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In this paper, a series of composite proton exchange membranes comprising a cobaltacarborane protonated H[Co(C2B9H11)2] named (H[COSANE]) and polybenzimidazole (PBI) for a high temperature proton exchange membrane fuel cell (PEMFC) is reported, with the aim of enhancing the proton conductivity of PBI membranes doped with phosphoric acid. The effects of the anion [Co(C2B9H11)2] concentration in three different polymeric matrices based on the PBI structure, poly(2,2'-(m-phenylene)-5,5'-bibenzimidazole) (PBI-1), poly[2,2'-(p-oxydiphenylene)-5,5'-bibenzimidazole] (PBI-2) and poly(2,2'-(p-hexafluoroisopropylidene)-5,5'-bibenzimidazole) (PBI-3), have been investigated. The conductivity, diffusivity and mobility are greater in the composite membrane poly(2,2'-(p-hexafluoroisopropylidene)-5,5'-bibenzimidazole) containing fluorinated groups, reaching a maximum when the amount of H[COSANE] was 15%. In general, all the prepared membranes displayed excellent and tunable properties as conducting materials, with conductivities higher than 0.03 S cm-1 above 140 °C. From an analysis of electrode polarization (EP) the proton diffusion coefficients and mobility have been calculated.

The rapid increasing of the population in combination with the emergence of new energy-consuming technologies has risen worldwide total energy consumption towards unprecedent values. Furthermore, fossil fuel reserves are running out very quickly and the polluting greenhouse gases emitted during their utilization need to be reduced. In this scenario, a few alternative energy sources have been proposed and, among these, proton exchange membrane (PEM) fuel cells are promising. Recently, polybenzimidazole-based polymers, featuring high chemical and thermal stability, in combination with fillers that can regulate the proton mobility, have attracted tremendous attention for their roles as PEMs in fuel cells. Recent advances in composite membranes based on polybenzimidazole (PBI) for high temperature PEM fuel cell applications are summarized and highlighted in this review. In addition, the challenges, future trends, and prospects of composite membranes based on PBI for solid electrolytes are also discussed.