高性能共价有机框架阴离子交换膜及其燃料电池与电解水应用

doi:10.11949/0438-1157.20251392

摘要/Abstract

摘要：

阴离子交换膜（AEM）是燃料电池与电解水制氢系统的核心组件，其离子电导率直接决定了器件的转换效率。针对传统 AEM 存在的离子传导率低的使用瓶颈，本文设计并制备了基于共价有机框架材料（COF）的高性能阴离子交换膜。通过门舒特金反应将功能化改性后的 COF 材料和聚芳基哌啶聚合物（PTP）化学键合，得到QPTP-COF AEM。多孔COF材料的引入大幅提升了膜内的自由体积，构建连续离子传输通道，降低离子传输阻力。结果表明，与QPTP AEM相比，QPTP-COF AEM的离子电导率可达 177.2 mS cm^-1。将其应用于燃料电池与电解水测试，均展现出优异的能量转换效率，为高性能 AEM 的设计提供了新策略。

关键词: 燃料电池, 电解水, 制氢, 阴离子交换膜, 共价有机框架材料（COF）, 自由体积

Abstract:

The anion exchange membrane (AEM) is the core component of fuel cells and water electrolysis hydrogen production systems, and its ionic conductivity directly determines the energy conversion efficiency of the device. In this work, a new type of AEM based on COF material was designed and fabricated to address the bottleneck of traditional AEM ionic conductivity. The QPTP-COF AEM was fabricated via the Menshutkin reaction, which enables covalent bonding between COF materials and polymer chains. Compared with the pristine QPTP membrane, the QPTP-COF AEM exhibits a higher hydroxide ion (OH⁻) conductivity of 177.2 mS cm^-1, and demonstrates excellent performance in both fuel cells and water electrolysis systems. This work provides a novel strategy for the design and preparation of high-performance AEMs.

Key words: fuel cell, water electrolysis, hydrogen production, anion exchange membrane, Covalent Organic Frameworks (COF), free volume

中图分类号:

TQ 028.8

马小琴, 赵晓辉, 付林, 强也, 白清川. 高性能共价有机框架阴离子交换膜及其燃料电池与电解水应用[J]. 化工学报, DOI: 10.11949/0438-1157.20251392.

Xiaoqin MA, Xiaohui ZHAO, Lin FU, Ye QIANG, Qingchuan BAI. High-performance covalent organic framework anion exchange membranes for fuel cells and water electrolysis[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251392.

图/表 12

图1 COF材料的制备路径

Fig. 1 The synthesis route of COF materials

图2 QPTP-COF AEMs的制备路径

Fig. 2 The synthesis route of QPTP-COF AEMs

图3 A-COF材料的（a）TEM谱图，（b）XRD谱图以及（e）（f）SEM谱图，修饰后的COF 材料的（c）TEM谱图，（d）XRD谱图以及（g）（h）SEM谱图

Fig. 3 (a) TEM spectrum, (b) XRD spectrum, and (e)(f) SEM spectrum of A-COF material; (c) TEM spectrum, (d) XRD spectrum, and (g)(h) SEM spectrum of modified COF material

图4 A-COF材料的（a）N2吸附/解吸等温线和（b）孔径分布图

Fig. 4 (a) N2 adsorption/desorption isotherms and (b) pore size distribution plot of A-COF material

图5 QPTP-COF AEM的（a）二维核磁谱图和（b）化学结构式。

Fig. 5 (a) 2D NMR spectrum and (b) chemical structure of QPTP-COF AEM

图6 QPTP-COF AEM的（a）SEM表面图和膜照片，（b）SEM截面图，（c）TEM图，QPTP AEM的（d）SEM表面图和膜照片，（e）SEM截面图和（f）TEM图，（g）QPTP-COF作为离聚物配置的催化剂浆料的TEM图

Fig. 6 (a) SEM surface image and membrane photograph, (b) SEM cross-sectional image and (c) TEM image of QPTP-COF AEM, (d) SEM surface image and membrane photograph, (e) SEM cross-sectional image and (f) TEM image of QPTP AEM, (g) TEM image of catalyst slurry configured with QPTP-COF as the ionomer

图7 QPTP-COF 和QPTP的TGA曲线

Fig. 7 TGA curves of QPTP-COF and QPTP

图8 QPTP-COF 和QPTP的（a）OH-电导率和（b）拉伸性能

Fig. 8 QPTP-COF and QPTP (a) OH- conductivity and (b) mechanical property

表1 QPTP AEM 和QPTP-COF AEM的性能

Table 1 The properties of QPTP AEM and QPTP-COF AEM

聚合物	吸水（%）^a	溶胀（%）^a	拉伸（MPa）^b	电导率（mS/cm）^a
QPTP	120.2±5.4	17.1±0.7	12.2±2.3	148.1±4.5
QPTP-COF	245.3±9.1	21.3±0.9	11.6±1.6	177.2±2.6

图10 QPTP-COF AEM耐碱测试后的（a）OH-电导率的保留率和（b）核磁谱图

Fig. 10 QPTP-COF AEM after alkali resistance test: (a) retention rate of OH- conductivity and (b) NMR spectrum

