Yi Zhi Zhuo

Enhancement of hydroxide conductivity by grafting flexible pendant imidazolium groups into poly(arylene ether sulfone) as anion exchange membranes

Anion exchange membranes (AEMs) have been recognized as one of the most prospective polyelectrolytes for fuel cells due to their faster electrode reaction kinetics and the potential of adopting cheaper metal catalysts against proton exchange membranes (PEMs). Herein, a series of poly(arylene ether sulfone)s containing a flexible pendant imidazolium cation were synthesized by grafting bromine-bearing imidazolium-based ionic liquids into a hydroxyl-bearing poly(ether sulfone) matrix. 1H NMR spectroscopy was used to confirm the as-synthesized copolymers. Atomic force microscopy (AFM) and small angle X-ray scattering (SAXS) were used to characterize the morphology of the membranes. The incorporation of the flexible side-chain imidazolium groups is beneficial to the aggregation of the ionic clusters leading to the formation of hydrophilic/hydrophobic phase-separated morphology and nano-channels. As a result, an enhancement in the ionic conductivity can be achieved. Therefore, the as-prepared AEMs possess higher ionic conductivity than traditional benzyl-type AEMs. The weight-based ion exchange capacity (IECw) of the membranes was in the range of 1.01–1.90 meq. g−1. Correspondingly, their ionic conductivity was in the range of 22.13–59.19 and 51.66–108.53 mS cm−1 at 30 and 80 °C, respectively. Moreover, the membranes also exhibit good alkaline stability and interesting single cell performance. This work presents a facile and universal route for the synthesis of AEMs with superior performance.

Phenolphthalein-based Poly(arylene ether sulfone nitrile)s Multiblock Copolymers As Anion Exchange Membranes for Alkaline Fuel Cells

A series of phenolphthalein-based poly(arylene ether sulfone nitrile)s (PESN) multiblock copolymers containing 1-methylimidazole groups (ImPESN) were synthesized to prepare anion exchange membranes (AEMs) for alkaline fuel cells. The ion groups were introduced selectively and densely on the unit of phenolphthalein as the hydrophilic segments, allowing for the formation of ion clusters. Strong polar nitrile groups were introduced into the hydrophobic segments with the intention of improving the dimensional stability of the AEMs. A well-controlled multiblock structure was responsible for the well-defined hydrophobic/hydrophilic phase separation and interconnected ion-transport channels, as confirmed by atomic force microscopy and small angle X-ray scattering. The ImPESN membranes with low swelling showed a relatively high water uptake, high hydroxide ion conductivity together with good mechanical, thermal and alkaline stability. The ionic conductivity of the membranes was in the range of 3.85-14.67×10(-2) S·cm(-1) from 30 to 80 °C. Moreover, a single H2/O2 fuel cell with the ImPESN membrane showed an open circuit voltage of 0.92 V and a maximum power density of 66.4 mW cm(-2) at 60 °C.

Comb-shaped phenolphthalein-based poly(ether sulfone)s as anion exchange membranes for alkaline fuel cells

A series of novel comb-shaped phenolphthalein-based poly(ether sulfone)s was synthesized for preparing anion exchange membranes (AEMs). Hexadecyldimethylamine with a long alkyl chain was used as the quaternization reagent to form a comb-shaped architecture of the copolymers. Due to the presence of a long alkyl side chain with hydrophobicity, the as-synthesized comb-shaped AEMs possess a self-anti-swelling property resulting in a low water uptake and swelling ratio. The PES-B100-C16 membrane exhibits excellent alkaline stability due to the presence of large volumetric β-alkyl chains linking to the cationic group that resist the attack of OH−, and retain available ionic conductivity in a 2 M KOH solution at 60 °C for 360 h. An open circuit voltage of the single cell reached 0.67 V, and the maximum power density was 43 mW cm2 at a current density of 125 mA cm−2 without optimization in a single H2/O2 alkaline fuel cell at 50 °C.

Influence of phenolphthalein groups on the structure and properties of poly(arylene ether sulfone nitrile)-based anion exchange membranes for fuel cells

Two series of novel poly(arylene ether sulfone nitrile) (PESN) multiblock copolymers are synthesized to prepare anion exchange membranes (AEMs) for alkaline fuel cells. To study the effect of phenolphthalein groups on the structure and properties of the membranes, the ion groups facilitating the formation of ion clusters are selectively and densely located on the phenolphthalein-sulfone segments of one and on the bisphenol A-sulfone segments of the other. The morphology and structure of the membranes are observed by atomic force microscopy and small angle X-ray scattering. The phenolphthalein-containing type endows the AEMs with a much clearer and more-defined microphase-separated structure leading to the formation of much larger and more developed interconnected ion-transport channels. As a result, high hydroxide conductivity (in the range of 2.04–12.98 × 10−2 S cm−1 from 30 to 80 °C) and H2/O2 fuel cell performance (an open circuit voltage of 0.92 V and a maximum power density of 66.4 mW cm−2 at 60 °C) can be achieved. Furthermore, the phenolphthalein-containing AEMs also show higher water uptake and mechanical strength, lower swelling ratio, and higher thermal and alkaline stability than the phenolphthalein-free AEMs.