Half-Cell Ion Concentration Polarization on Nafion-Coated Electrode

On ion-selective membranes, cation/anion-selective transport under electric field initiates ion concentration polarization (ICP); ion concentration increases at one side of the membrane (ion enrichment), whereas it decreases at the other side (ion depletion). This polarization always occurs as the pair of ion enrichment and ion depletion. Departing from such pair generation, we demonstrate that only half of ICP (either ion enrichment or ion depletion) can be solitary on a Nafion-coated electrode. Current-voltage-time responses and conductance measurement capture this half-cell ICP with qualitative in situ pH/ion concentration visualization. In this half-cell, ion depletion hinders an ion flux, whereas ion enrichment facilitates the flux, so a diode-like current rectification is observed even in high-voltage regime (<±200 V) with a rectification factor up to 500. The results in this work give us deeper understanding about ICP on the electrodes and also open the possibility to use half-cell ICP as a high-voltage ionic diode and related sensing/energy applications.