Origin of Limiting and Overlimiting Currents in Bipolar Membranes

[Image: see text] Bipolar membranes (BPMs), a special class of ion exchange membranes with the unique ability to electrochemically induce either water dissociation or recombination, are of growing interest for environmental applications including eliminating chemical dosage for pH adjustment, resource recovery, valorization of brines, and carbon capture. However, ion transport within BPMs, and particularly at its junction, has remained poorly understood. This work aims to theoretically and experimentally investigate ion transport in BPMs under both reverse and forward bias operation modes, taking into account the production or recombination of H(+) and OH(–), as well as the transport of salt ions (e.g., Na(+), Cl(–)) inside the membrane. We adopt a model based on the Nernst–Planck theory, that requires only three input parameters—membrane thickness, its charge density, and pK of proton adsorption—to predict the concentration profiles of four ions (H(+), OH(–), Na(+), and Cl(–)) inside the membrane and the resulting current–voltage curve. The model can predict most of the experimental results measured with a commercial BPM, including the observation of limiting and overlimiting currents, which emerge due to particular concentration profiles that develop inside the BPM. This work provides new insights into the physical phenomena in BPMs and helps identify optimal operating conditions for future environmental applications.