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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5131450· OSTI ID:1767720
 [1];  [2]
  1. Univ. of California, Riverside, CA (United States); OSTI
  2. Univ. of California, Riverside, CA (United States)
+ Show Author Affiliations
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.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1767720
Alternate ID(s):
OSTI ID: 1596890
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 152; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Monte Carlo methods
catalysis (heterogeneous)
charge transport
chemical thermodynamics
density functional theory
electrochemistry
electrodes
electrodes - solar
electrolytes
electrostatics
energy storage (including batteries and capacitors)
hydrogen and fuel cells
ionic liquids
materials and chemistry by design
mechanical behavior
phase transitions
solar (fuels)
synthesis (novel materials)
thermodynamic functions