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Title: 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 Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1143029
Report Number(s):
SAND2014-3546J; JCPSA6; 517025
Journal Information:
Journal of Chemical Physics, Vol. 141, Issue 5; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

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Cited By (9)

Oriented attachment growth of hundred-nanometer-size LaTaON 2 single crystals in molten salts for enhanced photoelectrochemical water splitting journal January 2018
Electrical double layer in molten salts with account of soft repulsions journal May 2019
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
The linear relationship derived from the deposition potential of Pb–Ln alloy and atomic radius journal January 2018
Influence of dielectric layers on estimates of diffusion coefficients and concentrations of ions from impedance spectroscopy journal December 2019
A systematic Monte Carlo simulation study of the primitive model electrical double layer over an extended range of concentrations, electrode charges, cation diameters and valences preprint January 2017
Analysis of electrical double layer structure in molten salts journal February 2019
Influence of dielectric layers on estimates of diffusion coefficients and concentrations of ions from impedance spectroscopy text January 2018
A multiscale model for charge inversion in electric double layers journal June 2018

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