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Long-Range Surface Forces in Salt-in-Ionic Liquids
Univ Illinois Urbana & Champaign, Dept Civil & Environm Engn, Urbana, IL 61801 USA..ORCID iD: 0009-0000-7280-6060
Harvard Univ, John A Paulson Sch Engn & Appl Sci, Cambridge, MA 02138 USA.;Imperial Coll London, Dept Mat, London SW7 2AZ, England..
Univ Illinois, Dept Chem, Urbana, IL 61801 USA..
Univ Illinois, Dept Mat Sci & Engn, Urbana, IL 61801 USA..
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2024 (English)In: ACS Nano, ISSN 1936-0851, E-ISSN 1936-086X, Vol. 18, no 50, p. 34007-34022Article 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 (ACS) , 2024. Vol. 18, no 50, p. 34007-34022
Keywords [en]
salt-in-ionic liquid, concentrated electrolytes, force measurements, electric double layer, MD simulation
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-358695DOI: 10.1021/acsnano.4c09355ISI: 001372140200001PubMedID: 39641512Scopus ID: 2-s2.0-85211495625OAI: oai:DiVA.org:kth-358695DiVA, id: diva2:1929445
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QC 20250120

Available from: 2025-01-20 Created: 2025-01-20 Last updated: 2025-01-20Bibliographically approved

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Rutland, Mark W.

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