This review discusses the progress of research on sulfonated poly(ether ether ketone) (SPEEK) and its composite membranes in proton exchange membrane fuel cells (PEMFCs). SPEEK is a promising material for replacing traditional perfluorosulfonic acid membranes due to its excellent thermal stability, mechanical property, and tunable proton conductivity. By adjusting the degree of sulfonation (DS) of SPEEK, the hydrophilicity and proton conductivity of the membrane can be controlled, while also balancing its mechanical, thermal, and chemical stability. Researchers have developed various composite membranes by combining SPEEK with a range of organic and inorganic materials, such as polybenzimidazole (PBI), fluoropolymers, and silica, to enhance the mechanical, chemical, and thermal stability of the membranes, while reducing fuel permeability and improving the overall performance of the fuel cell. Despite the significant potential of SPEEK and its composite membranes in PEMFCs, there are still challenges and room for improvement, including proton conductivity, chemical stability, cost-effectiveness, and environmental impact assessments.

This study systematically investigated the physicochemical properties and proton exchange membrane fuel cell (PEMFC) performance of perfluorosulfonic acid (PFSA) membranes with different thicknesses, which were prepared based on the resins produced by Dongyue (China) in comparison with commercial Nafion membranes. It was found that the water uptake of Dongyue membranes is significantly higher than that of Nafion, showing a significant upward trend with the thickness increase. The ion exchange capacity (IEC) of these membranes is ca. 1 mmol·g⁻¹. Moreover, the tensile strength of the Dongyue membrane was positively correlated with the thickness and was significantly higher than that of recast Nafion. Under 80 °C, all Dongyue membranes with various thicknesses (15~45 μm) exhibited PEMFC single-cell performance superior to that of Nafion. The maximum power density is observed with a thickness of 25 μm, reaching 851.76 mW·cm⁻², which is higher than that of Nafion (635.99 mW·cm⁻²). However, the oxidative stability of the prepared Dongyue PFSA series membranes exhibits a slight deficit compared to commercial Nafion membranes. Subsequently, the modification and optimization of preparation processes can be employed to improve the mechanical and chemical stability of Dongyue PFSA membranes.

Proton-exchange membranes (PEMs) are the pivotal components of vanadium redox flow batteries (VRFBs) and play a critical role in the comprehensive output performance of VRFB systems. Currently, the most widely commercialized membranes are Nafion series membranes produced by DuPont, Wilmington, DE, USA, but the high vanadium permeability and cost hinder their large-scale promotion. Hence, there is an active demand for developing a low-cost, high-performance, and energy-efficient PEM to promote the commercialization of VRFB systems. In this paper, sulfonated poly(ether ether ketone) (SPEEK) as matrix and zirconia nanoparticles as inorganic filler were used for composite modification to prepare a series of SPEEK–ZrO₂ organic–inorganic hybrid membranes for VRFBs. The thickness of these membranes was 50–100 μm. Compared with Nafion 115 (thickness 128 μm), composite membranes demonstrated obvious cost advantages. The results showed that the SP–Z-X series membranes had higher water uptake (53.26–71.1%) and proton conductivity (0.11–0.24 S cm⁻¹). SP–Z-5 displayed the best comprehensive output performance at 200 mA cm⁻² (CE: 99.01%, VE: 81.95%, EE: 81.11%). These hybrid membranes are very cost-effective and exhibit high potential for application in VRFB applications, and are expected to lead to the industrial application of VRFBs on a large scale.

High-temperature proton exchange membrane systems (HT-PEM) based on polybenzimidazole (PBI) membranes are a promising technology offering significant advantages over their low-temperature counterparts. A key challenge limiting its long-term durability is the leaching of phosphoric acid (PA) from the membrane during operation. This work introduces, for the first time, the strategy of modifying polybenzimidazole (PBI) membranes with amino-functionalized porous aromatic frameworks (PAF-20-NH₂) to fundamentally enhance their PA retention and operational stability, a critical challenge for high-temperature PEM technologies. We propose that the synergistic combination of the framework’s nanoscale porosity and the specific interaction of its amino groups create an unprecedented network for acid immobilization via reinforced hydrogen bonding. A comprehensive study of the membranes’ physicochemical and structural properties reveals that PAF-20-NH₂ modification results in a significant and quantitatively demonstrated improvement in acid retention capacity, directly translating into a notable increase in proton conductivity compared to both pristine PBI and membranes modified with the non-functionalized PAF-20. These findings establish a new, highly effective pathway for the rational design of next-generation high-performance PBI-based membranes.