Bipolar membranes (BPMs), typically laminated layers of anion-exchange and cation-exchange polymers, have the unique capability of splitting water at a potential near 0.83 V. Such membranes are used in electrodialysis membrane separation processes. They also have applications in water electrolyzers, CO₂ electrolysis cells, and self-humidifying fuel cells. We report here on recent developments regarding BPMs with a high interfacial area, 3D nanofiber junction.

Membranes were prepared by first creating a bipolar junction layer, by the simultaneous electrospinning of anion-exchange and cation-exchange polymers, with the addition of catalyst nanoparticles to facilitate water splitting. Solvent vapor exposure and hot-pressing closed all interfiber pores, to create a dense film of interpenetrating and interlocking nanofibers of positively and negatively charged polymers. In one fabrication method, dense films of solution cast anion and cation-exchange polymers were hot-pressed onto the opposing surfaces of the junction layer to create a tri-layer BPM. Membranes were also fabricated by electrospinning all three layers of the BPM: first spinning anion-exchange fibers, followed by dual fiber spinning with catalyst spraying, and then spinning only cation-exchange fibers. Solvent exposure and hot-pressing closed all interfiber voids.

BPMs were made with a junction layer 12-15 mm thick, where the total membrane thickness was 50-80 mm. Membranes were prepared with both hydrocarbon and fluoropolymer ionomers, e.g., sulfonated poly(ether ether ketone) or perfluorosulfonic acid as the cation-exchange polymer and either quaternized poly(phenylene oxide), AEMION^ä (an imidazolium-based polymer sold by Ionomr Innovations, Inc.), or PiperION (a poly(aryl piperidinium) from Versogen) as the anion-exchange polymer. A variety of different junction layer catalysts powders were examined, including Al(OH)₃ and graphene oxide. Membranes were evaluated in an H-cell for the collection of steady-state current-voltage data and in a flow cell for long-term constant current water splitting (electrolysis) operation, typically with an aqueous Na₂SO₄ electrolyte. The 3D junction membranes performed exceptionally well: (i) the water splitting potential was low (near the expected value of 0.83 V), (ii) the transmembrane voltage drop was small at high currents (e.g., a voltage drop of 1.1 V up to 1.1 A/cm²), and (iii) the extended bipolar reaction zone for water splitting with interlocking fibers allowed for high current density operation with no evidence of membrane degradation.

In this talk, the effect of membrane composition (the type/amount of anion and cation exchange polymers and choice of catalyst) and structure (the thickness of the layers) on short-term and long-term membrane performance will be discussed. Results will be presented for operating the bipolar membrane in water splitting and water generation modes.