Composite polymer membranes for proton exchange membrane fuel cells operating at elevated temperatures and reduced humidities.

摘要

Proton Exchange Membrane Fuel Cells (PEMFCs) are the leading candidate in the fuel cell technology due to the high power density, solid electrolyte, and low operational temperature. However, PEMFCs operating in the normal temperature range (60-80°C) face problems including poor carbon monoxide tolerance and heat rejection. The poisoning effect can be significantly relieved by operating the fuel cell at elevated temperature, which also improves the heat rejection and electrochemical kinetics. Low relative humidity (RH) operation is also desirable to simplify the reactant humidification system. However, at elevated temperatures, reduced RH PEMFC performance is seriously impaired due to irreversible water loss from presently employed state-of-the-art polymer membrane, Nafion.; This thesis focuses on developing polymer electrolyte membranes with high water retention ability for operation in elevated temperature (110-150°C), reduced humidity (∼50%RH) PEMFCs. One approach is to alter Nafion by adding inorganic particles such as TiO2, SiO2, Zr(HPO 4)2, etc. While the presence of these materials in Nafion has proven beneficial, a reduction or no improvement in the PEMFC performance of Nafion/TiO2 and Nafion/Zr(HPO4)2 membranes is observed with reduced particle sizes or increased particle loadings in Nafion. It is concluded that the PEMFC performance enhancement associated with addition of these inorganic particles was not due to the particle hydrophilicity. Rather, the particle, partially located in the hydrophobic region of the membrane, benefits the cell performance by altering the membrane structure. Water transport properties of some Nafion composite membranes were investigated by NMR methods including pulsed field gradient spin echo diffusion, spin-lattice relaxation, and spectral measurements. Compared to unmodified Nafion, composite membranes materials exhibit longer longitudinal relaxation time constant T1. In addition to the Nafion material, sulfonated styrene-ethylene/butylene-styrene triblock copolymer (sSEBS) was investigated as an alternate membrane candidate. sSEBS was modified through introduction of polymer crosslinks using benzephenone as a photoinitiator and addition of a titania co-phase. A photocrosslinked membrane initially containing 15% benzophenone and 3% titania laminated with a 10 mum Nafion layer was found to produce the best PEMFC performance (120°C, 50%RH).