Spectroscopic Investigation of the Acid and Water Uptake of Polybenzimidazole Membranes for Fuel Cells

Polybenzimidazole (PBI) doped with H3PO4 is the most commonly used membrane material for high-temperature polymer fuel cells. Proton conductivity is strongly dependent on acid doping and water content. Despite these facts, only little is known on the chemical equilibria of all species inside the membrane as a function of the composition of the ternary system PBI - H3PO4 - H2O. This includes details on the proton transfer processes, on the dominant conduction mechanisms and on the condensation equilibria, leading to the formation of diphosphoric acid and higher homologues species. In this study, Raman and NMR spectroscopy is used to investigate the chemical interactions between H3PO4, H2O and PBI vs. the H3PO4 doping level. We have obtained information on the H-bond formation between H3PO4 and the polymer chains, on tautomeric processes as well as on the presence of not directly bound H3PO4 at high doping levels. Investigations were performed with uncrosslinked and crosslinked m-PBI and AB-PBI [1-4]. [1] F. Conti, A. Majerus, V. Di Noto, C. Korte, W. Lehnert, D Stolten, Raman study of the polybenzimidazole–phosphoric acid interactions in membranes for fuel cells, Phys. Chem. Chem. Phys. 14 (2012) 10022. [2] F. Conti, S. Willbold, S. Mammi, C. Korte, W. Lehnert, D. Stolten, Carbon NMR investigation of the polybenzimidazole–dimethylacetamide interactions in membranes for fuel cells, New J. Chem. 37 (2013) 152. [3] A. Majerus, F. Conti, C. Korte, W. Lehnert, D. Stolten, Thermogravimetric and Spectroscopic Investigation of the Interaction between Polybenzimidazole and Phosphoric Acid, ECS Transaction (2013) accepted. [4] G. A. Giffin, F. Conti, S. Lavina, A. Majerus, G. Pace, C. Korte, W. Lehnert, V. Di Noto, A vibrational spectroscopic and modeling study of poly(2,5-benzimidazole) - phosphoric acid interactions, Int. J. Hydrogen Energy (2013) accepted.