Novel pore-filling membrane based on block sulfonated poly (ether sulphone) with enhanced proton conductivity and methanol resistance for direct methanol fuel cells

Abstract The problem remains unsolved in DMFCs applications that the increase in proton conductivity is usually caused the permeation of methanol. Herein, a novel kind of pore-filling membrane is investigated to meet this challenge. The porous substrate is fabricated from block poly (ether sulphone) with low degree of sulfonation, which form well-developed conductive channels owing to an aggregation of sulfonic acid groups, ensuring low methonal crossover and swelling ratio. The pore structures are achieved by a solution casting method which introduces alpha-cyclodextrin as the porogen. The resulting porous substrate possesses homogeneous opening pore structures. Then, the filling electrolyte, an organic-soluble tetrabutylammonium 4-vinylbenzene sulfonate, is used to fill the substrate and form a crosslinked network inside the pores to ensure high proton conductivity. The pore-filling membrane with block polymers shows higher proton conductivity (0.083 S cm −1 at 80 °C) than that prepared by random polymers (0.072 S cm −1 at 80 °C). Compared with Nafion 117, the composite membrane exhibits higher dimensional stability (6.6%) and methanol resistance (4.0 × 10 −7  cm 2  s −1 ). Furthermore, the pore-filling membrane outperforms Nafion 117 with an open circuit voltage of 0.61 V as well as a maximum power density of 46.8 mW/cm 2 under 10 M methanol condition.