Ogley, M.J.W., Menon, A.S., Johnston, B.J. et al. (10 more authors) (2024) Rethinking oxygen redox: does oxygen dimerization occur without oxidation in Li2NiO3? ACS Energy Letters, 9 (9). pp. 4607-4613. ISSN 2380-8195
Abstract
In layered lithium transition metal oxide cathodes, high-voltage operation is accompanied by the formation of oxygen dimers, which are widely used as an indicator of oxygen-redox activity. However, understanding the role that oxygen dimerization plays in facilitating charge compensation is still needed. Li2NiO3 (a 3d8L2-containing compound, where L is a ligand hole) is studied as a model system, where oxygen dimerization is shown to occur without cathode oxidation. Electrochemical cycling results in a net reduction of the cathode, accompanied by structural transformations, despite spectroscopic features of oxygen dimers arising at the top-of-charge. Here, oxygen dimerization is shown to coexist alongside a structurally transformed and electronically reduced cathode structure, thus highlighting that O dimerization is independent of bulk redox processes. This makes it clear that a thermodynamically derived transformation toward a reduced phase remains the only variable capable of generating O-O dimers in Li2NiO3
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © 2024 The Authors. This is an Open Access article distributed under the terms of the Creative Commons Attribution Licence (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. |
Keywords: | Dimerization; Electrodes; Oligomers; Oxides; Redox Reactions |
Dates: |
|
Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Engineering (Sheffield) > Department of Materials Science and Engineering (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 23 Sep 2024 10:03 |
Last Modified: | 23 Sep 2024 10:03 |
Published Version: | http://dx.doi.org/10.1021/acsenergylett.4c02031 |
Status: | Published |
Publisher: | American Chemical Society (ACS) |
Refereed: | Yes |
Identification Number: | 10.1021/acsenergylett.4c02031 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:217510 |