The strategy of micropore confinement via organic macrocyclic cavities for designing novel high-performance proton exchange membranes

The high-temperature hydrogen proton exchange membrane fuel cell is considered a disruptive technology for future energy applications. However, the weak binding strength between the proton carriers (phosphoric acid molecules) with polymer chains reduces the operational stability and proton transfer efficiency at conditions of high temperature and low humidity. In this work, a strategy of micropore confinement via organic macrocyclic cavities (sulfonic calix[4]arenes, sulfonic calix[8]arenes, sulfonated β-cyclodextrin) was developed for designing novel mixed matrix membranes functioning as high-temperature hydrogen proton exchange membranes. Benefitting from the confined micropores constructed by supramolecular cavities, the obtained mixed matrix membranes showed a higher uptake and retention capability of phosphoric acid as well as lower membrane swelling, yielding an enhanced proton conductivity. The proton conductivity of the mixed matrix membranes was 2-3 times higher while the conductivity attenuation was only 58.6% comparing with neat PBI membrane, (140℃, relative humidity = 0). In addition, due to the good compatibility caused by hydrogen bonding between fillers and polymer chains, the volume swelling was only 14% and the mechanical strength of the obtained mixed matrix membranes increased. We believe the strategy of micropore confinement via organic macrocyclic cavities for designing the novel mixed matrix membranes is thought to be of great significance for the research on high-temperature proton exchange membrane.