Structure-Transport Relationship of Perfluorosulfonic-Acid Membranes in Different Cationic Forms

Perfluorosulfonic-acid (PFSA) ionomers are widely used as solid electrolytes and ion-exchange membranes in electrochemical devices, wherein their properties are impacted by the interactions among the anionic sulfonate groups, mobile counter-ions (cations), and hydration levels. Cation-form and humidity collectively affect the structure/transport-property relationship, yet their interplay is still not well known. In this paper, we report changes in water uptake and conductivity of cation-exchanged PFSA in both vapor and liquid water, which are then correlated with changes in mechanical properties and nanostructure (hydrophilic-domain spacing and phase-separation). It is found that the magnitude of changes brought upon depends significantly on the membrane water content, with a master curve in terms of water volume fraction realized. Moreover, nanostructure and dynamical-mechanical behavior of the membrane is examined to establish structure/transport and transport/stability relationships. It is found that with increasing cation size (radius) and valence, the storage modulus increases, while the water uptake and conductivity decreases. In addition, regardless of the cation type, a universal relationship is found between the conductivity and modulus, indicative of a transport/stability tradeoff. The extent to which the cations impact the transport properties depends on the water content: at low hydration levels the controlling factor is the cation (and its interaction with the sulfonate sites), at increasing hydration the dominant factor becomes water volume fraction, although it is also controlled by the cations. Similarly, the decrease in hydrophilic domain spacing of PFSA exchanged with larger cations scales with cation radius at low water contents, but with Lewis acid strength (LAS) at higher hydration levels. The findings reported here not only provide valuable insights into the interaction between sulfonate groups, cations and water surrounding these ionic groups, but also for understanding cation contamination in fuel cells and redox flow batteries.