Long-term performance of hydrogen-bromine flow batteries using single-layered and multi-layered wire-electrospun SPEEK/PFSA/PVDF membranes

Abstract

Sulfonated poly (ether ketone) (SPEEK), perfluorosulfonic acid (PFSA), and polyvinylidene fluoride (PVDF) were wire-electrospun. Subsequently, multiple electrospun layers in different arrangements were hot-pressed into sustainable membranes for use in hydrogen-bromine flow batteries (HBFBs). The relationship between the electrospun layer composition and arrangement, membrane properties, and battery performance was explored. Wire-electrospinning and hot-pressing improved SPEEK and PFSA/PVDF compatibility, yielding dense membranes. Higher SPEEK contents lead to rougher morphologies, while the insulating nature of PVDF decreases the ion exchange capacity (IEC) and HBr uptake compared to commercial PFSA. The multi-layer assembly negatively impacted the membrane transport properties compared to the single-layer arrangement. Although wire-electrospinning improves the polymer dispersion and fixed charge density, SPEEK-rich regions of the blend membranes lack the high selectivity of PFSA, thus reducing the ionic conductivity. This is especially clear in the multi-layer membranes with accumulated SPEEK in the intermediate layer in the through-plane direction. Following initial property comparisons, thinner wire-electrospun SPEEK membranes were prepared with area resistance in the PFSA-comparable range. Among the wire-electrospun SPEEK/PFSA/PVDF membranes, the single-layered membrane with 8 wt% SPEEK (SPF1-8; 62 μm) displayed stable HBFB performance at 200 mA cm⁻² over 100 cycles (64 cm² active area). Based on the ex-situ measurements and cell performance results, a total of ∼10.5 wt% SPEEK is suggested as the limit for both single and multi-layered wire-electrospun membranes, combined with a maximum membrane thickness of ∼50 μm. This ensures robust HBFB performance, positioning wire-electrospun SPEEK/PFSA/PVDF membranes as a PFSA alternative in energy storage.