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dc.contributor.authorWang, Andrew A
dc.contributor.authorGunnarsdóttir, Anna B
dc.contributor.authorFawdon, Jack
dc.contributor.authorPasta, Mauro
dc.contributor.authorGrey, Clare P
dc.contributor.authorMonroe, Charles W
dc.date.accessioned2021-10-22T00:37:34Z
dc.date.available2021-10-22T00:37:34Z
dc.date.issued2021-08-15
dc.identifier.issn2380-8195
dc.identifier.otherPMC8438662
dc.identifier.other34541321
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/329742
dc.description.abstractSuperconcentrated electrolytes, being highly thermodynamically nonideal, provide a stringent proving ground for continuum transport theories. Herein, we test an ostensibly complete model of LiPF<sub>6</sub> in ethyl-methyl carbonate (EMC) based on the Onsager-Stefan-Maxwell theory from irreversible thermodynamics. We perform synchronous magnetic resonance imaging (MRI) and chronopotentiometry to examine how superconcentrated LiPF<sub>6</sub>:EMC responds to galvanostatic polarization and open-circuit relaxation. We simulate this experiment using an independently parametrized model with six composition-dependent electrolyte properties, quantified up to saturation. Spectroscopy reveals increasing ion association and solvent coordination with salt concentration. The potentiometric MRI data agree closely with the predicted ion distributions and overpotentials, providing a completely independent validation of the theory. Superconcentrated electrolytes exhibit strong cation-anion interactions and extreme solute-volume effects that mimic elevated lithium transference. Our simulations allow surface overpotentials to be extracted from cell-voltage data to track lithium interfaces. Potentiometric MRI is a powerful tool to illuminate electrolytic transport phenomena.
dc.languageeng
dc.rightsAttribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.sourceessn: 2380-8195
dc.sourcenlmid: 101697523
dc.titlePotentiometric MRI of a Superconcentrated Lithium Electrolyte: Testing the Irreversible Thermodynamics Approach.
dc.typeArticle
dc.date.updated2021-10-22T00:37:34Z
prism.endingPage3095
prism.issueIdentifier9
prism.publicationNameACS energy letters
prism.startingPage3086
prism.volume6
dc.identifier.doi10.17863/CAM.77188
rioxxterms.versionofrecord10.1021/acsenergylett.1c01213
rioxxterms.versionVoR
rioxxterms.licenseref.urihttps://creativecommons.org/licenses/by/4.0/
dc.contributor.orcidWang, Andrew A [0000-0003-1864-5213]
dc.contributor.orcidGunnarsdóttir, Anna B [0000-0001-6593-788X]
dc.contributor.orcidPasta, Mauro [0000-0002-2613-4555]
dc.contributor.orcidGrey, Clare P [0000-0001-5572-192X]
dc.contributor.orcidMonroe, Charles W [0000-0002-9894-5023]
pubs.funder-project-idEngineering and Physical Sciences Research Council (EP/R010145/1, EP/S003053/1)
pubs.funder-project-idEuropean Research Council (835073)


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Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International