Martínez de Irujo Labalde, X., Grievson, H., Mortimer, J.-M. et al. (6 more authors) (2023) Suppression of Fe-cation migration by indium substitution in LiFe<sub>2–<i>x</i></sub>In<i><sub>x</sub></i>SbO<sub>6</sub> cathode materials. Chemistry of Materials, 35 (1). pp. 337-346. ISSN 0897-4756
Abstract
Cation migration on electrochemical cycling can significantly influence the performance of li-ion cathode materials. Phases of composition LiFe2-xInxSbO6 (0 < x <1) adopt crystal structures described in space group Pnnm, consisting of a hexagonally close-packed array of oxide ions, with Fe/In and Sb cations ordered on octahedral sites, and lithium cations located within partially occupied tetrahedral sites. NPD, SXRD, and 57Fe Mössbauer data indicate that on reductive lithium insertion (either chemically or electrochemically), LiFe2SbO6 is converted to Li2Fe2SbO6 accompanied by large-scale cation migration, to form a partially Fe/Li cation-ordered and Fe2+/Fe3+ charge-ordered phase from which lithium cations cannot be easily removed, either chemically or electrochemically. Partial substitution of Fe with In suppresses the degree of cation migration that occurs on lithium insertion such that no structural change is observed when LiFeInSbO6 is converted into Li1.5FeInSbO6, allowing the system to be repeatedly electrochemically cycled between these two compositions. Phases with intermediate levels of In substitution exhibit low levels of Fe migration on Li insertion and electrochemical capacities which evolve on cycling. The mechanism by which the In3+ cations suppress the migration of Fe cations is discussed along with the cycling behavior of the LiFe1.5In0.5SbO6-Li1.75Fe1.5In0.5SbO6.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 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: | Cations; Diffraction; Genetics; Materials; Redox reactions |
Dates: |
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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: | 19 Jan 2023 15:06 |
Last Modified: | 19 Jan 2023 15:06 |
Published Version: | http://dx.doi.org/10.1021/acs.chemmater.2c03418 |
Status: | Published |
Publisher: | American Chemical Society (ACS) |
Refereed: | Yes |
Identification Number: | 10.1021/acs.chemmater.2c03418 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:195402 |