Understanding methods of preparation and characterization of pore-filling polymer composites for proton exchange membranes: a beginner’s guide

Composite membranes based on porous support membranes filled with a proton-conducting polymer appear to be a promising approach to develop novel proton exchange membranes (PEMs). It allows optimization of the properties of the filler and the matrix separately, e.g. for maximal conductivity of the former and maximal physical strength of the latter. In addition, the confinement itself can alter the properties of the filling ionomer, e.g. toward higher conductivity and selectivity due to alignment and restricted swelling. This article reviews the literature on PEMs prepared by filling of submicron and nanometric size pores with Nafion and other proton-conductive polymers. PEMs based on alternating perfluorinated and non-perfluorinated polymer systems and incorporation of fillers are briefly discussed too, as they share some structure/transport relationships with the pore-filling PEMs. We also review here the background knowledge on structural and transport properties of Nafion and proton-conducting polymers in general, as well as experimental methods concerned with preparation and characterization of pore-filling membranes. Such information will be useful for preparing next-generation composite membranes, which will allow maximal utilization of beneficial characteristics of polymeric proton conductors and understanding the complicated structure/transport relationships in the pore-filling composite PEMs.