Suppression of current-induced membrane discharge of bipolar membranes by regulating ion crossover transport

Abstract

Bipolar membranes (BPMs) exhibit the unique capability to regulate the operating environment of electrochemical system through the water dissociation-combination processes. However, the industrial utilization of BPMs is limited by instability and serious energy consumption. The current-induced membrane discharge (CIMD) at high-current conditions has a negative influence on the performance of anion-exchange membranes, but the underlying ion transport mechanisms in the BPMs remain unclear. Here, the CIMD-coupled Poisson-Nernst-Planck (PNP) equations are used to explore the ion transport mechanisms in the BPMs for both reverse bias and forward bias at neutral and acid-base conditions. It is demonstrated that the CIMD effect in the reverse-bias mode can be suppressed by enhancing the diffusive transport of salt counter-ions (Na+ and Cl−) into the BPMs, and that in the forward-bias mode with acid-base electrolytes can be suppressed by matching the transport rate of water counter-ions (H3O+ and OH−). Suppressing the CIMD can promote the water dissociation in the reverse-bias mode, as well as overcome the plateau of limiting current density and reduce the interfacial blockage of salt co-ions (Cl−) in the anion-exchange layer in the forward-bias mode with acid-base electrolytes. Our work highlights the importance of regulating ion crossover transport on improving the performance of BPMs.