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Low-cost anion exchange membrane fuel cells have been investigated as a promising alternative to proton exchange membrane fuel cells for the last decade. The major barriers to the viability of anion exchange membrane fuel cells are their unsatisfactory key components—anion exchange ionomers and membranes. Here, we present a series of durable poly(fluorenyl aryl piperidinium) ionomers and membranes where the membranes possess high OH− conductivity of 208 mS cm−1 at 80 °C, low H2 permeability, excellent mechanical properties (84.5 MPa TS), and 2000 h ex-situ durability in 1 M NaOH at 80 °C, while the ionomers have high water vapor permeability and low phenyl adsorption. Based on our rational design of poly(fluorenyl aryl piperidinium) membranes and ionomers, we demonstrate alkaline fuel cell performances of 2.34 W cm−2 in H2-O2 and 1.25 W cm−2 in H2-air (CO2-free) at 80 °C. The present cells can be operated stably under a 0.2 A cm−2 current density for ~200 h.

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Two series of random sulfonated poly-(benzothiazole-co-benzimidazole) polymers (sPBT-BI) with 70% and 60% degree of sulfonation were evaluated as proton exchange membranes. sPBT was also prepared for a comparative study. The mechanical properties of sPBT-BI were greatly enhanced by incorporation of benzimidazole (BI); sPBT-BI70-10 showed a tensile strength of 125 MPa and elongation at break of 38.9%, an increase of 56.5% and 145%, respectively, compared with sPBT. The solubility, dimensional stability, thermal properties, and oxidative stability of sPBT-BI were also improved. The ionic clusters of sPBT-BI membranes in both AFM phase images and TEM images became narrower with increasing amounts of BI while containing the same molar amount of sulfonic acid groups. This resulted in lower dimensional swelling and higher mechanical strength, but the proton conductivity decreased. However, high proton conductivity was achieved by incorporating an appropriate content of BI. PEMFC H 2 /air single cell performances and durabilities were improved by incorporation of 5% of BI units in sPBT.

Insufficient mechanical properties are one of the major obstacles for the commercialization of ultrahigh permeability thermally rearranged (TR) membranes in largescale gas separation applications. The incorporation of preformed benzoxazole/benzimidazole units into o-hydroxy copolyimide precursors, which themselves subsequently thermally rearrange to form additional benzoxazole units, were prepared for the first time. Using commercially available monomers, mechanically tough membranes prepared from random and block TR poly(benzoxazole-co-imide) copolymers (TR-PBOI) were investigated for gas separation. The effects of the chemical structures, copolymerization modes, and thermal holding time of o-hydroxy copolyimides on the molecular packing and properties, including gas transport, for the resulting TR-PBOI membranes have been examined in detail. After treatment at 400°C, tough TR-PBOI membranes exhibited tensile strengths of 71.4−113.9 MPa and elongation at break of 5.1−16.1%. Moreover, they presented higher or comparable gas transport performance as compared to those tough/robust TR membranes reported previously. Reported for the first time is a comparative investigation of the copolymerization mode (random or block) on membrane properties. The novel polymer architecture and systematic property studies promote a better understanding of the materials and process development of commercial TR membranes for gas separation applications.