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Multiscale electrochemistry of lithium manganese oxide (LiMn2O4): from single particles to ensembles and degrees of electrolyte wetting
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Tao, Binglin, McPherson, Ian J., Daviddi, Enrico, Bentley, Cameron Luke and Unwin, Patrick R. (2023) Multiscale electrochemistry of lithium manganese oxide (LiMn2O4): from single particles to ensembles and degrees of electrolyte wetting. ACS Sustainable Chemistry & Engineering, 11 (4). pp. 1459-1471. doi:10.1021/acssuschemeng.2c06075 ISSN 2168-0485.
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Official URL: https://doi.org/10.1021/acssuschemeng.2c06075
Abstract
Scanning electrochemical cell microscopy (SECCM) facilitates single particle measurements of battery materials using voltammetry at fast scan rates (1 V s–1), providing detailed insight into intrinsic particle kinetics, otherwise obscured by matrix effects. Here, we elucidate the electrochemistry of lithium manganese oxide (LiMn2O4) particles, using a series of SECCM probes of graded size to determine the evolution of electrochemical characteristics from the single particle to ensemble level. Nanometer scale control over the SECCM meniscus cell position and height further allows the study of variable particle/substrate electrolyte wetting, including comparison of fully wetted particles (where contact is also made with the underlying glassy carbon substrate electrode) vs partly wetted particles. We find ensembles of LiMn2O4 particles show voltammograms with much larger peak separations than those of single particles. In addition, if the SECCM meniscus is brought into contact with the substrate electrode, such that the particle–support contact changes from dry to wet, a further dramatic increase in peak separation is observed. Finite element method modeling of the system reveals the importance of finite electronic conductivity of the particles, contact resistance, surface kinetics, particle size, and contact area with the electrode surface in determining the voltammetric waveshape at fast scan rates, while the responses are relatively insensitive to Li+ diffusion coefficients over a range of typical values. The simulation results explain the variability in voltammetric responses seen at the single particle level and reveal some of the key factors responsible for the evolution of the response, from ensemble, contact, and wetting perspectives. The variables and considerations explored herein are applicable to any single entity (nanoscale) electrochemical study involving low conductivity materials and should serve as a useful guide for further investigations of this type. Overall, this study highlights the potential of multiscale measurements, where wetting, electronic contact, and ionic contact can be varied independently, to inform the design of practical composite electrodes.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QD Chemistry T Technology > TK Electrical engineering. Electronics Nuclear engineering |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
SWORD Depositor: | Library Publications Router | ||||||||||||
Library of Congress Subject Headings (LCSH): | Scanning electrochemical microscopy, Electrochemistry, Electrodes , Lithium ion batteries -- Material, Electrolytes | ||||||||||||
Journal or Publication Title: | ACS Sustainable Chemistry & Engineering | ||||||||||||
Publisher: | American Chemical Society (ACS) | ||||||||||||
ISSN: | 2168-0485 | ||||||||||||
Official Date: | 30 January 2023 | ||||||||||||
Dates: |
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Volume: | 11 | ||||||||||||
Number: | 4 | ||||||||||||
Page Range: | pp. 1459-1471 | ||||||||||||
DOI: | 10.1021/acssuschemeng.2c06075 | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Re-use Statement: | ** Article version: VoR ** From Crossref journal articles via Jisc Publications Router ** History: epub 12-01-2023; issued 12-01-2023. ** Licence for VoR version of this article starting on 13-01-2023: https://creativecommons.org/licenses/by/4.0/ | ||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||
Copyright Holders: | Copyright © 2023 The Authors. Published by American Chemical Society | ||||||||||||
Date of first compliant deposit: | 8 March 2023 | ||||||||||||
Date of first compliant Open Access: | 8 March 2023 | ||||||||||||
RIOXX Funder/Project Grant: |
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