Characterization of chaotic electroconvection near flat inert electrodes under oscillatory voltages

Abstract

The onset of electroconvective instability in an aqueous binary electrolyte under external oscillatory electric fields at a single constant frequency is investigated in a 2D parallel flat electrode setup. Direct numerical simulations (DNS) of the Poisson-Nernst-Planck equations coupled with the Navier-Stokes equations at a low Reynolds number are carried out. Previous studies show that direct current (DC) electric field can create electroconvection near ion-selecting membranes in microfluidic devices. In this study, we show that electroconvection can be generated near flat inert electrodes when the applied electric field is oscillatory in time. A range of applied voltage, the oscillation frequency and the ratio of ionic diffusivities is examined to characterize the regime in which electroconvection takes place. Similar to electroconvection under DC voltages, AC electroconvection occurs at sufficiently high applied voltages in units of thermal volts and is characterized by transverse instabilities, physically manifested by an array of counter-rotating vortices near the electrode surfaces. The oscillating external electric field periodically generate and destroy such unsteady vortical structures. As the oscillation frequency is reduced to O(10-1) of the intrinsic resistor-capacitor (RC) frequency of electrolyte, electroconvective instability is considerably amplified. This is accompanied by severe depletion of ionic species outside the thin electric double layer and by vigorous convective transport involving a wide range of scales including those comparable to the distance L between the parallel electrodes. The underlying mechanisms are distinctly nonlinear and multi-dimensional. However, at higher frequencies of order of the RC frequency, the electrolyte response becomes linear, and the present DNS prediction closely resembles those explained by 1D asymptotic studies. Electroconvective instability supports increased electric current across the system. Increasing anion diffusivity results in stronger amplification of electroconvection over all oscillation frequencies examined in this study. Such asymmetry in ionic diffusivity, however, does not yield consistent changes in statistics and energy spectrum at all wall-normal locations and frequencies, implying more complex dynamics and different scaling for electrolytes with unequal diffusivities. Electric current is substantially amplified beyond the ohmic current at high oscillation frequencies. Also, it is found that anion diffusivity higher than cation has stronger impact on smaller-scale motions (≲ 0.1L).