The proton exchange membrane (PEM) represents a pivotal material and a key challenge in developing fuel cell science and hydrogen technology. Nafion is the most promising polymer which will lead to its commercialisation. Hybrid membranes of nanosized tungsten oxide (WO₃) and Nafion were fabricated, characterised, and tested in a single cell. The incorporation of 10 wt% WO₃ resulted in 21% higher water uptake, 11.7% lower swelling ratio, almost doubling the hydration degree, and 13% higher mechanical stability of the hybrid membrane compared to the Nafion XL. Compared to commercial Nafion XL, the rNF–WO-10 hybrid membrane showed an 8.8% and 20% increase in current density of the cell at 0.4 V operating at 80 and 95 °C with 1.89 and 2.29 A/cm², respectively. The maximum power density has increased by 9% (0.76 W/cm²) and 19.9% (0.922 W/cm²) when operating at the same temperatures compared to the commercial Nafion XL membrane. Generally, considering the particular structure of Nafion XL, our Nafion-based membrane with 10 wt% WO₃ (rNF–WO-10) is a suitable PEM with a comparable performance at different operating conditions.

Perfluorosulfonic acid (PFSA) polymers such as Nafion are the most frequently used Proton Exchange Membrane (PEM) in PEM fuel cells. Nafion XL is one of the most recently developed membranes designed to enhance performance by employing a mechanically reinforced layer in the architecture and a chemical stabilizer. The influence of the water and acid pre-treatment process on the physicochemical properties of Nafion XL membrane and Membrane Electrode Assembly (MEA) was investigated. The obtained results indicate that the pre-treated membranes have higher water uptake and dimensional swelling ratios, i.e., higher hydrophilicity, while the untreated membrane demonstrated a higher ionic exchange capacity. Furthermore, the conductivity of the acid pre-treated Nafion XL membrane was ~ 9.7% higher compared to the untreated membrane. Additionally, the maximum power densities obtained at 80 °C using acid pre-treatment were ~ 0.8 and 0.93 W/cm² for re-cast Nafion and Nafion XL, respectively. However, the maximum generated powers for untreated membranes at the same condition were 0.36 and 0.66 W/cm² for re-cast Nafion and Nafion XL, respectively. The overall results indicated that the PEM’s pre-treatment process is essential to enhance performance.

Novel blend membranes containing S-PVA and PEBAX 1657 with a blend ratio of 8:2 (referred to as SPP) were prepared using a solution-casting technique. In the manufacturing process, sulfonated montmorillonite (S-MMT) in ratios of 0%, 3%, 5%, and 7% was used as a filler. The crystallinity of composite membranes has been investigated by X-ray diffraction (XRD), while the interaction between the components was evaluated using Fourier-transform infrared spectroscopy (FT-IR). With increasing filler content, good compatibility between the components due to hydrogen bonds was established, which ultimately resulted in improved tensile strength and chemical stability. In addition, due to the sulfonated moieties of S-MMT, the highest ion exchange capacity (0.46 meq/g) and water uptake (51.61%) can be achieved at the highest filler content with an acceptable swelling degree of 22.65%. The composite membrane with 7% S-MMT appears to be suitable for application in proton exchange membrane fuel cells (PEMFCs). Amongst the membranes studied, this membrane achieved the highest current density and power density in fuel cell tests, which were 149.5 mA/cm² and 49.51 mW/cm². Our fluorine-free composite membranes can become a promising new membrane family in PEMFC applications, offering an alternative to Nafion membranes.

Novel blend membranes containing S-PVA and PEBAX 1657 at a blend ratio of 8:2 were doped with varying amounts of titanium dioxide phosphate (TiO₂PO₄) as a nanoparticle filler at concentrations of 0, 3, 5, and 7 wt%. The membranes were fabricated using the solution-casting technique. The effect of the TiO₂PO₄ nanofiller on the polymer matrix was thoroughly investigated. Our aim was to investigate how the incorporation of TiO₂PO₄ nanofillers into non-fluorinated SPP-based membranes affects their structural, physicochemical, and electrochemical properties for application in fuel cells. Crystallinity of the samples was checked by means of X-ray diffraction (XRD), while FTIR was used to investigate the contact between the nanofiller and the polymers. The good compatibility resulted in strong interactions between the constituents and led to increased crystallinity of the membrane as well. Furthermore, SEM images confirmed the uniform distribution of the nanofiller. These structural features led to good thermal stability, as evidenced by thermogravimetric analysis (TGA), and good mechanical strength, as proved by tensile tests. Among the samples investigated, the highest water uptake of 51.70% was achieved on the composite membrane containing 3 wt% TiO₂PO₄, which also showed the highest ion exchange capacity at room temperature, reaching 1.13 meq/g. In line with these properties, among the synthesized membranes, the membrane labeled SPP 3% TiO₂PO₄ has the highest current density and power density, with values of 175.5 mA/cm² and 61.52 mW/cm², respectively.