ABSTRACTA series of poly(ether sulfone)-based anion exchange membranes (AEMs), tethering with guanidinium side chains with different spacers, were synthesized via azide-alkyne cycloaddition, deprotection, and the subsequent ion exchange reactions. The designed polymer structures were verified by the 1H NMR spectra. Because of the appropriate water uptake and formation of interconnected ionic clusters, the GPES-3C with propyl spacer showed higher conductivity than the GPES-1C and GPES-9C, with methylene and nonyl spacers, respectively. Comparatively, the GPES-EO AEM with two ethylene oxide (EO) spacers exhibited even higher conductivity, these can be interpreted by interconnectivity of ionic channels and hydrophilicity nature of the EO spacer. Additionally, although the GPES membranes displayed sufficient thermal stability, the chemical stability of as-prepared materials needs to be much improved for fuel cell applications. Overall, these results demonstrated that the properties of “pendent-type” AEM can be tuned facilely by the spacer types and lengths. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1313–1321

A mechanically robust and tough anion exchange membrane was constructed using the strategy of supramolecular modalities. After introducing a secondary amide as a hydrogen-bonding crosslinking motif into the side chain of the PPO backbone, the membrane exhibits high mechanical strength and excellent flexibility (101% elongation at break), as well as suppressed water uptake, enhanced thermal stability and good fuel cell performances.

A series of poly(phenylene oxide)s (PPOs) bearing a flexible pendent imidazolium cation were prepared by an azide–alkyne cycloaddition between azidomethylated PPO and a novel alkyne-containing imidazolium, and their structures were confirmed by 1H NMR, 13C NMR, and FT-IR. The corresponding anion exchange membranes (AEMs) showed distinct hydrophobic/hydrophilic phase-separated morphology at higher imidazolium content, as evidenced by AFM and SAXS techniques, which favors for the construction of interconnected hydroxide transport channels. As a result, the as-prepared AEMs exhibited higher conductivity (95 mS cm−1, 80 °C, 100% RH) than conventional imidazolium benzylic-type AEM (55 mS cm−1, 80 °C, 100% RH) with even lower IEC. Furthermore, the introduction of a 1,2,3-triazole moiety into the polymer side chain does not compromise its thermal and alkaline stability. This investigation demonstrated that the “click chemistry” strategy will benefit further tailoring of high performance AEMs with “side-chain-type” architectures.

•A novel adamantammonium cation with high alkaline stability for AEM applications was reported.•The benzyl type AEMs based on adamantammonium show improved alkaline durability than benzylmethylammonium-benchmark AEM.•The membranes exhibit high ionic conductivity and excellent dimensional stability.In the pursuit of alkali stable cation as functional group for anion exchange membranes (AEMs), a novel adamantammonium (AdA) cation, which replacing methyl group of conventional trimethylammonium by an adamantyl group, was synthesized and investigated. 1H NMR spectroscopy was employed to quantify the extent of decomposition and the results showed that > 99% adamantammonium remaining after 7 days immersion in 2 M NaOH (in D2O) at 80 °C. The AdA functionalized benzyl type poly(2,6-dimethyl phenylene oxide) polyelectrolytes, PPO-AdAs, were further prepared and characterized the AEM properties. Not only the chemical durability of these new PPO-AdA membranes, interestingly, but the conductivity and dimensional stability (water uptake and in-plane swelling) are superior to the benzylmethylammonium-benchmark PPO-based AEM (PPO-TMA). With the similar IEC values, the water uptake of PPO-AdA-41 sample is much lower than PPO-TMA-28, however, the conductivity of the former (15.7 mS cm-1, chloride conductivity at 50 °C) is higher than the latter (13.3 mS cm-1). Overall, the results of this study offer a base-stable cation, adamantammonium, and the corresponding adamantammonium-based AEMs for fuel cell applications with the advantages of chemical stability, enhanced conductivity and excellent dimensional stability as well as facial functionalization technique.Download high-res image (134KB)Download full-size image