Branched Poly(arylene ether ketone sulfone)s with Ultradensely Sulfonated Branched Centers for Proton Exchange Membranes: Effect of the Positions of the Sulfonic Acid Groups

Branched sulfonated polymers present considerable potential for application as proton exchange membranes, yet investigation of branched polymers containing sulfonated branched centers remains to be advanced. Herein, we report a series of polymers with ultradensely sulfonated branched centers, namely, B-x-SPAEKS, where x represents the degree of branching. In comparison with the analogous polymers bearing sulfonated branched arms, B-x-SPAEKS showed a reduced water affinity, resulting in less swelling and lower proton conductivity. The water uptake, swelling ratio (in-plane), and proton conductivity of B-10-SPAEKS at 80 °C were 52.2%, 57.7%, and 23.6% lower than their counterparts, respectively. However, further analysis revealed that B-x-SPAEKS featured significantly better proton conduction under the same water content due to the formation of larger hydrophilic clusters (∼10 nm) that promoted efficient proton transportation. B-12.5-SPAEKS exhibited a proton conductivity of 138.8 mS cm-1 and a swelling ratio (in-plane) of only 11.6% at 80 °C, both of which were superior to Nafion 117. In addition, a decent single-cell performance of B-12.5-SPAEKS was also achieved. Consequently, the decoration of sulfonic acid groups on the branched centers represents a very promising strategy, enabling outstanding proton conductivity and dimensional stability simultaneously even with low water content.