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Title: Oxidative Decomposition Mechanisms of Lithium Peroxide Clusters: An Ab Initio Study

Abstract

Oxidative decomposition of solid lithium peroxide is an important part of the charging process in a Li-O-2 battery. In this paper, we investigate oxidative decomposition mechanisms of lithium peroxide clusters as molecular models for solid lithium peroxide using density functional methods to understand charging processes in advanced energy storage systems. Most calculations are done using a (Li2O2)(4) cluster with similar results obtained from a larger (Li2O2)(16) cluster. Reaction pathways of the clusters involving different sequences of oxidation, oxygen evolution, lithium cation removal, and spin excitation are investigated. The computations suggest that certain oxidative decomposition routes may not have dependence on the oxygen evolution or Li-ion removal kinetics due to the exothermicity of oxygen removal and Li+ removal (by solvent) upon oxidation. The computed charge potentials evaluated using a tetramer model indicates that it is possible to have low overcharge potential provided there exists a good electronic conductivity to facilitate the oxidative decomposition. Finally, oxidation potentials of a series of LixOy clusters are investigated to assess their dependence on stoichiometry and how the local site from which the electrons are being removed affects the charge potentials.

Authors:
;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Joint Center for Energy Storage Research (JCESR)
OSTI Identifier:
1530195
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Molecular Physics
Additional Journal Information:
Journal Volume: 117; Journal Issue: 9-12
Country of Publication:
United States
Language:
English
Subject:
charge overpotential; density functional theory; lithium peroxide; oxidative decomposition

Citation Formats

Assary, Rajeev S., and Curtiss, Larry A. Oxidative Decomposition Mechanisms of Lithium Peroxide Clusters: An Ab Initio Study. United States: N. p., 2019. Web. doi:10.1080/00268976.2018.1559955.
Assary, Rajeev S., & Curtiss, Larry A. Oxidative Decomposition Mechanisms of Lithium Peroxide Clusters: An Ab Initio Study. United States. doi:10.1080/00268976.2018.1559955.
Assary, Rajeev S., and Curtiss, Larry A. Tue . "Oxidative Decomposition Mechanisms of Lithium Peroxide Clusters: An Ab Initio Study". United States. doi:10.1080/00268976.2018.1559955.
@article{osti_1530195,
title = {Oxidative Decomposition Mechanisms of Lithium Peroxide Clusters: An Ab Initio Study},
author = {Assary, Rajeev S. and Curtiss, Larry A.},
abstractNote = {Oxidative decomposition of solid lithium peroxide is an important part of the charging process in a Li-O-2 battery. In this paper, we investigate oxidative decomposition mechanisms of lithium peroxide clusters as molecular models for solid lithium peroxide using density functional methods to understand charging processes in advanced energy storage systems. Most calculations are done using a (Li2O2)(4) cluster with similar results obtained from a larger (Li2O2)(16) cluster. Reaction pathways of the clusters involving different sequences of oxidation, oxygen evolution, lithium cation removal, and spin excitation are investigated. The computations suggest that certain oxidative decomposition routes may not have dependence on the oxygen evolution or Li-ion removal kinetics due to the exothermicity of oxygen removal and Li+ removal (by solvent) upon oxidation. The computed charge potentials evaluated using a tetramer model indicates that it is possible to have low overcharge potential provided there exists a good electronic conductivity to facilitate the oxidative decomposition. Finally, oxidation potentials of a series of LixOy clusters are investigated to assess their dependence on stoichiometry and how the local site from which the electrons are being removed affects the charge potentials.},
doi = {10.1080/00268976.2018.1559955},
journal = {Molecular Physics},
number = 9-12,
volume = 117,
place = {United States},
year = {2019},
month = {6}
}