Design of non-fluorinated proton exchange membranes from Poly(Terphenyl fluorenyl isatin) with fluorene-linked sulfonate groups and microblock structures

IF 8.4 1区 工程技术 Q1 ENGINEERING, CHEMICAL
Chaoyi Ba , Shu Xu , Christopher G. Arges , Jae Hyung Park , Jinkyu Park , Meltem Urgun-Demirtas
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Abstract

Proton exchange membranes (PEMs) are essential components in energy storage and conversion devices, such as fuel cells and electrolyzers. In this study, we developed a series of non-fluorinated PEMs from poly (terphenyl fluorenyl isatin) with fluorene-pendent disulfonate groups. These polymers feature a microblock structure composed of hydrophobic blocks, hydrophilic blocks, and alternating blocks, arising from the differences in reactivity, concentration, and solubility between the hydrophobic p-terphenyl and hydrophilic disulfonated fluorene monomers. As a result, the sulfonic acid groups are unevenly distributed along the polymer chains, forming densely charged regions (IEC = 3.52 meq/g) with large ion clusters and lightly charged regions (IEC = 2.16 meq/g) with small ion clusters. This microstructure, combined with the degree of sulfonation, significantly influences the overall properties of the membranes, including robust mechanical strength (47.1–63.2 MPa), high thermal stability (up to 270 °C), low swelling ratio (18–25 % at 80 °C), and high proton conductivity (136–169 mS/cm in deionized water at 80 °C). The PFLSH60 membrane demonstrated comparable fuel cell performance to Nafion 212. Its hydrogen crossover current density was more than two times lower (0.86 mA/cm2 for PFLSH60 compared to 1.83 mA/cm2 for Nafion 212) under testing conditions of 80 °C and 100 % RH. This significantly reduced crossover improves fuel utilization in fuel cell stacks. This work offers valuable insights into the design of robust, high-performance PEMs by systematically analyzing the relationships between membrane structure, properties, and performance.

Abstract Image

设计具有芴连接磺酸基团和微块结构的聚(三联苯芴基靛红)非氟质子交换膜
质子交换膜(PEM)是燃料电池和电解槽等能量储存和转换设备的重要组成部分。在这项研究中,我们利用带有芴附二磺酸基团的聚(三联苯芴基)靛红开发出了一系列非氟质子交换膜。由于疏水性对三联苯单体和亲水性二磺化芴单体的反应活性、浓度和溶解度不同,这些聚合物具有由疏水嵌段、亲水嵌段和交替嵌段组成的微嵌段结构。因此,磺酸基团沿着聚合物链分布不均,形成了带有大离子团簇的强电荷区(IEC = 3.52 meq/g)和带有小离子团簇的弱电荷区(IEC = 2.16 meq/g)。这种微观结构与磺化程度相结合,极大地影响了膜的整体性能,包括强大的机械强度(47.1-63.2 兆帕)、高热稳定性(高达 270 °C)、低膨胀率(80 °C 时为 18-25%)和高质子传导率(80 °C 时在去离子水中为 136-169 mS/cm)。PFLSH60 膜的燃料电池性能与 Nafion 212 相当。在 80 °C 和 100 % 相对湿度的测试条件下,其氢交叉电流密度降低了两倍多(PFLSH60 为 0.86 mA/cm2,而 Nafion 212 为 1.83 mA/cm2)。交叉电流的大幅减少提高了燃料电池堆中燃料的利用率。这项工作通过系统分析膜结构、特性和性能之间的关系,为设计坚固耐用的高性能 PEM 提供了宝贵的见解。
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来源期刊
Journal of Membrane Science
Journal of Membrane Science 工程技术-高分子科学
CiteScore
17.10
自引率
17.90%
发文量
1031
审稿时长
2.5 months
期刊介绍: The Journal of Membrane Science is a publication that focuses on membrane systems and is aimed at academic and industrial chemists, chemical engineers, materials scientists, and membranologists. It publishes original research and reviews on various aspects of membrane transport, membrane formation/structure, fouling, module/process design, and processes/applications. The journal primarily focuses on the structure, function, and performance of non-biological membranes but also includes papers that relate to biological membranes. The Journal of Membrane Science publishes Full Text Papers, State-of-the-Art Reviews, Letters to the Editor, and Perspectives.
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