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Long-Range Surface Forces in Salt-in-Ionic Liquids
University of Illinois at Urbana−Champaign, USA.
Harvard University, USA; Imperial College of London, UK.
University of Illinois at Urbana−Champaign, USA.
University of Illinois at Urbana−Champaign, USA.
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2024 (English)In: ACS Nano, ISSN 1936-0851, E-ISSN 1936-086X, Vol. 18, no 50, p. 34007-22Article in journal (Refereed) Published
Abstract [en]

Ionic liquids (ILs) are a promising class of electrolytes with a unique combination of properties, such as extremely low vapor pressures and nonflammability. Doping ILs with alkali metal salts creates an electrolyte that is of interest for battery technology. These salt-in-ionic liquids (SiILs) are a class of superconcentrated, strongly correlated, and asymmetric electrolytes. Notably, the transference numbers of the alkali metal cations have been found to be negative. Here, we investigate Na-based SiILs with a surface force apparatus, X-ray scattering, and atomic force microscopy. We find evidence of confinement-induced structural changes, giving rise to long-range interactions. Force curves also reveal an electrolyte structure consistent with our predictions from theory and simulations. The long-range steric interactions in SiILs reflect the high aspect ratio of compressible aggregates at the interfaces rather than the purely electrostatic origin predicted by the classical electrolyte theory. This conclusion is supported by the reported anomalous negative transference numbers, which can be explained within the same aggregation framework. The interfacial nanostructure should impact the formation of the solid electrolyte interphase in SiILs. 

Place, publisher, year, edition, pages
American Chemical Society , 2024. Vol. 18, no 50, p. 34007-22
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:ri:diva-76308DOI: 10.1021/acsnano.4c09355Scopus ID: 2-s2.0-85211495625OAI: oai:DiVA.org:ri-76308DiVA, id: diva2:1932779
Note

National Science Foundation Grant DMR 1904681 (RMEM),National Science Foundation Grant CBET 1916609 (RMEM),U.S. Army DEVCOM ARL Army Research Office W911NF-24-1-0209 (RMEM), Swedish Research Council, VR ProjectNo. 2017-04080 (MWR), Swedish Foundation for StrategicResearch Project No. EM16-0013, “REFIT” (MWR), Amar G.Bose Research Grant (MM and MZB), National ScienceFoundation Graduate Research Fellowship Grant No. 2141064(DMM)G Center for Enhanced Nanofluidic Transport CENT(DMM and MZB), Energy Frontier Research Center fundedby the U.S. Department of Energy (DOE), Office of Science,Basic Energy Sciences (BES), under Award # DE-SC0019112(D.M.M. and M.Z.B.), Department of Navy Award N00014-20-1-2418 issued by the Office of Naval Research

Available from: 2025-01-29 Created: 2025-01-29 Last updated: 2025-09-23Bibliographically approved

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Rutland, Mark W.

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