Ion-specific phenomena limit energy recovery in forward-biased bipolar membranes

The ability for bipolar membranes (BPMs) to interconvert voltage and pH makes them attractive materials for use in energy conversion and storage. Reverse-biased BPMs, which use electrical voltage to dissociate water into acid and base, have become increasingly well studied. However, forward-biased BPMs (FB-BPMs), in which voltage is extracted from pH gradients through recombination, require further study. Here physics-based modeling elucidates how the complex coupling of transport and kinetics dictates the performance of FB-BPMs in electrochemical devices. Simulations reveal that the open-circuit potential of FB-BPMs is dictated by the balance of ion recombination and crossover, where recombination of buffering counter-ions attenuates the open-circuit potential. Counter-ion mass-transport limitations and uptake of ionic impurities limit achievable current densities by reducing the applied pH gradient or the available fixed-charge sites that mediate recombination. The model highlights the importance of selective ion management in mitigating energy losses and provides insight into the rational material design of FB-BPMs for energy applications. Forward-biased bipolar membranes (FB-BPMs), which recover potential from pH gradients through ion–ion recombination, show promise for application in sustainable devices. The authors use physics-based modeling to elucidate how ion-specific phenomena dictate performance, reveal how selective ion management can mitigate energy losses and provide insights into the rational design of next-generation FB-BPMs.