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Title: Interference of electrical double layers: Confinement effects on structure, dynamics, and screening of ionic liquids

Abstract

Ionic liquids are widely used as electrolytes in electronic devices in which they are subject to nanoconfinement within nanopores or nanofilms. Because the intrinsic width of an electrical double layer is on the order of several nanometers, nanoconfinement is expected to fundamentally alter the double layer properties. Furthermore, in confined systems, a large portion of the ions are interfacial, e.g., at the electrode interface, leading to significant deviations of electrostatic screening and ion dynamics as compared to bulk properties. In this article, we systematically investigate the interference between electrical double layers for nanoconfined ionic liquids and the resulting influence on the structure, dynamics, and screening behavior. We perform molecular dynamics simulations for the ionic liquids [BMIm+][BF$$^-_4$$] and [BMIm+][PF$$^-_6$$] confined between two flat electrodes at systematic separation distances between 1.5 nm and 4.5 nm for both conducting and insulating boundary conditions. We find that while ion dynamics is expectedly slower than in the bulk (by ~2 orders of magnitude), there is an unexpected non-linear trend with the confinement length that leads to a local maximum in dynamic rates at ~3.5–4.5 nm confinement. We show that this nonlinear trend is due to the ion correlation that arises from the interference between opposite double layers. We further evaluate confinement effects on the ion structure and capacitance and investigate the influence of electronic polarization of the ionic liquid on the resulting properties. This systematic evaluation of the connection between electrostatic screening and structure and dynamics of ionic liquids in confined systems is important for the fundamental understanding of electrochemical supercapacitors.

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Georgia Inst. of Technology, Atlanta, GA (United States). Georgia Tech Research Institute
Publication Date:
Research Org.:
Georgia Institute of Technology, Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1803949
Alternate Identifier(s):
OSTI ID: 1600589
Grant/Contract Number:  
SC0020279
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Park, Suehyun, and McDaniel, Jesse G. Interference of electrical double layers: Confinement effects on structure, dynamics, and screening of ionic liquids. United States: N. p., 2020. Web. doi:10.1063/1.5144260.
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Park, Suehyun, & McDaniel, Jesse G. Interference of electrical double layers: Confinement effects on structure, dynamics, and screening of ionic liquids. United States. https://doi.org/10.1063/1.5144260
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Park, Suehyun, and McDaniel, Jesse G. Wed . "Interference of electrical double layers: Confinement effects on structure, dynamics, and screening of ionic liquids". United States. https://doi.org/10.1063/1.5144260. https://www.osti.gov/servlets/purl/1803949.
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@article{osti_1803949,
title = {Interference of electrical double layers: Confinement effects on structure, dynamics, and screening of ionic liquids},
author = {Park, Suehyun and McDaniel, Jesse G.},
abstractNote = {Ionic liquids are widely used as electrolytes in electronic devices in which they are subject to nanoconfinement within nanopores or nanofilms. Because the intrinsic width of an electrical double layer is on the order of several nanometers, nanoconfinement is expected to fundamentally alter the double layer properties. Furthermore, in confined systems, a large portion of the ions are interfacial, e.g., at the electrode interface, leading to significant deviations of electrostatic screening and ion dynamics as compared to bulk properties. In this article, we systematically investigate the interference between electrical double layers for nanoconfined ionic liquids and the resulting influence on the structure, dynamics, and screening behavior. We perform molecular dynamics simulations for the ionic liquids [BMIm+][BF$^-_4$] and [BMIm+][PF$^-_6$] confined between two flat electrodes at systematic separation distances between 1.5 nm and 4.5 nm for both conducting and insulating boundary conditions. We find that while ion dynamics is expectedly slower than in the bulk (by ~2 orders of magnitude), there is an unexpected non-linear trend with the confinement length that leads to a local maximum in dynamic rates at ~3.5–4.5 nm confinement. We show that this nonlinear trend is due to the ion correlation that arises from the interference between opposite double layers. We further evaluate confinement effects on the ion structure and capacitance and investigate the influence of electronic polarization of the ionic liquid on the resulting properties. This systematic evaluation of the connection between electrostatic screening and structure and dynamics of ionic liquids in confined systems is important for the fundamental understanding of electrochemical supercapacitors.},
doi = {10.1063/1.5144260},
journal = {Journal of Chemical Physics},
number = 7,
volume = 152,
place = {United States},
year = {Wed Feb 19 00:00:00 EST 2020},
month = {Wed Feb 19 00:00:00 EST 2020}
}
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https://doi.org/10.1063/1.5144260
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