The introduction of hydrophobic side chain structures in anion exchange membranes (AEMs) to facilitate ion transport has been widely studied; however, low or moderate hydrophobic hydrocarbon and semifluorinated side chains are insufficient to induce a high degree of microphase separation. Herein, we design and prepare poly(aryl piperidinium) AEMs with completely methylene-free perfluorinated side chains, which can maximize the thermodynamic incompatibility between main- and side chains, thus enhancing microphase separation at medium ion exchange capacities (IECs). According to the molecular dynamics study, the methylene-free perfluorinated side chain leads to better hydration of cations. The hydroxide conductivity of the methylene-free perfluorinated side chain-grafted PAP-pF-1 membrane reaches 124.9 mS cm at 80 °C, and the PAP-sF-1 with semifluorinated side chains and PAP-CH-1 with hydrocarbon side chains show lower conductivity (116.8 and 104.0 mS cm). The H/O fuel cell using the PAP-pF-1 membrane demonstrates a remarkable peak power density (1651 mW cm at 80 °C) and durability (greater than 300 h). This work provides a novel insight into enhancing microphase separation in AEMs; it opens up new possibilities for developing high-performance AEMs.
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