Yanchao Zhang , Yiman Gu , Zhanyu Li , Shiyao Sun , Xiangwei Li , Baozeng Sun , Xiaoyu Yu , Zhe Wang
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At 80 °C, the ionic conductivity of QPTPF<sub>6</sub>D-25% AEM reached 151.02 mS cm<sup>−1</sup>. Incorporation of hydrophobic fluorinated groups and rigid aryl rings to maintain high mechanical properties (above 40 MPa under hydrated condition) and low swelling ratio (below 22.69%). Ether-free main-chain type AEMs were prepared to have better alkali resistance, and QPTPF<sub>6</sub>D-25% AEM was soaked in 2 M NaOH for 1800 h, and the ion retention rate remained above 95%. In addition, the QPTPF<sub>6</sub>D-25% AEM's peak power density (PPD) was 616.93 mW cm<sup>−2</sup> under 100 % RH and 1.75 bar test conditions. 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Ether-free main-chain type AEMs were prepared to have better alkali resistance, and QPTPF<sub>6</sub>D-25% AEM was soaked in 2 M NaOH for 1800 h, and the ion retention rate remained above 95%. In addition, the QPTPF<sub>6</sub>D-25% AEM's peak power density (PPD) was 616.93 mW cm<sup>−2</sup> under 100 % RH and 1.75 bar test conditions. 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引用次数: 0
摘要
阴离子交换膜(AEMs)面临诸多挑战,其耐碱性稳定性差、离子电导率低、尺寸稳定性差等缺点阻碍了其广泛应用。本文采用超强酸催化缩聚反应,成功制备了一系列含柔性联苯(1,2-二苯基乙烷)的氟化聚芳基哌啶阴离子交换膜(QPTPF6D-x)。柔性联苯是一种含有可折叠的旋转烷基链的芳香单体。促进了哌啶阳离子基团的聚集,与氟化基团构建更明显的微相分离结构,有效提高了导电性能。在80℃时,QPTPF6D-25% AEM的离子电导率达到151.02 mS cm−1。加入疏水氟化基团和刚性芳基环,以保持高机械性能(在水合条件下高于40 MPa)和低膨胀率(低于22.69%)。制备的无醚主链型AEM具有较好的耐碱性,将QPTPF6D-25% AEM在2 M NaOH中浸泡1800 h,离子保留率保持在95%以上。此外,在100% RH和1.75 bar的测试条件下,QPTPF6D-25% AEM的峰值功率密度(PPD)为616.93 mW cm−2。同时,通过密度泛函理论(DFT)证实了引入柔性联苯和氟基团的优势。
High-performance fluorinated poly(aryl-piperidine) anion exchange membranes containing flexible biphenyls: Realize effective regulation between ionic conductivity and dimensional stability
The anion exchange membranes (AEMs) face many challenges, and drawbacks such as poor alkali resistance stability, low ionic conductivity, and poor dimensional stability have hindered widespread applications. Herein, a series of fluorinated poly(aryl-piperidine) anion exchange membranes (QPTPF6D-x) containing flexible biphenyls (1,2-diphenylethanes) were successfully prepared by using an ultra-strong acid-catalyzed polycondensation reaction. Flexible biphenyl is an aromatic monomer containing a collapsible rotary alkyl chain. It promotes the aggregation of piperidinium cationic groups and the construction of a more obvious microphase separated structure with fluorinated groups, effectively improving the conduction. At 80 °C, the ionic conductivity of QPTPF6D-25% AEM reached 151.02 mS cm−1. Incorporation of hydrophobic fluorinated groups and rigid aryl rings to maintain high mechanical properties (above 40 MPa under hydrated condition) and low swelling ratio (below 22.69%). Ether-free main-chain type AEMs were prepared to have better alkali resistance, and QPTPF6D-25% AEM was soaked in 2 M NaOH for 1800 h, and the ion retention rate remained above 95%. In addition, the QPTPF6D-25% AEM's peak power density (PPD) was 616.93 mW cm−2 under 100 % RH and 1.75 bar test conditions. Meanwhile, the advantages of introducing flexible biphenyl and fluorinated groups were confirmed by density functional theory (DFT).
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