Abstract
Electro-thermodynamics provides a consistent framework to derive continuum models for electrochemical systems. For the application to a specific experimental system, the general model must be equipped with two additional ingredients: a free energy model to calculate the chemical potentials and a kinetic model for the kinetic coefficients. Suitable free energy models for liquid electrolytes incorporating ion–solvent interaction, finite ion sizes and solvation already exist and have been validated against experimental measurements. In this work, we focus on the modeling of the mobility coefficients based on Maxwell–Stefan setting and incorporate them into the general electro-thermodynamic framework. Moreover, we discuss the impact of model parameter on conductivity, transference numbers and salt diffusion coefficient. In particular, the focus is set on the solvation of ions and incomplete dissociation of a non-dilute electrolyte.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
D. Bothe, W. Dreyer, Acta Mech. 226, 1757 (2015)
A.J. Bard, L.R. Faulkner, Electrochemical Methods: Fundamentals and Applications (Wiley, New York, 2000)
A.M. Bizeray, D.A. Howey, C.W. Monroe, J. Electrochem. Soc. 163, E223 (2016)
J.E. Dykstra, P.M. Biesheuvel, H. Bruning, A. Ter Heijne, Phys. Rev. E 90, 013302 (2014)
M.M. Doeff, L. Edman, S.E. Sloop, J. Kerr, L.C. De Jonghe, J. Power Sources 89, 227 (2000)
W. Dreyer, C. Guhlke, M. Landstorfer, Electrochem. Commun. 43, 75 (2014)
W. Dreyer, C. Guhlke, M. Landstorfer, R. Müller, Eur. J. Appl. Math. 29, 708 (2018)
S.R. de Groot, P. Mazur, Non-Equilibrium Thermodynamics (North Holland, Amsterdam, 1962)
W. Dreyer, C. Guhlke, R. Müller, Phys. Chem. Chem. Phys. 15, 7075 (2013)
W. Dreyer, C. Guhlke, R. Müller, Phys. Chem. Chem. Phys. 17, 27176 (2015)
W. Dreyer, C. Guhlke, R. Müller, Phys. Chem. Chem. Phys. 18, 24966 (2016)
W. Dreyer, C. Guhlke, R. Müller, Entropy 20, 939 (2018)
R. Datta, S.A. Vilekar, Chem. Eng. Sci. 65, 5976 (2010)
M.S. Kilic, M.Z. Bazant, A. Ajdari, Phys. Rev. E 75, 021502 (2007)
M. Landstorfer, C. Guhlke, W. Dreyer, Electrochim. Acta 201, 187 (2016)
C.W. Monroe, C. Delacourt, Electrochim. Acta 114, 649 (2013)
Y. Ma, M. Doyle, T.F. Fuller, M.M. Doeff, L.C. De Jonghe, J. Newman, J. Electrochem. Soc. 142, 1859 (1995)
C.W. Monroe, Ionic mobility and diffusivity, in Encyclopedia of Applied Electrochemistry, edited by G. Kreysa, K. Ota, R.F. Savinell (Springer, New York, 2014), pp. 1125–1130
I. Müller, Thermodynamics (Pitman Publishing, London, 1985)
J. Newman, K.E. Thomas-Alyea, Electrochemical Systems (Wiley, Hoboken, NJ, 2004)
Y.S. Oren, P.M. Biesheuvel, Phys. Rev. Appl. 9, 024034 (2018)
A.M. Ramos, Appl. Math. Model. 40, 115 (2016)
R.H. Stokes, B.J. Levien, J. Am. Chem. Soc. 68, 1852 (1946)
W.H. Smyrl, J. Newman, J. Phys. Chem. 72, 4660 (1968)
G.L. Standart, R. Taylor, R. Krishna, Chem. Eng. Commun. 3, 277 (1979)
M. Tedesco, H.V.M. Hamelers, P.M. Biesheuvel, J. Membrane Sci. 531, 172 (2017)
R. Taylor, R. Krishna, in Multicomponent Mass Transfer (John Wiley & Sons, New York, 1993), Vol. 2
C. Truesdell, J. Chem. Phys. 37, 2336 (1962)
G. Wedler, Lehrbuch der Physikalischen Chemie (Wiley-, Weinheim, 2004)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Dreyer, W., Guhlke, C. & Müller, R. The impact of solvation and dissociation on the transport parameters of liquid electrolytes: continuum modeling and numerical study. Eur. Phys. J. Spec. Top. 227, 2515–2538 (2019). https://doi.org/10.1140/epjst/e2019-800133-2
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1140/epjst/e2019-800133-2