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Title: Interfacial ionic 'liquids': connecting static and dynamic structures

Abstract

It is well known that room temperature ionic liquids (RTILs) often adopt a charge-separated layered structure, i.e. with alternating cation- and anion-rich layers, at electrified interfaces. However, the dynamic response of the layered structure to temporal variations in applied potential is not well understood. For this research, we used in situ, real-time x-ray reflectivity to study the potential-dependent electric double layer (EDL) structure of an imidazolium-based RTIL on charged epitaxial graphene during potential cycling as a function of temperature. The results suggest that the graphene–RTIL interfacial structure is bistable in which the EDL structure at any intermediate potential can be described by the combination of two extreme-potential structures whose proportions vary depending on the polarity and magnitude of the applied potential. This picture is supported by the EDL structures obtained by fully atomistic molecular dynamics simulations at various static potentials. Lastly, the potential-driven transition between the two structures is characterized by an increasing width but with an approximately fixed hysteresis magnitude as a function of temperature. The results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (~0.15 eV).

Authors:
 [1];  [1];  [2];  [1];  [2];  [2];  [3];  [3];  [4];  [4];  [1]
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  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Vanderbilt Univ., Nashville, TN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Drexel Univ., Philadelphia, PA (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1286835
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physics. Condensed Matter
Additional Journal Information:
Journal Volume: 27; Journal Issue: 3; Journal ID: ISSN 0953-8984
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Uysal, Ahmet, Zhou, Hua, Feng, Guang, Lee, Sang Soo, Li, Song, Cummings, Peter T., Fulvio, Pasquale F., Dai, Sheng, McDonough, John K., Gogotsi, Yury G., and Fenter, Paul. Interfacial ionic 'liquids': connecting static and dynamic structures. United States: N. p., 2014. Web. doi:10.1088/0953-8984/27/3/032101.
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Uysal, Ahmet, Zhou, Hua, Feng, Guang, Lee, Sang Soo, Li, Song, Cummings, Peter T., Fulvio, Pasquale F., Dai, Sheng, McDonough, John K., Gogotsi, Yury G., & Fenter, Paul. Interfacial ionic 'liquids': connecting static and dynamic structures. United States. https://doi.org/10.1088/0953-8984/27/3/032101
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Uysal, Ahmet, Zhou, Hua, Feng, Guang, Lee, Sang Soo, Li, Song, Cummings, Peter T., Fulvio, Pasquale F., Dai, Sheng, McDonough, John K., Gogotsi, Yury G., and Fenter, Paul. Fri . "Interfacial ionic 'liquids': connecting static and dynamic structures". United States. https://doi.org/10.1088/0953-8984/27/3/032101. https://www.osti.gov/servlets/purl/1286835.
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@article{osti_1286835,
title = {Interfacial ionic 'liquids': connecting static and dynamic structures},
author = {Uysal, Ahmet and Zhou, Hua and Feng, Guang and Lee, Sang Soo and Li, Song and Cummings, Peter T. and Fulvio, Pasquale F. and Dai, Sheng and McDonough, John K. and Gogotsi, Yury G. and Fenter, Paul},
abstractNote = {It is well known that room temperature ionic liquids (RTILs) often adopt a charge-separated layered structure, i.e. with alternating cation- and anion-rich layers, at electrified interfaces. However, the dynamic response of the layered structure to temporal variations in applied potential is not well understood. For this research, we used in situ, real-time x-ray reflectivity to study the potential-dependent electric double layer (EDL) structure of an imidazolium-based RTIL on charged epitaxial graphene during potential cycling as a function of temperature. The results suggest that the graphene–RTIL interfacial structure is bistable in which the EDL structure at any intermediate potential can be described by the combination of two extreme-potential structures whose proportions vary depending on the polarity and magnitude of the applied potential. This picture is supported by the EDL structures obtained by fully atomistic molecular dynamics simulations at various static potentials. Lastly, the potential-driven transition between the two structures is characterized by an increasing width but with an approximately fixed hysteresis magnitude as a function of temperature. The results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (~0.15 eV).},
doi = {10.1088/0953-8984/27/3/032101},
journal = {Journal of Physics. Condensed Matter},
number = 3,
volume = 27,
place = {United States},
year = {Fri Dec 05 00:00:00 EST 2014},
month = {Fri Dec 05 00:00:00 EST 2014}
}
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https://doi.org/10.1088/0953-8984/27/3/032101
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