(388i) Kinetic Charge Inversion in Ionic-Liquid Electric Double Layers | AIChE

(388i) Kinetic Charge Inversion in Ionic-Liquid Electric Double Layers


Wu, J. - Presenter, University of California at Riverside

The charging kinetics of electric double layers (EDLs) has a pivotal role in the performance of a wide variety of nanostructured devices. Despite the prevalent use of ionic liquids as the electrolyte, relatively little is known on the charging behavior from a microscopic perspective. Here we study the charging kinetics of ionic-liquid EDLs using a classical time-dependent density functional theory that captures the molecular excluded volume effects and electrostatic correlations. By examining variations of the ionic density profiles and the charging density in response to an electrode voltage, we find that at certain conditions the electrode charge shows a rapid surge in its initial response, rises quickly to the maximum, and then slowly decays towards equilibrium. The electrode charge and voltage may have opposite signs when the cell width is commensurate with the layer-by-layer ionic distributions. This unusual charging behavior can be explained in terms of the oscillatory structure of ionic liquids near the electrodes.