Sulfonated poly(ether ether ketone) composite membranes based on amino-modified halloysite nanotubes that effectively immobilize phosphotungstic acid

In this work, we prepared amino-modified halloysite nanotubes (PEI-DHNTs) via the co-deposition of self-polymerized dopamine and polyethylenimine (PEI) on the surface of nanotubes, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Thermogravimetric analysis (TGA). A series of composite proton exchange membranes (PEMs) were prepared by incorporating PEI-DHNTs and phosphotungstic acid (HPW) into sulfonated poly(ether ether ketone) (SPEEK). It was found that both PEI-DHNTs and HPW were well dispersed in the polymer matrix, exhibiting excellent filler-matrix compatibility. The composite membranes demonstrated enhanced proton conductivity, reaching as high as 0.078 S cm −1 with 33.3 wt.% HPW loading, which was ~90% higher than that of SPEEK control membrane. Such improvement was mainly attributed to the strong acid–base pairs formed by PEI-DHNT with both SPEEK and HPW, which shortened proton hopping distance and created more continuous proton conduction pathways. Furthermore, the membrane conductivity remained almost constant after 1 year's immersion in liquid water, indicating the successful immobilization of HPW in the composite membranes. Graphical Amino-modified halloysite nanotubes (PEI-DHNTs) were prepared and used to successfully immobilize phosphotungstic acid (HPW) in sulfonated poly(ether ether ketone) (SPEEK) composite membranes. Due to the strong acid-base pairing between PEI-DHNTs and SPEEK/HPW, the shorter proton-hopping distance and more continuous proton conduction pathways result in as high as ~90% improvement in proton conductivity for the composite membranes. Furthermore, the membrane conductivity remain almost constant after 1 year's immersion in liquid water.