Capacitance and Structure of Electric Double Layers: Comparing Brownian Dynamics and Classical Density Functional Theory

Peter Cats, Ranisha Sharishma Sitlapersad*, W.K. den Otter, Anthony R. Thornton, René van Roij

*Corresponding author for this work

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We present a study of the structure and differential capacitance of electric double layers of aqueous electrolytes. We consider electric double layer capacitors (EDLC) composed of spherical cations and anions in a dielectric continuum confined between a planar cathode and anode. The model system includes steric as well as Coulombic ion-ion and ion-electrode interactions. We compare results of computationally expensive, but “exact” , Brownian Dynamics (BD) simulations with approximate, but cheap, calculations based on classical Density Functional Theory (DFT). Excellent overall agreement is found for a large set of system parameters, including variations in concentration, ionic size- and valency-asymmetries, applied voltages and electrode separation, provided the differences between the canonical ensemble of the BD simulations and the grand-canonical ensemble of DFT are properly taken into account. In particular, a careful distinction is made between the differential capacitance at fixed number of ions and the differential capacitance at fixed ionic chemical potential. Furthermore, we derive and exploit their thermodynamic relations. In the future these relations will also be useful for comparing and contrasting experimental data with theories for supercapactitors and other systems. The quantitative agreement between simulation and theory indicates that the presented DFT is capable of accounting accurately for coupled Coulombic and packing effects. Hence it is a promising candidate to cheaply study room temperature ionic liquids at much lower dielectric constants than that of water.
Original languageEnglish
JournalJournal of Solution Chemistry
Publication statusE-pub ahead of print/First online - 12 Jul 2021


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