DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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.

Authors:
 [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
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)
OSTI Identifier:
1143029
Report Number(s):
SAND2014-3546J
Journal ID: ISSN 0021-9606; JCPSA6; 517025
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; 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

Citation Formats

Frischknecht, Amalie L., Halligan, Deaglan O., and Parks, Michael L. Electrical double layers and differential capacitance in molten salts from density functional theory. United States: N. p., 2014. Web. doi:10.1063/1.4891368.
Frischknecht, Amalie L., Halligan, Deaglan O., & Parks, Michael L. Electrical double layers and differential capacitance in molten salts from density functional theory. United States. https://doi.org/10.1063/1.4891368
Frischknecht, Amalie L., Halligan, Deaglan O., and Parks, Michael L. Tue . "Electrical double layers and differential capacitance in molten salts from density functional theory". United States. https://doi.org/10.1063/1.4891368. https://www.osti.gov/servlets/purl/1143029.
@article{osti_1143029,
title = {Electrical double layers and differential capacitance in molten salts from density functional theory},
author = {Frischknecht, Amalie L. and Halligan, Deaglan O. and Parks, Michael L.},
abstractNote = {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.},
doi = {10.1063/1.4891368},
journal = {Journal of Chemical Physics},
number = 5,
volume = 141,
place = {United States},
year = {Tue Aug 05 00:00:00 EDT 2014},
month = {Tue Aug 05 00:00:00 EDT 2014}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Grand canonical Monte Carlo investigations of electrical double layer in molten salts
journal, October 2008

  • Lamperski, Stanisław; Kłos, Jacek
  • The Journal of Chemical Physics, Vol. 129, Issue 16
  • DOI: 10.1063/1.2933434

Differential capacitance of the double layer at the electrode/ionic liquids interface
journal, January 2010

  • Lockett, Vera; Horne, Mike; Sedev, Rossen
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 39
  • DOI: 10.1039/c0cp00170h

Studies in statistical mechanics of Coulombic systems. I. Equation of state for the restricted primitive model
journal, November 1976

  • Larsen, Bjo/rn
  • The Journal of Chemical Physics, Vol. 65, Issue 9
  • DOI: 10.1063/1.433596

Numerical challenges in the application of density functional theory to biology and nanotechnology
journal, November 2002

  • Frink, L. J. D.; Salinger, A. G.; Sears, M. P.
  • Journal of Physics: Condensed Matter, Vol. 14, Issue 46
  • DOI: 10.1088/0953-8984/14/46/320

Monte Carlo study of the capacitance of the double layer in a model molten salt
journal, March 1999

  • Boda, Dezső; Henderson, Douglas; Chan, Kwong-Yu
  • The Journal of Chemical Physics, Vol. 110, Issue 11
  • DOI: 10.1063/1.478429

Ionic sizes and born repulsive parameters in the NaCl-type alkali halides—II
journal, January 1964


The fluid–solid equilibrium for a charged hard sphere model revisited
journal, July 2003

  • Vega, Carlos; Abascal, José L. F.; McBride, Carl
  • The Journal of Chemical Physics, Vol. 119, Issue 2
  • DOI: 10.1063/1.1576374

Toward Quantitative Coarse-Grained Models of Lipids with Fluids Density Functional Theory
journal, March 2012

  • Frink, Laura J. Douglas; Frischknecht, Amalie L.; Heroux, Michael A.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 4
  • DOI: 10.1021/ct200707b

Fundamental measure theory for hard-sphere mixtures revisited: the White Bear version
journal, November 2002


The capacitance of the diffuse layer of electric double layer of electrodes in molten salts
journal, February 2006


Equilibrium Thermodynamic Properties of the Mixture of Hard Spheres
journal, February 1971

  • Mansoori, G. A.; Carnahan, N. F.; Starling, K. E.
  • The Journal of Chemical Physics, Vol. 54, Issue 4
  • DOI: 10.1063/1.1675048

Molten salts near a charged surface: integral equation approximation for a model of KCl
journal, November 2001


Adsorption and the Differential Capacitance of the Electrical Double-layer at Platinum/Halide Metal Interfaces
journal, October 1965


The electrical double layer in molten salts
journal, May 1970

  • Graves, A. D.; Inman, D.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 25, Issue 3
  • DOI: 10.1016/s0022-0728(70)80098-5

Electrochemical interface between an ionic liquid and a model metallic electrode
journal, February 2007

  • Reed, Stewart K.; Lanning, Oliver J.; Madden, Paul A.
  • The Journal of Chemical Physics, Vol. 126, Issue 8
  • DOI: 10.1063/1.2464084

Density functional theory for differential capacitance of planar electric double layers in ionic liquids
journal, March 2011


Density Functional Study of the Electric Double Layer Formed by a High Density Electrolyte
journal, November 2011

  • Henderson, Douglas; Lamperski, Stanisław; Jin, Zhehui
  • The Journal of Physical Chemistry B, Vol. 115, Issue 44
  • DOI: 10.1021/jp2078105

Molecular dynamics simulations of atomically flat and nanoporous electrodes with a molten salt electrolyte
journal, January 2010

  • Vatamanu, Jenel; Borodin, Oleg; Smith, Grant D.
  • Phys. Chem. Chem. Phys., Vol. 12, Issue 1
  • DOI: 10.1039/b917592j

Phase diagrams of charged colloids from thermodynamic integration
journal, October 2009


Modeling Thermal Abuse in Transportation Batteries
journal, March 2011

  • Muller, Richard; Schultz, Peter; Cygan, Randall
  • ECS Meeting Abstracts, Vol. MA2011-01, Issue 10, p. 468-468
  • DOI: 10.1149/ma2011-01/10/468

