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Differential capacitance of ionic liquid interface with graphite: the story of two double layers

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Abstract

We combine electronic density functional theory for the screening properties of graphite with a mean-field theory of the double layer in ionic liquids to reveal what underpins the morphology of the voltage dependence of electrical capacitance of a flat graphite/ionic liquids interface.

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Notes

  1. There are currently hot discussions about the degree of ionic dissociation in RTILs., including the extreme point of view that most of the ions in RTILs are bound in ion pairs, giving rise to a dielectric constant of about 10, with only a small number of virtually free moving ions, bringing the properties of RTILs close to those of dilute ionic solutions [14]. However, this point of view is at odds with a number of experimental facts and computer simulations[15]. Therefore, before further tests of this hypothesis have been performed, we will not explore the opportunity of adopting much lower effective concentrations of free ions, which would bring \(C_{0}\) to much more reasonable, smaller values. Small values of effective concentrations of ions, would cause small values of \(\gamma \), which would make all the capacitance curves U-shaped; moreover the total capacitance of the interface would be entirely dominated by the double layer capacitance in RTILs, and there would be no effect of the substrate.

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Acknowledgments

AAK is thankful to EPSRC for grant EP/H004319/1. WS and NBL acknowledge support from the DFG under FOR 1376, and thank the Baden- Württemberg grid for a generous grant of computer time.

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Authors and Affiliations

  1. Section of Chemical Physics, Department of Chemistry, Faculty of Natural Sciences, Imperial College, London, UK

    A. A. Kornyshev

  2. Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU) and Donostia International Physics Center (DIPC), P.K. 1072, Donostia, Spain

    N. B. Luque

  3. Institute of Theoretical Chemistry, Ulm University, 89069, Ulm, Germany

    W. Schmickler

Authors
  1. A. A. Kornyshev
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  2. N. B. Luque
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  3. W. Schmickler
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Correspondence to A. A. Kornyshev or W. Schmickler.

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Kornyshev, A.A., Luque, N.B. & Schmickler, W. Differential capacitance of ionic liquid interface with graphite: the story of two double layers. J Solid State Electrochem 18, 1345–1349 (2014). https://doi.org/10.1007/s10008-013-2316-8

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  • DOI: https://doi.org/10.1007/s10008-013-2316-8

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