Positron annihilation lifetime spectroscopic analysis of Nafion and graft‐type polymer electrolyte membranes for fuel cell application

Abstract

AbstractThe subnano free‐volume hole features of Nafion‐212 and poly(styrene sulfonic acid) grafted poly(ethylene‐co‐tetrafluoroethylene) polymer electrolyte membranes are investigated by using the positron annihilation lifetime spectroscopic analyses with three‐ and four‐component models (i.e., one‐ and two‐ortho‐positronium [o‐Ps] components). The four‐component model provides a more adequate description of free‐volume hole features for both membranes, in which the longer o‐Ps lifetime is assigned to the larger free volume hole sizes in the mobile side chains, while the shorter o‐Ps lifetime is associated with the smaller free volume hole sizes within the backbones (the rigid amorphous fractions and the crystalline‐amorphous interfaces) and the interfaces between the main chains and the side chains. The o‐Ps annihilation is found to occur primarily in the side chains. The subnano volume hole features revealed by the positron annihilation lifetime (PAL) spectra suggest the primary water uptake and conductance in the side chains and the possible presence of water molecules in the rigid amorphous fractions and the interfaces. Note that the three‐component model as usually reported in the literature may underestimate the lifetime and intensity of ortho‐positronium annihilation.