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Electrical double layers and differential capacitance in molten salts from density functional theory

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4891368· OSTI ID:1143029
 [1];  [2];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Purdue Univ., West Lafayette, IN (United States). Department of Computer Science
+ Show Author Affiliations
Classical density functional theory (DFT) is used to calculate the structure of the electrical double layer and the differential capacitance of model molten salts. The DFT is shown to give good qualitative agreement with Monte Carlo simulations in the molten salt regime. The DFT is then applied to three common molten salts, KCl, LiCl, and LiKCl, modeled as charged hard spheres near a planar charged surface. The DFT predicts strong layering of the ions near the surface, with the oscillatory density profiles extending to larger distances for larger electrostatic interactions resulting from either lower temperature or lower dielectric constant. In conclusion, overall the differential capacitance is found to be bell-shaped, in agreement with recent theories and simulations for ionic liquids and molten salts, but contrary to the results of the classical Gouy-Chapman theory.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1143029
Report Number(s):
SAND2014--3546J; 517025
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 141; ISSN JCPSA6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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A systematic Monte Carlo simulation study of the primitive model planar electrical double layer over an extended range of concentrations, electrode charges, cation diameters and valences journal February 2018
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Influence of dielectric layers on estimates of diffusion coefficients and concentrations of ions from impedance spectroscopy journal December 2019
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