Reaction mechanism studies towards effective fabrication of lithium-rich anti-perovskites Li3OX (X = Cl, Br)

Authors

Shuai Li, University of Nevada, Las Vegas
Jinlong Zhu, University of Nevada, Las VegasFollow
Yonggang Wang, University of Nevada, Las VegasFollow
John Howard, University of Nevada, Las VegasFollow
X Lü, Los Alamos National Laboratory
Y Li, University of Texas at AustinFollow
Ravhi Kumar, University of Nevada, Las VegasFollow
Liping Wang, University of Nevada, Las VegasFollow
L L. Daemen, Oak Ridge National LabFollow
Y Zhao, University of Nevada, Las VegasFollow

Document Type

Article

Publication Date

1-1-2016

Publication Title

Solid State Ionics

Volume

284

First page number:

14

Last page number:

19

Abstract

Lithium-rich anti-perovskites (LiRAPs), with general formula Li3OX (X = Cl, Br), recently reported as superionic conductors with 3-dimensional Li+ migrating channels, are emerging as promising candidates for solid electrolytes in all-solid-state lithium-ion batteries (LIBs). However, great challenges remain in the fabrication of pure LiRAPs due to difficulties such as low yield, impurity phases, thermodynamic instabilities, and moisture-sensitivity. In this work, we thoroughly studied the formation mechanism of Li3OCl and Li3OBr using various solid-state reaction routes. Different experimental strategies were developed to improve the syntheses, namely, for the purposes of phase stability, phase purity, and large-scale production. One feasible method is to use the strong reducing agents Li metal or LiH to eliminate the OH species. The results show that LiH is more effective than Li metal, mainly due to negatively charged H- and reaction uniformity. The other successful method employs a solid diffusion approach using Li2O and LiX as the starting reagents, thereby avoiding OH entirely; ball milling of reagents under Ar atmosphere was utilized to decrease initial grain size and increase the reaction rate. Fourier transform infrared spectroscopy (FTIR), thermal analyses, and first-principles calculations were performed to give indications on the reaction pathway. © 2015 Elsevier B.V. All rights reserved.

Keywords

Lithium-ion battery; Lithium-rich anti-perovskite; Solid electrolyte; Solid-state reaction

Language

English

Repository Citation

Li, S., Zhu, J., Wang, Y., Howard, J., Lü, X., Li, Y., Kumar, R., Wang, L., Daemen, L. L., Zhao, Y. (2016). Reaction mechanism studies towards effective fabrication of lithium-rich anti-perovskites Li3OX (X = Cl, Br). Solid State Ionics, 284 14-19.
http://dx.doi.org/10.1016/j.ssi.2015.11.027