journal article·2024-12-17Open access

Long-Range Surface Forces in Salt-in-Ionic Liquids

Xuhui Zhang, Zachary A. H. Goodwin, Alexis G. Hoane, Alex Deptula, Daniel M. Markiewitz, Nicola Molinari, Qianlu Zheng, Hua Li, Michael McEldrew, Boris Kozinsky, Martin Z. Bazant, Cecilia Leal, Rob Atkin, Andrew A. Gewirth, Mark W. Rutland, Rosa M. Espinosa-Marzal

ACS Nano· Volume 18· Issue 50

Abstract

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.
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Research context

OpenAlex topics: Ionic liquids properties and applications · Advanced Battery Materials and Technologies · Advancements in Battery Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Civil and Environmental Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States

John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States

Department of Materials, Imperial College of London, South Kensington Campus, London SW7 2AZ, U.K.

Department of Chemistry, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States

Department of Materials Science and Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States

Robert Bosch LLC, Research and Technology Center, Cambridge, Massachusetts 02142, United States

School of Molecular Sciences, The University of Western Australia, Perth, Western Australia 6009, Australia

Centre for Microscopy, Characterisation and Analysis, The University of Western Australia, Perth, Western Australia 6009, Australia

Department of Mathematics, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States

Department of Chemistry, KTH Royal Institute of Technology, Stockholm 100 44, Sweden

School of Chemistry, University of New South Wales, Sydney 2052, Australia

Laboratoire de Tribologie et Dynamique des Systèmes, École Centrale de Lyon, Lyon 69130, France

Bioeconomy and Health, Materials and Surface Design, RISE Research Institutes of Sweden, Stockholm 114 28, Sweden

Funding

Energy Frontier Research Centers · National Science Foundation Graduate Research Fellowship Program · Vetenskapsr??det · Massachusetts Institute of Technology · U.S. Department of Defense · National Science Foundation · Stiftelsen f??r Strategisk Forskning · U.S. Army DEVCOM ARL Army Research Office · Center for Enhanced Nanofluidic Transport

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