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Cited by 1,098Electrostatics and Colloid InteractionsIonic liquids properties and applicationsElectrohydrodynamics and Fluid Dynamics

Double Layer in Ionic Liquids: Overscreening versus Crowding

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Bazant, Martin Z., Storey, Brian D., Kornyshev, Alexei A.·2011·Physical Review Letters
DOI 10.1103/physrevlett.106.046102
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Abstract

We develop a simple Landau-Ginzburg-type continuum theory of solvent-free ionic liquids and use it to predict the structure of the electrical double layer. The model captures overscreening from short-range correlations, dominant at small voltages, and steric constraints of finite ion sizes, which prevail at large voltages. Increasing the voltage gradually suppresses overscreening in favor of the crowding of counterions in a condensed inner layer near the electrode. This prediction, the ion profiles, and the capacitance-voltage dependence are consistent with recent computer simulations and experiments on room-temperature ionic liquids, using a correlation length of order the ion size.

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  • In a highly concentrated condition, alternative layers of cations and anions can be formed at the interface due to overscreening or crowding effect, when role of anions becomes more significant.

    “Moreover, in a highly concentrated condition, alternative layers of cations and anions can be formed at the interface due to the so-called 'overscreening e ect' or 'crowding e ect' [43,44], when the role of anions should become more significant.”

    From Effect of Hofmeister Anions on Interfacial Properties of Mica Surface in Concentrated Aqueous Solution (2020) · cites this paper as [43]

    The Introduction and Fig. 1 caption describe alternating counterion-rich and coion-rich layers at an ionic-liquid electrode, with overscreening at moderate voltage and counterion crowding at high voltage. They do not say that anions specifically become more significant; which ions are counterions or coions depends on the electrode charge. Page numbers are not available for these passages in our copy. (LLM, conf=0.85)

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  • According to the theoretical model for ionic liquids and molten salts, ion correlation and finite ion-size lead to overscreening and crowding in the Stern layer.

    “According to the theoretical model for ionic liquids and molten salts [43], ion correlation and finite ion-size lead to 'overscreening' and 'crowding' in the Stern layer.”

    From Effect of Hofmeister Anions on Interfacial Properties of Mica Surface in Concentrated Aqueous Solution (2020) · cites this paper as [43]

    The Abstract (p. 1) attributes overscreening to short-range ion correlations and crowding to finite ion size in a condensed inner layer near the electrode. The Conclusion describes the model as applying to ionic liquids and molten salts. Our copy does not specifically locate both effects in the Stern layer; it describes them as features of the electrical double layer. (LLM, conf=0.83)

    Experimental — accuracy not yet measured

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Research works printed but not linked: 38

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Authors
Bazant, M. Z., Storey, B. D., & Kornyshev, A. A.
Affiliations
  • Massachusetts Institute of Technology (US)
  • Franklin W. Olin College of Engineering (US)
  • Imperial College London (GB)
ORCID
Venue
Physical Review Letters
Publisher
American Physical Society (APS)
Published
2011-01-24
Volume
106
Issue
4
Pages
046102-046102
ISSN
  • 0031-9007 (ISSN-L)
  • 1079-7114
DOI
10.1103/physrevlett.106.046102
OpenAlex
W2053340393
Cited by
1,098
References
44
Citations by year
2026: 79 · 2025: 72 · 2024: 80 · 2023: 75 · 2022: 96 · 2021: 95 · 2020: 92 · 2019: 68 · 2018: 74 · 2017: 74 · 2016: 51 · 2015: 63 · 2014: 60 · 2013: 56 · 2012: 41
FWCI
37.77
Type
journal article
Language
en
Open access
Licence
Locations
  • Physical Review Letters (publishedVersion)
  • PubMed (publishedVersion)
  • arXiv (Cornell University) (submittedVersion)
  • DSpace@MIT (Massachusetts Institute of Technology) (submittedVersion, cc-by-nc)
  • arXiv (Cornell University)
  • APS
Funders
National Science Foundation
Topics
  • Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Electrostatics and Colloid Interactions
  • Physical Sciences › Chemical Engineering › Catalysis › Ionic liquids properties and applications
  • Physical Sciences › Engineering › Electrical and Electronic Engineering › Electrohydrodynamics and Fluid Dynamics
Keywords
ionic liquids, electric double layer, overscreening, ion size effects, ion profiles, short-range correlations, room temperature ionic liquids

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