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Oxygen Loss on Disordered Li-Excess, Mn-Rich Li-Ion Cathode Li(2)MnO(2)F through First-Principles Modeling

[Image: see text] Oxygen evolution energies were calculated for the {100}, {110}, {111}, and {112} type facets of the rock-salt-structured cation-disordered Li-excess, Mn-rich Li-ion (DRX) cathode Li(2)MnO(2)F at the fully lithiated, 25% delithiation, and 50% delithiation states. Our calculations sh...

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Autores principales: Burns, Jordan, Persson, Kristin A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10653073/
https://www.ncbi.nlm.nih.gov/pubmed/38027546
http://dx.doi.org/10.1021/acs.chemmater.3c01815
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author Burns, Jordan
Persson, Kristin A.
author_facet Burns, Jordan
Persson, Kristin A.
author_sort Burns, Jordan
collection PubMed
description [Image: see text] Oxygen evolution energies were calculated for the {100}, {110}, {111}, and {112} type facets of the rock-salt-structured cation-disordered Li-excess, Mn-rich Li-ion (DRX) cathode Li(2)MnO(2)F at the fully lithiated, 25% delithiation, and 50% delithiation states. Our calculations showed that Li(2)MnO(2)F remains much more robust to O loss than its nonfluorinated counterparts, as has been shown in experimental work. In particular, the {110} and {112} facets are the most resilient against O loss. Focusing on the {100} type facet, which previous work has shown to be the most likely exposed facet of Li(2)MnO(2)F, it was found that higher proportions of Li in an O coordination shell lead to lower O evolution energy (Ẽ(O)) and facilitate O loss. It was also found that at higher states of delithiation, surface fluorine had a weaker effect in increasing Ẽ(O), meaning the protective effect of F against O loss is more effective at higher lithiation states. Electronic structure chemical bonding analysis revealed weaker bonding interactions between Li and O correlated with lower Ẽ(O) and hence a higher propensity for surface O loss..
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spelling pubmed-106530732023-11-16 Oxygen Loss on Disordered Li-Excess, Mn-Rich Li-Ion Cathode Li(2)MnO(2)F through First-Principles Modeling Burns, Jordan Persson, Kristin A. Chem Mater [Image: see text] Oxygen evolution energies were calculated for the {100}, {110}, {111}, and {112} type facets of the rock-salt-structured cation-disordered Li-excess, Mn-rich Li-ion (DRX) cathode Li(2)MnO(2)F at the fully lithiated, 25% delithiation, and 50% delithiation states. Our calculations showed that Li(2)MnO(2)F remains much more robust to O loss than its nonfluorinated counterparts, as has been shown in experimental work. In particular, the {110} and {112} facets are the most resilient against O loss. Focusing on the {100} type facet, which previous work has shown to be the most likely exposed facet of Li(2)MnO(2)F, it was found that higher proportions of Li in an O coordination shell lead to lower O evolution energy (Ẽ(O)) and facilitate O loss. It was also found that at higher states of delithiation, surface fluorine had a weaker effect in increasing Ẽ(O), meaning the protective effect of F against O loss is more effective at higher lithiation states. Electronic structure chemical bonding analysis revealed weaker bonding interactions between Li and O correlated with lower Ẽ(O) and hence a higher propensity for surface O loss.. American Chemical Society 2023-10-23 /pmc/articles/PMC10653073/ /pubmed/38027546 http://dx.doi.org/10.1021/acs.chemmater.3c01815 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Burns, Jordan
Persson, Kristin A.
Oxygen Loss on Disordered Li-Excess, Mn-Rich Li-Ion Cathode Li(2)MnO(2)F through First-Principles Modeling
title Oxygen Loss on Disordered Li-Excess, Mn-Rich Li-Ion Cathode Li(2)MnO(2)F through First-Principles Modeling
title_full Oxygen Loss on Disordered Li-Excess, Mn-Rich Li-Ion Cathode Li(2)MnO(2)F through First-Principles Modeling
title_fullStr Oxygen Loss on Disordered Li-Excess, Mn-Rich Li-Ion Cathode Li(2)MnO(2)F through First-Principles Modeling
title_full_unstemmed Oxygen Loss on Disordered Li-Excess, Mn-Rich Li-Ion Cathode Li(2)MnO(2)F through First-Principles Modeling
title_short Oxygen Loss on Disordered Li-Excess, Mn-Rich Li-Ion Cathode Li(2)MnO(2)F through First-Principles Modeling
title_sort oxygen loss on disordered li-excess, mn-rich li-ion cathode li(2)mno(2)f through first-principles modeling
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10653073/
https://www.ncbi.nlm.nih.gov/pubmed/38027546
http://dx.doi.org/10.1021/acs.chemmater.3c01815
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