Highly Conductive and Mechanically Stable Imidazole-Rich Cross-Linked Networks for High-Temperature Proton Exchange Membrane Fuel Cells
Xiaobai Li, Hongwei Ma, Peng Wang, Zhenchao Liu, Jinwu Peng, Wei Hu, Zhenhua Jiang, Baijun Liu, Michael D. Guiver
Abstract
Phosphoric acid-doped polybenzimidazole (PA-PBI) used in high-temperature proton exchange membranes (HT-PEMs) frequently suffers from a serious loss of mechanical strength because of the "plasticizing effect" of the dopant acid. Conventional cross-linking approaches generally enhance membrane stability. However, acid doping levels (ADLs) and consequently proton conductivity inevitably decrease. This is due to the formation of more compact molecular structures and a reduced amount of functional imidazole units, caused by their consumption in introducing the cross-linker. To resolve the common problems of current PA-PBI-based HT-PEMs, herein, a highly acidophilic imidazole-rich cross-linked network with superior "antiplasticizing" ability is constructed based on a novel multifunctional cross-linker. This unique bischloro/bibenzimidazole ("A2B2-type") molecular structure has extremely high reactivity, including "self-reaction" among the cross-linkers and "inter-reaction" between the cross-linker and PBI molecules. The resulting imidazole-rich cross-linked membranes exhibit the desired combination of high ADLs, high conductivity, outstanding dimensional–mechanical stability, and excellent fuel cell performance. In comparison to a corresponding linear PBI membrane, one membrane with a high content of the cross-linker of 30% has a 100 wt % increased acid uptake, a doubling in proton conductivity at 200 °C, and a maximum power density of 533 mW·cm–2 at 160 °C without humidification.