In this paper, using patented nano-additive based polymer synthesis technology, a novel approach to the design and fabrication of high temperature proton exchange membrane (PEM) has been developed. The presence of sulfonated octaphenyl POSS (S-POSS) in a PBI-PA (polybenzimidazole-phosphoric acid) membrane results in a 40–50% increase in conductivity at 120–200$deg relative to non-sulfonated silica or POSS control fillers at comparable weight percent filler loadings and PBI molecular masses, and also relative to unfilled PBI-PA membranes. In addition, the presence of S-POSS and silica both result in physical reinforcement of the membrane and increased its modulus and mechanical integrity, but only S-POSS offers the benefits of both increased conductivity and increased modulus. Isophthalic acid and 3,3’-diaminobenzidine (DAB) were polymerized in the presence of polyphosphoric acid (PPA) and S-POSS nanoadditive, and the degree of polymerization was monitored by viscosity and torque change measurements. Molecular mass was determined by inherent viscosity measurements of samples removed from the reaction solution. Membranes were prepared by casting the reaction solution and allowing PPA to hydrolyze to PA under ambient conditions. The membranes were characterized for acid content, in-plane conductivity, tensile modulus and shear modulus, and were roll-milled to achieve the desired thickness for membrane electrode assembly (MEA) fabrication.

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