Construction of Proton Transport Highways Induced by Polarity-Driving in Proton Exchange Membranes to Enhance the Performance of Fuel Cells.

The approach to constructing proton transport channels via direct adjustments, including hydrophilia and analytical acid concentration in hydrophilic domains, has been proved to be circumscribed when encouraging the flatter hydrophilic-hydrophobic microphase separation structures and reducing conductivity activation energy. Here, we propose a constructive solution by regulating the polarity of hydrophobic domains, which indirectly varies the aggregation and connection of hydrophilic ion clusters during membrane formation, enabling orderly self-assembly and homogeneously distributed microphase structures. Accordingly, a series of comb-shaped polymers were synthesized with diversified optimization, and more uniformly distributed ion cluster lattices were subsequently observed using high-resolution transmission electron microscopy. Simultaneously, combining with density functional theory calculations, we analyzed the mechanism of membrane degradations caused by hydroxyl radical attacks. Experimental results demonstrated that, facilitated by proper molecule polarity, beneficial changes of bond dissociation energy could extend the membrane lifetime more than the protection from side chains near ether bonds, which were deemed to reduce the probability of attacks by the steric effect. With the optimal strategy chosen among various trials, the maximum power density of direct methanol fuel cell and H2/air proton exchange membrane fuel cell was enhanced to 95 and 485 mW cm-2, respectively.