Multi-functionalized acid-base double-shell nanotubes are incorporated into the proton exchange membrane to cope with low humidity conditions

Abstract

Proton exchange membranes (PEM) with high proton conductivity and water retention are critical to the commercial application of proton exchange membrane fuel cells (PEMFC). In this study, acid-base double-shell nanotubes with carboxylate inner shell and an imidazole outer shell (DSNT-A@B) are synthesized via continuous distillation-precipitation polymerization using halloysite nanotubes (HNTs) as seeds. Then, it is incorporated into sulfonated poly (ether ether ketone) matrix to prepare composite membranes. The carboxylic inner shell can increase the content of combined water, thereby giving the composite membrane higher water retention. The imidazole shell acts as basic shell to create acid-base pairs with the membrane and inner shell to promote proton conductivity following the Grotthuss mechanism. The results show that when the blending amount is 5 wt%, the proton conductivity of the composite membrane reaches 0.336 S/cm at 80 °C and 100% relative humidity (RH), which is twice as high as that of the original membrane. In particular, the water loss of SPEEK/DSNT-A@B-10 composite membrane is only 54.55% at 40 °C and 20% RH, which is 32.77% lower than the SPEEK membrane. Therefore, this DSNT-A@B/SPEEK composite membrane can be used as a potential candidate for high temperature and low humidity fuel cells.