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Polybenzimidazole (PBI) activated with H3PO4 is one of the membranes of choice to replace Nafion® in PEMFCs in order to allow their use above 100 °C. The limits of PBI in terms of acid leaching and low conductivity below 160 °C can be overcome by a proper monomer tailoring, and by the addition of new fillers. Here, we report on new pyridine‐based PBI membranes with: (i) imidazole‐silica (SiO2‐Im) and (ii) mesostructured silica (SBA‐15) fillers. Both the thermal stability and the permanent conductivity are improved by adding 5 wt.‐% of filler, but SiO2‐Im gives the best results. Permanent conductivity values higher than 10–3 S cm–1 are obtained at 120 °C and 50% R.H. Vibrational spectroscopies (FT‐IR and Raman) are used to investigate the relationships among the polymer, the filler and the activating H3PO4 acid.

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This review article presents recent studies on nanostructured glass-ceramic materials with substantially improved electrical (ionic or electronic) conductivity or with an extended temperature stability range of highly conducting high-temperature crystalline phases. Such materials were synthesized by the thermal nanocrystallization of selected electrically conducting oxide glasses. Various nanostructured systems have been described, including glass-ceramics based on ion conductive glasses (silver iodate and bismuth oxide ones) and electronic conductive glasses (vanadate-phosphate and olivine-like ones). Most systems under consideration have been studied with the practical aim of using them as electrode or solid electrolyte materials for rechargeable Li-ion, Na-ion, all-solid batteries, or solid oxide fuel cells. It has been shown that the conductivity enhancement of glass-ceramics is closely correlated with their dual microstructure, consisting of nanocrystallites (5–100 nm) confined in the glassy matrix. The disordered interfacial regions in those materials form “easy conduction” paths. It has also been shown that the glassy matrices may be a suitable environment for phases, which in bulk form are stable at high temperatures, and may exist when confined in nanograins embedded in the glassy matrix even at room temperature. Many complementary experimental techniques probing the electrical conductivity, long- and short-range structure, microstructure at the nanometer scale, or thermal transitions have been used to characterize the glass-ceramic systems under consideration. Their results have helped to explain the correlations between the microstructure and the properties of these systems.

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