Parallel Segregated Schur Complement Methods for Fluid Density Functional Theories
journal, January 2007

  • Heroux, Michael A.; Salinger, Andrew G.; Frink, Laura J. D.
  • SIAM Journal on Scientific Computing, Vol. 29, Issue 5
  • DOI: 10.1137/060661594

Ionic dynamics in the LiCl–KCl system at liquid state
journal, September 1982

  • Lantelme, Frédéric; Turq, Pierre
  • The Journal of Chemical Physics, Vol. 77, Issue 6
  • DOI: 10.1063/1.444192

Adsorption of organic substances and double-layer structure at the solid electrode—molten salt interface
journal, December 1981


Differential Capacitance of the Electrical Double Layer in Imidazolium-Based Ionic Liquids:  Influence of Potential, Cation Size, and Temperature
journal, April 2008

  • Lockett, Vera; Sedev, Rossen; Ralston, John
  • The Journal of Physical Chemistry C, Vol. 112, Issue 19
  • DOI: 10.1021/jp7100732

Fluid-solid equilibrium of a charged hard-sphere model
journal, September 1996

  • Vega, Carlos; Bresme, Fernando; Abascal, José L. F.
  • Physical Review E, Vol. 54, Issue 3
  • DOI: 10.1103/PhysRevE.54.2746

Electrical Double Layer Properties in Diameter Asymmetric Molten Salt Investigated by Grand Canonical Monte Carlo Method
journal, July 2010

  • Kłos, Jacek; Lamperski, Stanisław
  • The Journal of Physical Chemistry C, Vol. 114, Issue 31
  • DOI: 10.1021/jp104402u

A classical density functional theory for interfacial layering of ionic liquids
journal, January 2011

  • Wu, Jianzhong; Jiang, Tao; Jiang, De-en
  • Soft Matter, Vol. 7, Issue 23
  • DOI: 10.1039/c1sm06089a

Monte Carlo Simulation for the Double Layer Structure of an Ionic Liquid Using a Dimer Model: A Comparison with the Density Functional Theory
journal, August 2012

  • Bhuiyan, Lutful Bari; Lamperski, Stanisław; Wu, Jianzhong
  • The Journal of Physical Chemistry B, Vol. 116, Issue 34
  • DOI: 10.1021/jp304362y

Effective forces in colloidal mixtures: From depletion attraction to accumulation repulsion
journal, June 2002


Towards a microscopic theory of wetting by ionic solutions. I. Surface properties of the semi-primitive model
journal, September 2006


Structures of hard-sphere fluids from a modified fundamental-measure theory
journal, December 2002

  • Yu, Yang-Xin; Wu, Jianzhong
  • The Journal of Chemical Physics, Vol. 117, Issue 22
  • DOI: 10.1063/1.1520530

A density functional calculation of the liquid-solid phase diagram of a charged-hard-spheres model of a salt
journal, March 1987


Thermally activated (“thermal”) battery technology
journal, October 2006


A Classical Density Functional Theory of Ionic Liquids
journal, April 2011

  • Forsman, Jan; Woodward, Clifford E.; Trulsson, Martin
  • The Journal of Physical Chemistry B, Vol. 115, Issue 16
  • DOI: 10.1021/jp111747w

A Treatment of the Exclusion Volume Term in the Inhomogeneous Poisson-Boltzmann Theory for an Ion-Dipole Mixture
journal, January 2001

  • Outhwaite, C. W.; Lamperski, S.
  • Condensed Matter Physics, Vol. 4, Issue 4, p. 739
  • DOI: 10.5488/cmp.4.4.739

The electrical double layer: recent experimental and theoretical developments
journal, July 1990


Electrochemical Properties of the Double Layer of an Ionic Liquid Using a Dimer Model Electrolyte and Density Functional Theory
journal, February 2012

  • Henderson, Douglas; Wu, Jianzhong
  • The Journal of Physical Chemistry B, Vol. 116, Issue 8
  • DOI: 10.1021/jp212082k

Double-Layer in Ionic Liquids:  Paradigm Change?
journal, May 2007

  • Kornyshev, Alexei A.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 20
  • DOI: 10.1021/jp067857o

Works referencing / citing this record:

Oriented attachment growth of hundred-nanometer-size LaTaON 2 single crystals in molten salts for enhanced photoelectrochemical water splitting
journal, January 2018

  • Zhou, Junkang; Zhou, Chenguang; Shi, Zhan
  • Journal of Materials Chemistry A, Vol. 6, Issue 17
  • DOI: 10.1039/c8ta02233j

Electrical double layer in molten salts with account of soft repulsions
journal, May 2019

  • Kłos, Jacek; Lamperski, Stanisław
  • The Journal of Chemical Physics, Vol. 150, Issue 18
  • DOI: 10.1063/1.5093198

The linear relationship derived from the deposition potential of Pb–Ln alloy and atomic radius
journal, January 2018

  • Xu, Hengbin; Qu, Jiamiao; Zhang, Milin
  • New Journal of Chemistry, Vol. 42, Issue 20
  • DOI: 10.1039/c8nj03342k

Influence of dielectric layers on estimates of diffusion coefficients and concentrations of ions from impedance spectroscopy
journal, December 2019


Analysis of electrical double layer structure in molten salts
journal, February 2019

  • Kłos, Jacek; Lamperski, Stanisław
  • The Journal of Chemical Physics, Vol. 150, Issue 6
  • DOI: 10.1063/1.5082561

A multiscale model for charge inversion in electric double layers
journal, June 2018

  • Mashayak, S. Y.; Aluru, N. R.
  • The Journal of Chemical Physics, Vol. 148, Issue 21
  • DOI: 10.1063/1.5026975