High-performance proton exchange membrane derived from N-heterocycle poly(aryl ether sulfone)s with ether-free hydrophilic blocks and exhibiting good stability and proton-conducting performance

Abstract

The trade-off issue between proton conduction properties and stability is a constraint on the commercial application of non-fluorinated proton exchange membranes for fuel cells. To alleviate the issue, the multi-block N-heterocycle poly(aryl ether sulfone)s with ether-free hydrophilic blocks (b-SPDPESs), which is composited by diphenyl sulfone moieties and biphthalazindione structures with dense pendant benzenesulfonic groups, are developed to prepare high-performance membranes. The self-assembly effect of block copolymers not only improves the membrane stability but also constructs regular proton conduction channels. Moreover, the conduction channel consists of hydrophilic blocks without ether bonds, which effectively improves the tolerance of the membrane to radicals. The hydrogen-bond network between sulfonic groups and N-heterocycles in the channel improves the proton conduction efficiency, inhibits the swelling of the membrane, and improves the stability of the membrane. As a result, the swelling degree of b-SPDPESs membrane is only 15.8 %, the proton conductivity is as high as 238 mS cm⁻¹, the membrane aging broken time at 80 °C is between 4 and 6.6 h, and the fuel cells loading the membranes and feeding with hydrogen and air perform the max power density of between 0.65 and 1.25 W cm⁻². Modulating the sequence structure of chains and constructing multiblock polymers containing ether-free N-heretrocyclic blocks with sulfonic groups improve the stability of membranes while ensuring their proton conductivity.