High-performance sandwich-structure PI/SPEEK+HPW nanofiber composite membrane with balanced proton conductivity and stability

Due to its uncomplicated manufacturing procedure for large-scale industrialization and adaptable conductivity, the competitive proton exchange membrane (PEM) matrix employed is sulfonated poly (ether ether ketone). However, the conflict between the strong proton conductivity and high stability of SPEEK-based PEM constantly upsets the equilibrium; the primary chain of SPEEK will conduct more protons if additional sulfonic acid is introduced, but it also causes a high swelling ratio and lowers stability. To tackle this challenging issue, we coupled the high intrinsic proton conductivity of phosphotungstic acid (HPW) and the excellent stability of polyimide (PI) nanofibers in a single PEM. In particular, sandwich-structure hybrid membranes (PI/SPEEK + HPW) were created to reduce HPW loss under operational conditions, further improving stability. Consequently, the swelling ratio and conductivity of the premium sandwich-structure PI/SPEEK + HPW-20 were 29% and 223.4 mS cm−1 under 60 °C and 100% RH, their respective values were 8% larger than those of SPEEK. Its proton conductivity reached 170.9 mS cm−1 during 13 days of exposure under 60 °C and 100% RH, which would be 30% better than that of SPEEK over the same treatment. Protons in these membranes were transported through Grotthus and vehicle mechanism, and the establishment of an acid-rich layer at the surface among PI nanofiber with HPW/SPEEK, which was confirmed by FTIR, XPS, and TEM, is responsible for these superior performances. From our point of view, our findings might encourage more studies into the creation of high-performance PEM.