DFT and thermodynamics calculations of surface cation release in LiCoO2

Ali Abbaspour-Tamijani; Joseph W Bennett; Diamond T Jones; Natalia Cartagena-Gonzalez; Zachary R Jones; Elizabeth D Laudadio; Robert J Hamers; Juan A Santana; Sara E Mason

doi:10.1016/j.apsusc.2020.145865

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DFT and thermodynamics calculations of surface cation release in LiCoO2

Journal article

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DFT and thermodynamics calculations of surface cation release in LiCoO2

Ali Abbaspour-Tamijani, Joseph W Bennett, Diamond T Jones, Natalia Cartagena-Gonzalez, Zachary R Jones, Elizabeth D Laudadio, Robert J Hamers, Juan A Santana and Sara E Mason

Applied surface science, Vol.515, p.145865

06/15/2020

DOI: 10.1016/j.apsusc.2020.145865

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Abstract

[Display omitted] •DFT + Thermodynamics to predict cobalt release from oxide surfaces in water.•DFT vibrational analysis of surface termination-specific modes.•Benchmarking provides upper- and lower-bounds for modeled surface properties.•In water, surface Co release from lithium cobalt oxide is at least 7% at neutral pH. While complex metal oxides (CMOs) such as LiCoO2 (LCO) are currently used in multiple electronic devices, their environmental impacts are not well understood. In this work, we apply density functional theory (DFT) and thermodynamics modeling to study LCO surface transformations. We performed Raman studies on bulk LCO, and compared experimental and computational results. Full vibrational analysis of the model LCO surfaces show localized surface modes that are distinct from bulk, varying in Li and OH surface terminations. Central to this study are calculations to assess the dependence of the DFT + thermodynamics methodology on computational parameters, such as the choice of the exchange-correlation functional, and model geometry, specifically varying slab thickness and supercell dimensions. We discuss how the results can be used to establish upper- and lower-bounds for favorable surface cation vacancy formation under varying pH conditions. The model predicts that at a pH of 7, up to 16% of surface Co will undergo dissolution. We go on to discuss how these model results relate to experimental dissolution studies. We also extrapolate how our results can provide useful insights to guide the (re)design of CMOs with tailored ion release behavior.

Complex metal oxides

DFT

Dissolution

Environmental chemistry

Ion release

Li-ion battery

Details

Title: Subtitle: DFT and thermodynamics calculations of surface cation release in LiCoO2
Creators: Ali Abbaspour-Tamijani - Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA
Joseph W Bennett - Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA
Diamond T Jones - Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA
Natalia Cartagena-Gonzalez - Department of Chemistry, The University of Puerto Rico at Cayey, P. O. Box 372230, Cayey, PR 00737-2230, USA
Zachary R Jones - Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706, USA
Elizabeth D Laudadio - Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706, USA
Robert J Hamers - Department of Chemistry, University of Wisconsin-Madison, Madison, WI 53706, USA
Juan A Santana - Department of Chemistry, The University of Puerto Rico at Cayey, P. O. Box 372230, Cayey, PR 00737-2230, USA
Sara E Mason - Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA
Resource Type: Journal article
Publication Details: Applied surface science, Vol.515, p.145865
Publisher: Elsevier B.V
DOI: 10.1016/j.apsusc.2020.145865
ISSN: 0169-4332
eISSN: 1873-5584
Grant note: DOI: 10.13039/100000001, name: National Science Foundation
Language: English
Date published: 06/15/2020
Academic Unit: Chemistry
Record Identifier: 9984216727602771

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