Ab Initio Atomistic Thermodynamics Study of the (001) Surface of LiCoO2 in a Water Environment and Implications for Reactivity under Ambient Conditions

Xu Huang; Joseph W Bennett; Mimi N Hang; Elizabeth D Laudadio; Robert J Hamers; Sara E Mason

doi:10.1021/acs.jpcc.6b12163

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Ab Initio Atomistic Thermodynamics Study of the (001) Surface of LiCoO2 in a Water Environment and Implications for Reactivity under Ambient Conditions

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Ab Initio Atomistic Thermodynamics Study of the (001) Surface of LiCoO2 in a Water Environment and Implications for Reactivity under Ambient Conditions

Xu Huang, Joseph W Bennett, Mimi N Hang, Elizabeth D Laudadio, Robert J Hamers and Sara E Mason

Journal of physical chemistry. C, Vol.121(9), pp.5069-5080

03/09/2017

DOI: 10.1021/acs.jpcc.6b12163

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Abstract

We use GGA + U methodology to model the bulk and surface structure of varying stoichiometries of the (001) surface of LiCoO2. The DFT energies obtained for these surface-slab models are used for two thermodynamic analyses to assess the relative stabilities of different surface configurations, including hydroxylation. In the first approach, surface free energies are calculated within a thermodynamic framework, and the second approach is a surface-solvent ion exchange model. We find that, for both models, the −CoO–H1/2 surface is the most stable structure near the O-rich limit, which corresponds to ambient conditions. We find that surfaces terminated with Li are higher in energy, and we go on to show that H and Li behave differently on the (001) LiCoO2 surface. The optimized geometries show that terminal Li and H occupy nonequivalent surface sites. In terms of electronic structure, Li and H terminations exhibit distinct bandgap characters, and there is also a distinctive distribution of charge at the surface. We go on to probe how the variable Li and H terminations affect reactivity, as probed through phosphate adsorption studies.

Details

Title: Subtitle: Ab Initio Atomistic Thermodynamics Study of the (001) Surface of LiCoO2 in a Water Environment and Implications for Reactivity under Ambient Conditions
Creators: Xu Huang - University of Iowa
Joseph W Bennett - University of Iowa
Mimi N Hang - University of Wisconsin-Madison
Elizabeth D Laudadio - University of Wisconsin-Madison
Robert J Hamers - University of Wisconsin-Madison
Sara E Mason - University of Iowa
Resource Type: Journal article
Publication Details: Journal of physical chemistry. C, Vol.121(9), pp.5069-5080
DOI: 10.1021/acs.jpcc.6b12163
NLM abbreviation: J Phys Chem C Nanomater Interfaces
ISSN: 1932-7447
eISSN: 1932-7455
Publisher: American Chemical Society
Grant note: DOI: 10.13039/100000165, name: Division of Chemistry, award: CHE-1503408
Language: English
Date published: 03/09/2017
Academic Unit: Chemistry
Record Identifier: 9983985917502771

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