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Title: Wettability of ultra-small pores of carbon electrodes by size-asymmetric ionic fluids

Abstract

Recently, we studied the phase behavior of ionic fluids under confinement using the classical density functional theory within the framework of the restricted primitive model. Additionally, the theoretical results indicate that narrowing the pore size may lead to a drastic reduction in the electric double layer capacitance, while increasing the surface electrical potential would improve the ionic accessibility of micropores. In this work, we extend the theoretical investigation to systems containing size-asymmetric electrolytes that may exhibit a vapor-liquid like phase transition in the bulk phase. The effects of pore size and surface electric potential on the phase diagram and microscopic structures of the confined electrolytes were studied over a broad range of parameters. We found that decreasing the pore size or increasing the surface potential could destabilize the liquid phase in micropores, and capillary evaporation could occur regardless of the size asymmetry between cations and anions. Compared to that in a symmetric ionic system, the vapor-liquid phase separation is more likely to take place as the size asymmetry becomes more pronounced. The phase transition would alter the “accessibility” of ions to micropores and lead to coexisting micropores with different surface charge densities as identified by Monte Carlo simulation.

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Univ. of California, Riverside, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1767720
Alternate Identifier(s):
OSTI ID: 1596890
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 5; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); solar (fuels); energy storage (including batteries and capacitors); hydrogen and fuel cells; electrodes - solar; mechanical behavior; charge transport; materials and chemistry by design; synthesis (novel materials); ionic liquids; chemical thermodynamics; thermodynamic functions; electrochemistry; electrodes; electrostatics; density functional theory; phase transitions; electrolytes; Monte Carlo methods

Citation Formats

Liu, Kun, and Wu, Jianzhong. Wettability of ultra-small pores of carbon electrodes by size-asymmetric ionic fluids. United States: N. p., 2020. Web. doi:10.1063/1.5131450.
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Liu, Kun, & Wu, Jianzhong. Wettability of ultra-small pores of carbon electrodes by size-asymmetric ionic fluids. United States. https://doi.org/10.1063/1.5131450
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Liu, Kun, and Wu, Jianzhong. Mon . "Wettability of ultra-small pores of carbon electrodes by size-asymmetric ionic fluids". United States. https://doi.org/10.1063/1.5131450. https://www.osti.gov/servlets/purl/1767720.
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@article{osti_1767720,
title = {Wettability of ultra-small pores of carbon electrodes by size-asymmetric ionic fluids},
author = {Liu, Kun and Wu, Jianzhong},
abstractNote = {Recently, we studied the phase behavior of ionic fluids under confinement using the classical density functional theory within the framework of the restricted primitive model. Additionally, the theoretical results indicate that narrowing the pore size may lead to a drastic reduction in the electric double layer capacitance, while increasing the surface electrical potential would improve the ionic accessibility of micropores. In this work, we extend the theoretical investigation to systems containing size-asymmetric electrolytes that may exhibit a vapor-liquid like phase transition in the bulk phase. The effects of pore size and surface electric potential on the phase diagram and microscopic structures of the confined electrolytes were studied over a broad range of parameters. We found that decreasing the pore size or increasing the surface potential could destabilize the liquid phase in micropores, and capillary evaporation could occur regardless of the size asymmetry between cations and anions. Compared to that in a symmetric ionic system, the vapor-liquid phase separation is more likely to take place as the size asymmetry becomes more pronounced. The phase transition would alter the “accessibility” of ions to micropores and lead to coexisting micropores with different surface charge densities as identified by Monte Carlo simulation.},
doi = {10.1063/1.5131450},
journal = {Journal of Chemical Physics},
number = 5,
volume = 152,
place = {United States},
year = {Mon Feb 03 00:00:00 EST 2020},
month = {Mon Feb 03 00:00:00 EST 2020}
}
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https://doi.org/10.1063/1.5131450
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