b29aff458807d8058767
Author(s)
Schlem, Roman
Muy, Sokseiha
Prinz, Nils
Banik, Ananya
Shao-Horn, Yang
Zobel, Mirijam
Zeier, Wolfgang G.
Date Issued
February 2020
Journal
Advanced Energy Materials
Publisher
Wiley
Citation
Schlem, Roman et al. "Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li3MCl6(M = Y, Er) Superionic Conductors." Advanced Energy Materials 10, 6 (February 2020): 1903719 © 2019 The Authors
Version
Final published version
Abstract
The lithium-conducting, rare-earth halides, Li₃MX₆ (M = Y, Er; X = Cl, Br), have garnered significantly rising interest recently, as they have been reported to have oxidative stability and high ionic conductivities. However, while a multitude of materials exhibit a superionic conductivity close to 1 mS cm⁻¹, the exact design strategies to further improve the ionic transport properties have not been established yet. Here, the influence of the employed synthesis method of mechanochemical milling, compared to subsequent crystallization routines as well as classic solid-state syntheses on the structure and resulting transport behavior of Li₃ErCl₆ and Li₃YCl₆ are explored. Using a combination of X-ray diffraction, pair distribution function analysis, density functional theory, and impedance spectroscopy, insights into the average and local structural features that influence the underlying transport are provided. The existence of a cation defect within the structure in which Er/Y are disordered to a new position strongly benefits the transport properties. A synthetically tuned, increasing degree of this disordering leads to a decreasing activation energy and increasing ionic conductivity. This work sheds light on the possible synthesis strategies and helps to systematically understand and further improve the properties of this class of materials.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Massachusetts Institute of Technology. Research Laboratory of Electronics
Terms of Use
Creative Commons Attribution 4.0 International license
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1002/aenm.201903719
