Unraveling the nanostructures and self-assembly behavior of perfluorosulfonic acid in water/ethanol solvent: Effect of EW and side-chain chemistry

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The perfluorosulfonic acid (PFSA) ionomers are key materials for proton exchange membranes (PEMs) and catalyst layers (CLs). Their morphology is profoundly influenced by the chain assembly behavior of PFSA in dispersions. Hence, we combine the characterization techniques of dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and cryo-transmission electron microscopy (Cryo-TEM) to study the nanostructures of PFSA dispersions, and provide a structure model for diverse PFSA ionomers in water/ethanol solvent. It is seen that PFSA ionomers self-assembly into a rod-like particle in dilute dispersion. As the concentration increases, the primary rod aggregates gradually assemble into a swollen- or Gaussian-network structure. Beyond this feature, we see that different PFSA ionomers show different nanostructures in dispersion. For the long-side-chain (LSC) PFSA ionomers, the 800-LSC PFSA tends to form monodisperse rod-like aggregates that is in a highly ordered arrangement with a rod diameter of 3.16 nm and a length of 28.72 nm. As the equivalent weight (EW) increases to 960, the poor solubility of the main chains in water/ethanol solvents leads to the “end-to-end” assemblies of the primary rod particles and dendritic secondary aggregates. The short-side-chain (SSC) PFSA ionomer that shares the same backbone with 960-LSC PFSA exhibit remarkable mono-dispersity and ordered arrangement of rod-like aggregates in water/ethanol solvents due to the strong electrostatic repulsion.