Abstract
We study the linear stability analysis of time-dependent electrodeposition in a charged random porous medium, whose pore surface charges can generally be of any sign, that is flanked by a pair of planar metal electrodes. Discretization of the linear stability problem results in a generalized eigenvalue problem for the dispersion relation that is solved numerically, which agrees well with the analytical approximation obtained from a boundary layer analysis valid at high wavenumbers. Under galvanostatic conditions in which an overlimiting current is applied, in the classical case of zero pore surface charges, the voltage and electric field at the cathode diverge when the bulk electrolyte concentration there vanishes at Sand's time. The same phenomenon happens for positive surface charges but at a time earlier than Sand's time. In contrast, negative surface charges allow the electrochemical system to sustain an overlimiting current via surface conduction past Sand's time, keeping the voltage and electric field bounded. Therefore, at Sand's time, negative surface charges greatly reduce the electrode surface instabilities while zero and positive surface charges magnify them. We compare theoretical predictions for overall electrode surface stabilization from the linear stability analysis with published experimental data for copper electrodeposition in cellulose nitrate membranes and demonstrate good agreement between theory and experiment. We also use the linear stability analysis as a tool to analyze how the crystal grain size changes with duty cycle during pulse electroplating.