Electrical double layer in ionic liquids: structural transitions from multilayer to monolayer structure at the interface

K. Kirchner, T. Kirchner, V. Ivaništšev, M.V. Fedorov

Research output: Contribution to journalConference Contribution

82 Citations (Scopus)

Abstract

We have studied structural transitions in the electrical double layer of ionic liquids by molecular dynamics simulations. A model coarse grained room temperature ionic liquid (RTIL) with asymmetric sized ions confined between two oppositely charged walls has been used. The simulations have been performed at different temperatures and electrode charge density values. We found that for the studied charge densities the electrical double layer has a multilayered structure with multiple alternating layers of counter- and co-ions at the electrode-RTIL interface; however, at certain charge densities the alternating multilayer structure of the electrical double layer undergoes a structural transition to a surface-frozen monolayer of densely packed counter-ions (Moiré-like structure). At this point the dense ordered monolayer of counter-ions close to the electrode surface coexists with apparently non-structured RTIL further from the electrode. These findings might bring possible explanations to experimental observations of formation of Moiré-like structures in ionic liquids at electrified interfaces. Moreover, we report the formation of herring-bone interfacial structures at high surface charge densities, that appear as a result of superposition of two ordered monolayers of RTIL ions at the electrode-RTIL interface. Similar structures were observed experimentally; however, to the best of our knowledge they have not been modelled by simulations. We discuss the dependence of the electrical double layer structure in RTILs on the ion size and the surface charge density at the electrodes.
Original languageEnglish
Pages (from-to)762-771
Number of pages10
JournalElectrochimica Acta
Volume110
DOIs
Publication statusPublished - 1 Jan 2013
Event63rd Annual Meeting of the International Society of Electrochemistry - Prague, Czech Republic
Duration: 19 Aug 201224 Aug 2012

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Ionic Liquids
Ionic liquids
Monolayers
Multilayers
Charge density
Electrodes
liquids
electrodes
Ions
room temperature
ions
counters
Radiation counters
Surface charge
Temperature
simulation
laminates
bones
Molecular dynamics
Bone

Keywords

  • surface-frozen Moiré-like structure
  • electric double layer
  • ionic liquids
  • molecular dynamics simulations
  • structural transition

Cite this

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title = "Electrical double layer in ionic liquids: structural transitions from multilayer to monolayer structure at the interface",
abstract = "We have studied structural transitions in the electrical double layer of ionic liquids by molecular dynamics simulations. A model coarse grained room temperature ionic liquid (RTIL) with asymmetric sized ions confined between two oppositely charged walls has been used. The simulations have been performed at different temperatures and electrode charge density values. We found that for the studied charge densities the electrical double layer has a multilayered structure with multiple alternating layers of counter- and co-ions at the electrode-RTIL interface; however, at certain charge densities the alternating multilayer structure of the electrical double layer undergoes a structural transition to a surface-frozen monolayer of densely packed counter-ions (Moir{\'e}-like structure). At this point the dense ordered monolayer of counter-ions close to the electrode surface coexists with apparently non-structured RTIL further from the electrode. These findings might bring possible explanations to experimental observations of formation of Moir{\'e}-like structures in ionic liquids at electrified interfaces. Moreover, we report the formation of herring-bone interfacial structures at high surface charge densities, that appear as a result of superposition of two ordered monolayers of RTIL ions at the electrode-RTIL interface. Similar structures were observed experimentally; however, to the best of our knowledge they have not been modelled by simulations. We discuss the dependence of the electrical double layer structure in RTILs on the ion size and the surface charge density at the electrodes.",
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author = "K. Kirchner and T. Kirchner and V. Ivaništšev and M.V. Fedorov",
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Electrical double layer in ionic liquids : structural transitions from multilayer to monolayer structure at the interface. / Kirchner, K.; Kirchner, T.; Ivaništšev, V.; Fedorov, M.V.

In: Electrochimica Acta, Vol. 110, 01.01.2013, p. 762-771.

Research output: Contribution to journalConference Contribution

TY - JOUR

T1 - Electrical double layer in ionic liquids

T2 - structural transitions from multilayer to monolayer structure at the interface

AU - Kirchner, K.

AU - Kirchner, T.

AU - Ivaništšev, V.

AU - Fedorov, M.V.

PY - 2013/1/1

Y1 - 2013/1/1

N2 - We have studied structural transitions in the electrical double layer of ionic liquids by molecular dynamics simulations. A model coarse grained room temperature ionic liquid (RTIL) with asymmetric sized ions confined between two oppositely charged walls has been used. The simulations have been performed at different temperatures and electrode charge density values. We found that for the studied charge densities the electrical double layer has a multilayered structure with multiple alternating layers of counter- and co-ions at the electrode-RTIL interface; however, at certain charge densities the alternating multilayer structure of the electrical double layer undergoes a structural transition to a surface-frozen monolayer of densely packed counter-ions (Moiré-like structure). At this point the dense ordered monolayer of counter-ions close to the electrode surface coexists with apparently non-structured RTIL further from the electrode. These findings might bring possible explanations to experimental observations of formation of Moiré-like structures in ionic liquids at electrified interfaces. Moreover, we report the formation of herring-bone interfacial structures at high surface charge densities, that appear as a result of superposition of two ordered monolayers of RTIL ions at the electrode-RTIL interface. Similar structures were observed experimentally; however, to the best of our knowledge they have not been modelled by simulations. We discuss the dependence of the electrical double layer structure in RTILs on the ion size and the surface charge density at the electrodes.

AB - We have studied structural transitions in the electrical double layer of ionic liquids by molecular dynamics simulations. A model coarse grained room temperature ionic liquid (RTIL) with asymmetric sized ions confined between two oppositely charged walls has been used. The simulations have been performed at different temperatures and electrode charge density values. We found that for the studied charge densities the electrical double layer has a multilayered structure with multiple alternating layers of counter- and co-ions at the electrode-RTIL interface; however, at certain charge densities the alternating multilayer structure of the electrical double layer undergoes a structural transition to a surface-frozen monolayer of densely packed counter-ions (Moiré-like structure). At this point the dense ordered monolayer of counter-ions close to the electrode surface coexists with apparently non-structured RTIL further from the electrode. These findings might bring possible explanations to experimental observations of formation of Moiré-like structures in ionic liquids at electrified interfaces. Moreover, we report the formation of herring-bone interfacial structures at high surface charge densities, that appear as a result of superposition of two ordered monolayers of RTIL ions at the electrode-RTIL interface. Similar structures were observed experimentally; however, to the best of our knowledge they have not been modelled by simulations. We discuss the dependence of the electrical double layer structure in RTILs on the ion size and the surface charge density at the electrodes.

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KW - molecular dynamics simulations

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