West, A. orcid.org/0000-0002-5492-2102, Zhao, Y.R., Middlemiss, L.R. et al. (2 more authors) (2024) Oxygen redox activity in battery cathodes and the role of underbonded oxygen. Zeitschrift für anorganische und allgemeine Chemie, 650 (23). e202400067. ISSN 0044-2313
Abstract
It is widely recognised that oxygen redox makes a significant contribution to the high capacity of some cathode materials in addition to transition metal redox. We attribute this to the presence of underbonded oxide ions, either in bulk structures or at surfaces, which are the initial source of oxygen redox during charging. Underbonded oxide ions experience departures from local electroneutrality; examples include Li4Mn5O12 spinel and Li‐rich layered rock salt structures but not stoichiometric LiCoO2 or Li2MnO3. Underbonded oxide ions ionise more readily than fully‐stabilised lattice oxide ions since, using an ionic bonding description, they are associated with a deficiency of positive charge in the coordination sphere of surrounding cations. Pauling’s electrostatic bond strength criterion gives a simple guide to structures or compositions that show departures from local electroneutrality and provides the starting point for a new way to consider oxygen redox. Li4Mn5O12 behaves as an anode due to Mn redox below 3V and as a cathode due to reversible oxygen redox above ~3.8 V. Underbonded oxygens are also identified in other structures, including high capacity Li‐rich layered rock salt structures.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2024 The Author(s). Zeitschrift für anorganische und allgemeine Chemie published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited: https://creativecommons.org/licenses/by/4.0/ |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Engineering (Sheffield) > School of Chemical, Materials and Biological Engineering |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 19 Nov 2024 16:32 |
Last Modified: | 25 Feb 2025 12:35 |
Status: | Published |
Publisher: | Wiley |
Refereed: | Yes |
Identification Number: | 10.1002/zaac.202400067 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:219779 |