Surface Morphology and Surface Stability against Oxygen Loss of the Lithium-Excess Li 2 MnO 3 Cathode Material as a Function of Lithium Concentration

Date Published
09/2016
Publication Type
Journal Article
Authors
DOI
10.1021/acsami.6b07259
Abstract

There is a growing appreciation for the role of surface reactivity and subsequent reconstruction affecting the performance of high-voltage, high-capacity Li-ion cathode materials. In particular, the promising Li-excess materials are known to exhibit significant vulnerability toward oxygen release, which can cause surface densification and impede Li intercalation. Here we focus on the end member, Li2MnO3, as a Li-excess, Mn-rich representative of this class of materials and systematically elucidate all possible stoichiometric low Miller index surfaces with various cation ordering on each surface. We apply surface cation reconstruction rules that depend on the local environment, including target Mn–Li site exchanges, and optimize the resulting surface Li configurations using metadynamics. The equilibrium Wulff shape shows dominant (001), (010) surface facets, and almost all facets exhibit favorable Mn reconstruction. Most importantly, we find that while all equilibrium LixMnO3 surfaces become unstable toward oxygen release for x < 1.7, some facets are consistently more resistant than others which may provide a design metric for more stable particle morphologies and enhanced surface oxygen retention.

Journal
ACS Applied Materials & Interfaces
Volume
8
Year of Publication
2016
Issue
38
Pagination
25595 - 25602
ISSN Number
1944-8244
Short Title
ACS Appl. Mater. Interfaces
Refereed Designation
Refereed
Organizations
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