Designing Advanced Alkaline Polymer Electrolytes for Fuel Cell Applications (2011)

Although the polymer electrolyte fuel cell (PEFC) is a superior power source for electric vehicles, the high cost of this technology has served as the primary barrier to the large-scale commercialization. Over the last decade, researchers have pursued lower-cost next-generation materials for fuel cells, and alkaline polymer electrolytes (APEs) have emerged as an enabling material for platinum-free fuel cells. To fulfill the requirements of fuel cell applications, the APE must be as conductive and stable as its acidic counterpart, such as Nafion. This benchmark has proved challenging for APEs because the conductivity of OH(-) is intrinsically lower than that of H(+), and the stability of the cationic functional group in APEs, typically quaternary ammonia (-NR(3)(+)), is usually lower than that of the sulfonic functional group (-SO(3)(-)) in acidic polymer electrolytes. To improve the ionic conductivity, APEs are often designed to be of high ion-exchange capacity (IEC). This modification has caused unfavorable changes in the materials: these high IEC APEs absorb excessive amounts of water, leading to significant swelling and a decline in mechanical strength of the membrane. Cross-linking the polymer chains does not completely solve the problem because stable ionomer solutions would not be available for PEFC assembly. In this Account, we report our recent progress in the development of advanced APEs, which are highly resistant to swelling and show conductivities comparable with Nafion at typical temperatures for fuel-cell operation. We have proposed two strategies for improving the performance of APEs: self-cross-linking and self-aggregating designs. The self-cross-linking design builds on conventional cross-linking methods and works for APEs with high IEC. The self-aggregating design improves the effective mobility of OH(-) and boosts the ionic conductivity of APEs with low IEC. For APEs with high IEC, cross-linking is necessary to restrict the swelling of the membrane. In our self-cross-linking design, a short-range cross-linker, tertiary amino groups, is grafted onto the quaternary ammonia polysulfone (QAPS) so that the cross-linking process can only occur during membrane casting. Thus, we obtain both the stable ionomer solution and the cross-linked membrane. The self-cross-linked QAPS (xQAPS) possesses a tight-binding structure and is highly resistant to swelling: even at 80 °C, the membrane swells by less than 3%. For APEs with low IEC, the key is to design efficient OH(-) conducting channels. In our self-aggregating design, long alkyl side-chains are attached to the QAPS. Based on both the transmission electron microscopy (TEM) observations and the molecular dynamics (MD) simulations, these added hydrophobic groups effectively drive the microscopic phase separation of the hydrophilic and hydrophobic domains and produce enlarged and aggregated ionic channels. The ionic conductivity of the self-aggregated QAPS (aQAPS) is three-fold higher than that of the conventional QAPS and is comparable to that of Nafion at elevated temperatures (e.g., greater than 0.1 S/cm at 80 °C).