A new type of bipolar membrane (BPM) with a high interfacial area 3D water splitting junction has been fabricated and tested. BPMs were made by single and dual fiber electrospinning, followed by dimethylformamide vapor exposure and hot-pressing, with sulfonated poly(ether ether ketone) as the cation-exchange polymer and quaternized poly(phenylene oxide) as the anion-exchange material. Al(OH)₃ nanoparticles were added to the junction to facilitate water splitting. The resultant trilayer membrane had an inner bipolar junction (interpenetrating anion-exchange and cation-exchange polymer nanofibers) ∼10 μm in thickness with dense/neat ionomer outer layers. The extended bipolar reaction zone enabled water splitting at ultra-high current densities (up to 1.1 A cm⁻²) with no evidence of membrane dehydration or blistering, which is common for a planar junction BPM. The novel electrospun membrane morphology offers significant benefits for electrodialysis separations, electrochemical hydrogen generation, and self-humidifying fuel cells, where high operating current densities and membrane stability are required.

The lamination of a cation exchange layer (CEL) and an anion exchange layer (AEL) to form a hybrid bipolar membrane (BPM) can have several unique advantages over conventional monopolar ion exchange membranes in (photo-)electrolysis. Upon application of a reverse bias, the ordinarily slow water dissociation reaction at the AEL/CEL junction of the BPM is dramatically accelerated by the large electric field at the interface and by the presence of catalyst in the junction. Using electrochemical impedance spectroscopy (EIS), we have found a counterbalanced role of the electric field and the junction catalyst in accelerating water dissociation in a BPM. Experimental BPMs were prepared from a crosslinked AEL and a Nafion CEL, with a graphite oxide (GO) catalyst deposited at the junction using layer-by-layer (LBL) assembly. BPMs with an interfacial catalyst layer were found to have smaller electric fields at the interface compared to samples with no added catalyst. A comprehensive numerical simulation model showed that the damping of the electric field in BPMs with a catalyst layer is a result of a higher water dissociation product (H⁺/OH⁻) flux, which neutralizes the net charge density of the CEL and AEL. This conclusion is further substantiated by EIS studies of a high-performance 3D junction BPM that shows a low electric field due to the facile catalytic generation and transport of H⁺ and OH⁻. Numerical modeling of these effects in the BPM provides a prescription for designing membranes that function at lower overpotential. The potential drop across the synthetic BPM was lower than that of a commercial BPM by more than 200 mV at >100 mA cm⁻² reverse bias current density, with the two membranes having similar long-term stability.

A fuel cell is an electrochemical device that converts the chemical energy of a fuel and oxidant into electricity. Cation-exchange and anion-exchange membranes play an important role in hydrogen fed proton-exchange membrane (PEM) and anion-exchange membrane (AEM) fuel cells, respectively. Over the past 10 years, there has been growing interest in using nanofiber electrospinning to fabricate fuel cell PEMs and AEMs with improved properties, e.g., a high ion conductivity with low in-plane water swelling and good mechanical strength under wet and dry conditions. Electrospinning is used to create either reinforcing scaffolds that can be pore-filled with an ionomer or precursor mats of interwoven ionomer and reinforcing polymers, which after suitable processing (densification) form a functional membrane. In this review paper, methods of nanofiber composite PEMs and AEMs fabrication are reviewed and the properties of these membranes are discussed and contrasted with the properties of fuel cell membranes prepared using conventional methods. The information and discussions contained herein are intended to provide inspiration for the design of high-performance next-generation fuel cell ion-exchange membranes.

The regenerative H₂/Br₂-HBr fuel cell, utilizing an oxidant solution of Br₂ in aqueous HBr, shows a number of benefits for grid-scale electricity storage. The membrane-electrode assembly, a key component of a fuel cell, contains a proton-conducting membrane, typically based on the perfluorosulfonic acid (PFSA) ionomer. Unfortunately, the high cost of PFSA membranes and their relatively high bromine crossover are serious drawbacks. Nanofiber composite membranes can overcome these limitations. In this work, composite membranes were prepared from electrospun dual-fiber mats containing Nafion^® PFSA ionomer for facile proton transport and an uncharged polymer, polyphenylsulfone (PPSU), for mechanical reinforcement, and swelling control. After electrospinning, Nafion/PPSU mats were converted into composite membranes by softening the PPSU fibers, through exposure to chloroform vapor, thus filling the voids between ionomer nanofibers. It was demonstrated that the relative membrane selectivity, referenced to Nafion^® 115, increased with increasing PPSU content, e.g., a selectivity of 11 at 25 vol% of Nafion fibers. H₂-Br₂ fuel cell power output with a 65 μm thick membrane containing 55 vol% Nafion fibers was somewhat better than that of a 150 μm Nafion^® 115 reference, but its cost advantage due to a four-fold decrease in PFSA content and a lower bromine species crossover make it an attractive candidate for use in H₂/Br₂-HBr systems.