Novel polybenzimidazole derivatives for high temperature polymer electrolyte membrane fuel cell applications

Recent advances have made polymer electrolyte membrane fuel cells (PEMFCs) a leading alternative to internal combustion engines for both stationary and transportation applications. In particular, high temperature polymer electrolyte membranes operational above 120°C without humidification offer many advantages including fast electrode kinetics, high tolerance to fuel impurities and simple thermal and water management systems.; A series of polybenzimidazole (PBI) derivatives including pyridine-based PBI (PPBI) and sulfonated PBI (SPBI) homopolymers and copolymers have been synthesized using polyphosphoric acid (PPA) as both solvent and polycondensation agent. High molecular weight PBI derivative polymers were obtained with well controlled backbone structures in terms of pyridine ring content, polymer backbone rigidity and degree of sulfonation. A novel process, termed the PPA process, has been developed to prepare phosphoric acid (PA) doped PBI membranes by direct-casting of the PPA polymerization solution without isolation or re-dissolution of the polymers. The subsequent hydrolysis of PPA to PA by moisture absorbed from the atmosphere usually induced a transition from the solution-like state to a gel-like state and produced PA doped PBI membranes with a desirable suite of physiochemical properties characterized by the PA doping levels, mechanical properties and proton conductivities.; The effects of the polymer backbone structure on the polymer characteristics and membrane properties, i.e., the structure-property relationships of the PBI derivative polymers have been studied. The incorporation of additional basic nitrogen containing pyridine rings and sulfonic acid groups enhanced the polymer solubility in acid and dipolar solvents while retaining the inherently high thermal stability of the PBI heteroaromatic backbone. In particular, the degradation of the SPBI polymers with reasonable high molecular weights commenced above 450°C, notably higher than other sulfonated aromatic polymers. 31P-NMR technique was also used together with the titration and conductivity measurements to study the hydrolysis processes of PBI polymers with different structures and to further understand the effect of the polymer structure, PPA solution parameters and process conditions on the resulting membrane properties. The PA doped PBI membranes from the PPA process generally exhibited high acid doping levels from approximately 10–50 moles of PA per PBI repeat unit, which contributed to their unprecedented high proton conductivity values in the range of 0.1–0.3 S/cm. Owing to the high molecular weight of the PBI polymers and the unique gel structures resulting from the PPA process, these membranes exhibited high mechanical properties at high acid doping levels. It has been shown that the PBIs with more para linkages generally gave membranes with higher PA doping levels, higher mechanical properties and higher proton conductivities. Preliminary fuel cell performance evaluations on selected PBI polymer compositions together with a ∼1200 hours' long-term fuel cell test demonstrated the feasibility of the novel PBI derivative polymer electrolyte membranes from the PPA process for operating a fuel cell at temperatures in excess of 120°C without any external humidification or pressure requirements.