Structural Forces in Ionic Liquids: The Role of Ionic Size Asymmetry

de Souza, J. Pedro; Pivnic, Karina; Bazant, Martin Z.; Urbakh, Michael; Kornyshev, Alexei A.

doi:10.1021/acs.jpcb.1c09441

Title: Structural Forces in Ionic Liquids: The Role of Ionic Size Asymmetry

Journal Article · Tue Feb 08 00:00:00 EST 2022 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/acs.jpcb.1c09441· OSTI ID:1862875

^[1]; Pivnic, Karina ^[2];

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Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
School of Chemistry, The Sackler Center for Computational Molecular and Materials Science, Tel Aviv University, Tel Aviv, 6997801, Israel
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States, Department of Mathematics, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, London, W12 0BZ 2AZ, United Kingdom, Thomas Young Centre for Theory and Simulation of Materials, Imperial College London, South Kensington Campus, London, SW7 2AZ, United Kingdom

Ionic liquids (ILs) are charged fluids composed of anions and cations of different size and shape. The ordering of charge and density in ILs confined between charged interfaces underlies numerous applications of IL electrolytes. Here, we analyze the screening behavior and the resulting structural forces of a representative IL confined between two charge-varied plates. Using both molecular dynamics simulations and a continuum theory, we contrast the screening features of a more-realistic asymmetric system and a less-realistic symmetric one. The ionic size asymmetry plays a nontrivial role in charge screening, affecting both the ionic density profiles and the disjoining pressure distance dependence. Ionic systems with size asymmetry are stronger coupled systems, and this manifests itself both in their response to the electrode polarization and spontaneous structure formation at the interface. Analytical expressions for decay lengths of the disjoining pressure are obtained in agreement with the pressure profiles computed from molecular dynamics simulations.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Enhanced Nanofluidic Transport (CENT)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Leverhulme Trust; Israel Science Foundation (ISF); German Research Foundation (DFG)

Grant/Contract Number:: SC0019112; 1122374; RPG-2016- 223; 1141/18; BA 1008/21

OSTI ID:: 1862875

Alternate ID(s):: OSTI ID: 1904363

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Vol. 126 Journal Issue: 6; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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