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Title: Hysteretic order-disorder transitions of ionic liquid double layer structure on graphite

Abstract

Understanding the electrical double layer (EDL) structure at the solid/liquid interface is critical towards realizing the full potential of electrochemical applications using ionic liquids. Here, the out-of-plane and in-plane EDL structures of PYR14-TFSI on graphite (HOPG) have been studied by in-situ electrochemical atomic force microscopy (AFM) and molecular dynamics (MD) simulation. AFM results revealed that the first adsorbed ion layer on HOPG consists of both disordered and ordered lateral domains. It has been found that the neighboring molecules in the x-y plane form intricate ordered lateral structures on length scale of hundreds of nanometers, and the out-of-plane EDL structure is independent of the in-plane structure. MD simulations under zero polarization showed that in the first adsorbed layer, cations have one preferred orientation while anions have two preferred orientations in relation to the HOPG surface, which might be the origin of the complex lateral ordering. When polarizing the surface, a hysteretic order-disorder transition of the lateral ordering in the first adsorbed layer can be observed by in-situ AFM, and the ordered domains disappear for high positive or negative voltages. Finally, comparison with bias-dependent MD reveals that the existence of a bimodal anion distribution in the first absorbed layer can be linkedmore » to the observed transitions giving new insights into the origin of the structural domains, which can help understand unusual charge and discharge kinetics observed in similar systems.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [2];  [2];  [3]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Huazhong University of Science and Technology (HUST), Wuhan (China)
  3. Univ. of Tennessee, Knoxville, TN (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1528714
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 60; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Tsai, Wan-Yu, Come, Jeremy E., Zhao, Wei, Wang, Runxi, Feng, Guang, Prasad Thapaliya, Bishnu, Dai, Sheng, Collins, Liam F., and Balke, Nina. Hysteretic order-disorder transitions of ionic liquid double layer structure on graphite. United States: N. p., 2019. Web. doi:10.1016/j.nanoen.2019.04.022.
Tsai, Wan-Yu, Come, Jeremy E., Zhao, Wei, Wang, Runxi, Feng, Guang, Prasad Thapaliya, Bishnu, Dai, Sheng, Collins, Liam F., & Balke, Nina. Hysteretic order-disorder transitions of ionic liquid double layer structure on graphite. United States. https://doi.org/10.1016/j.nanoen.2019.04.022
Tsai, Wan-Yu, Come, Jeremy E., Zhao, Wei, Wang, Runxi, Feng, Guang, Prasad Thapaliya, Bishnu, Dai, Sheng, Collins, Liam F., and Balke, Nina. 2019. "Hysteretic order-disorder transitions of ionic liquid double layer structure on graphite". United States. https://doi.org/10.1016/j.nanoen.2019.04.022. https://www.osti.gov/servlets/purl/1528714.
@article{osti_1528714,
title = {Hysteretic order-disorder transitions of ionic liquid double layer structure on graphite},
author = {Tsai, Wan-Yu and Come, Jeremy E. and Zhao, Wei and Wang, Runxi and Feng, Guang and Prasad Thapaliya, Bishnu and Dai, Sheng and Collins, Liam F. and Balke, Nina},
abstractNote = {Understanding the electrical double layer (EDL) structure at the solid/liquid interface is critical towards realizing the full potential of electrochemical applications using ionic liquids. Here, the out-of-plane and in-plane EDL structures of PYR14-TFSI on graphite (HOPG) have been studied by in-situ electrochemical atomic force microscopy (AFM) and molecular dynamics (MD) simulation. AFM results revealed that the first adsorbed ion layer on HOPG consists of both disordered and ordered lateral domains. It has been found that the neighboring molecules in the x-y plane form intricate ordered lateral structures on length scale of hundreds of nanometers, and the out-of-plane EDL structure is independent of the in-plane structure. MD simulations under zero polarization showed that in the first adsorbed layer, cations have one preferred orientation while anions have two preferred orientations in relation to the HOPG surface, which might be the origin of the complex lateral ordering. When polarizing the surface, a hysteretic order-disorder transition of the lateral ordering in the first adsorbed layer can be observed by in-situ AFM, and the ordered domains disappear for high positive or negative voltages. Finally, comparison with bias-dependent MD reveals that the existence of a bimodal anion distribution in the first absorbed layer can be linked to the observed transitions giving new insights into the origin of the structural domains, which can help understand unusual charge and discharge kinetics observed in similar systems.},
doi = {10.1016/j.nanoen.2019.04.022},
url = {https://www.osti.gov/biblio/1528714}, journal = {Nano Energy},
issn = {2211-2855},
number = C,
volume = 60,
place = {United States},
year = {Tue Apr 09 00:00:00 EDT 2019},
month = {Tue Apr 09 00:00:00 EDT 2019}
}

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