From electroconvective vortices to current hot spots on ion selective membranes subject to concentration polarization

Electroconvective instabilities near ion-selective surfaces have been shown to greatly enhance ion transport and play a significant role in a wide range of applications in electrochemistry. When the driving voltage exceeds a threshold, electroconvection becomes chaotic and leads to intermittent spikes of current density on the ion-selective surface. We present an investigation of this phenomenon by considering a canonical setting consisting of a symmetric binary electrolyte next to a flat, ion-selective membrane subject to an external driving voltage. By tracking individual rolls of vortices, we reveal the common mechanism under which the three-way coupled fluid dynamics, ion transport, and electrostatic effects lead to advective displacement of ion concentration field, sustained vortices and vortex migration, and current hot spots on the membrane.