Evaluation of Amorphous Oxide Coatings for High-Voltage Li-Ion Battery Applications Using a First-Principles Framework

Date Published
07/2020
Publication Type
Journal Article
Authors
DOI
10.1021/acsami.0c10000
Abstract

Cathode surface coatings are widely used industrially as a means to suppress degradation and improve electrochemical performance of lithium-ion batteries. However, developing an optimal coating is challenging, as different coating materials may enhance one aspect of performance while hindering another. To elucidate the fundamental thermodynamic and transport properties of amorphous cathode coating materials, here, we present a framework for calculating and analyzing the Li+ and O2– transport and the stability against delithiation in such materials. Our framework includes systematic workflows of ab-initio molecular dynamics calculations to obtain amorphous structures and diffusion trajectories coupled with an analysis of critical changes of the active-ion local environment during diffusion. Based on these data, we provide an estimate of room-temperature diffusivities, including statistical error bars, and the evaluation of the coating suitability in terms of its ability to facilitate Li+ transport while blocking O2– transport. Finally, we add the thermodynamic stability analysis of the coating chemistry within the operating voltage of common Li-ion cathodes. We apply this framework to two commonly used amorphous coating materials, Al2O3 and ZnO. We find that (1) in general, a higher Li+ content increases both Li+ and O2– diffusivities in both Al2O3 and ZnO. Also, Li+ and O2– diffuse much faster in ZnO than in Al2O3. (2) However, neither Al2O3 nor ZnO is expected to retain a significant concentration of Li+ at high charge. (3) ZnO performs much more poorly in terms of O2– blocking, and hence, Al2O3 is preferred for high-voltage cathode applications. These results will help to quantitatively evaluate amorphous materials, such as metal oxides and fluorides, for different performance metrics and facilitate the development of optimal cathode coatings.

Journal
ACS Applied Materials & Interfaces
Volume
12
Year of Publication
2020
Issue
31
Pagination
35748 - 35756
ISSN Number
1944-8244
Short Title
ACS Appl. Mater. Interfaces
Refereed Designation
Refereed
Organizations
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