Structurally Well-Defined Anion-Exchange Membranes Containing Perfluoroalkyl and Ammonium-Functionalized Fluorenyl Groups

[Image: see text] Novel anion-conductive polymers containing perfluoroalkyl and ammonium-functionalized fluorene groups were synthesized and characterized. The quaternized polymers synthesized using a dimethylaminated fluorene monomer had a well-defined chemical structure in which each fluorenyl group was substituted with two ammonium groups at specific positions. The resulting polymers had a high molecular weight (M(n) = 8.9–13.8 kDa, M(w) = 13.7–24.5 kDa) to provide bendable thin membranes with the ion-exchange capacity (IEC) ranging from 0.7 to 1.9 mequiv g(–1) by solution casting. Both transmission electron microscopy images and small-angle X-ray scattering patterns suggested that the polymer membranes possessed a nanoscale phase-separated morphology based on the hydrophilic/hydrophobic differences in the polymer components. Unlike typical anion-exchange membranes found in the literature, hydroxide ion conductivity of the membranes did not increase with increasing IEC because of their high swelling capability in water. The membrane with IEC = 1.2 mequiv g(–1) showed balanced properties of high hydroxide ion conductivity (81 mS cm(–1) at 80 °C in water) and mechanical strength (>100% elongation and 14 MPa maximum stress at 80 °C, 60% relative humidity). The polymer main chains were stable in 4 M KOH for 1000 h, whereas the trimethylbenzyl-type ammonium groups degraded under the conditions to cause loss in the hydroxide ion conductivity. An H(2)/O(2) fuel cell with the membrane with IEC = 1.2 mequiv g(–1) exhibited a maximum power density of 242 mW cm(–2) at 580 mA cm(–2) current density.