We present a new approach of morphological transformation for effective proton transport within ionomers, even at partially hydrated states. Highly sulfonated poly(phenylene sulfide nitrile) (XESPSN) random network copolymers were synthesized as alternatives to state-of-the-art perfluorinated polymers such as Nafion^®. A combination of thermal annealing and cross-linking, which was conducted at 250 °C by simple trimerisation of ethynyl groups at the chain termini, results in a morphological transformation. The resulting nanophase separation between the hydrophilic and hydrophobic domains forms well-connected hydrophilic nanochannels for dramatically enhanced proton conduction, even at partially hydrated conditions. For instance, the proton conductivity of XESPSN60 was 160% higher than that of Nafion^® 212 at 80 °C and 50% relative humidity. The water uptake and dimensional swelling were also reduced and mechanical properties and oxidative stability were improved after three-dimensional network formation. The fuel cell performance of XESPSN membranes exhibited a significantly higher maximum power density than that of Nafion^® 212 under partially hydrated environments.

High performance of SnP₂O₇-based intermediate temperature fuel cells was obtained with a quaternary ammonium-biphosphate ion-pair coordinated polymer electrolyte.