Oxygen Dimerization as a Defect-Driven Process in Bulk LiNiO 2

To explore the possibility of oxygen dimerization-particularly, the formation of molecular oxygen-like species-in the bulk of LiNiO lithium ion cathode materials at high states of charge, we conduct a redox-product structure search inspired by recent methodological developments for point-defect stru...

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Bibliographic Details
Published inACS energy letters Vol. 9; no. 8; pp. 4180 - 4187
Main Authors Squires, Alexander G, Ganeshkumar, Lavan, Savory, Christopher N, Kavanagh, Seán R, Scanlon, David O
Format Journal Article
LanguageEnglish
Published United States 09.08.2024
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Summary:To explore the possibility of oxygen dimerization-particularly, the formation of molecular oxygen-like species-in the bulk of LiNiO lithium ion cathode materials at high states of charge, we conduct a redox-product structure search inspired by recent methodological developments for point-defect structure prediction. We find that (1) delithiated Li NiO ( = 1) has good kinetic stability toward decomposition into molecular oxygen and reduced transition-metal oxides but (2) defects can act as nucleation sites for oxygen dimerization. These results help reconcile conflicting reports on the formation of bulk molecular oxygen in LiNiO and other nickel-rich cathode materials, highlighting the role of defect chemistry in driving the bulk degradation of these compounds.
ISSN:2380-8195
2380-8195
DOI:10.1021/acsenergylett.4c01307