图7 QPTP-COF 和QPTP的（a）吸水率和（b）溶胀率

Fig. 7 QPTP-COF and QPTP (a) water uptake and (b) swelling ratio

图11 QPTP-COF AEM 和QPTP AEM的（a）燃料电池性能（0 kPa），（b）燃料电池性能（100 kPa），（c）电解水性能和（d）相关性能对比图。

Fig. 11 QPTP-COF AEM and QPTP AEM (a) fuel cell performance (0 kPa), (b)fuel cell performance (100 kPa), (c) water electrolysis performance and (d) Comparative performance diagram

参考文献 33

[1]	Zeng G H, Liu M B, Lei Z X, et al. Optimal configuration of hydrogen energy storage in an integrated energy system considering variable hydrogen production efficiency[J]. Journal of Energy Storage, 2024, 98: 113044.
[2]	Shu K Y, Guan B, Zhuang Z Q, et al. Reshaping the energy landscape: Explorations and strategic perspectives on hydrogen energy preparation, efficient storage, safe transportation and wide applications[J]. International Journal of Hydrogen Energy, 2025, 97: 160-213.
[3]	Wei X Y, Sharma S, Waeber A, et al. Environmental implications of solid oxide fuel cell system for hydrogen sustainability[J]. Resources, Conservation and Recycling, 2025, 215: 108134.
[4]	Navinkumar T M, Bharatiraja C. Sustainable hydrogen energy fuel cell electric vehicles: A critical review of system components and innovative development recommendations[J]. Renewable and Sustainable Energy Reviews, 2025, 215: 115601.
[5]	Laleh S S, Rezaei Mousavi H S, Rabet S, et al. Solar thermal assisted proton exchange membrane electrolyzer and solid oxide fuel cell system based on biomass gasification for green power and hydrogen production: Multi-objective optimization and exergoeconomic analysis[J]. Energy Conversion and Management, 2025, 337: 119900.
[6]	Wang Z Y, Sun G, Lewis N H C, et al. Water-mediated ion transport in an anion exchange membrane[J]. Nature Communications, 2025, 16: 1099.
[7]	Kim H, Jeon S, Choi J, et al. Interfacially Assembled Anion Exchange Membranes for Water Electrolysis[J]. ACS Nano, 2024, 18(47): 32694-32704.
[8]	Muhyuddin M, Santoro C, Osmieri L, et al. Anion-Exchange-Membrane Electrolysis with Alkali-Free Water Feed[J]. Chemical Reviews, 2025(15), 125: 6906-6976.
[9]	Altinisik H, Celebi C, Ozden A, et al. A review on membranes for anion exchange membrane water electrolyzers[J]. Renewable and Sustainable Energy Reviews, 2026, 226: 116277.
[10]	Song W J, Ge X L, Wu L, et al. Bottlenecks of commercializing anion exchange membranes for energy devices[J]. Joule, 2025, 9(8): 102051.
[11]	Moghaddam M S, Kafshgari M S, Bahari A, et al. Types, properties, and applications of non-precious oxygen reduction reaction electrocatalyst: A review[J]. Journal of Energy Chemistry, 2025, 107: 305-344.
[12]	Wang N, Ou P F, Miao R K, et al. Doping Shortens the Metal/Metal Distance and Promotes OH Coverage in Non-Noble Acidic Oxygen Evolution Reaction Catalysts[J]. Journal of the American Chemical Society, 2023(14), 145: 7829-7836.
[13]	Mao J Y, Wang X C, Nie Y T, et al. Anion exchange ionomers for anion exchange membrane fuel cells: properties, advances, and future directions[J]. International Journal of Hydrogen Energy, 2025, 196: 152593.
[14]	Liu L, Deng Y K, Zhang W L, et al. Highly alkali-stable polyolefin-based anion exchange membrane enabled by N-cyclic quaternary ammoniums for alkaline fuel cells[J]. Journal of Membrane Science, 2023, 672: 121441.
[15]	Cao D F, Nie F M, Liu M, et al. Crosslinked anion exchange membranes prepared from highly reactive polyethylene and polypropylene intermediates[J]. Journal of Membrane Science, 2022, 661: 120921.
[16]	Chen J J, Shen C H, Gao S. Polyepichlorohydrin grafted poly(phenylene oxide) to construct hydrophilic and hydrophobic microphase separation anion exchange membrane[J]. Reactive and Functional Polymers, 2024, 195: 105808.
[17]	Ng W K, Wong W Y, Loh K S, et al. A comprehensive overview of polyphenylene oxide-based anion exchange membranes from the perspective of ionic conductivity and alkaline stability[J]. Journal of Industrial and Engineering Chemistry, 2024, 138: 49-71.
[18]	Ma X Q, Xiang Q, Yuan W, et al. Localized stacked hyper branched anion exchange membrane for fuel cell[J]. Journal of Membrane Science, 2024, 694: 122432.
[19]	Yuan C L, Chen Y H, Lu X L, et al. Reducing hydroxide transport resistance by introducing high fractional free volume into anion exchange membranes[J]. Journal of Membrane Science, 2024, 701: 122769.
[20]	Sun S Y, Zhao J L, Wu J Y, et al. Covalent organic frameworks engineered poly(aryl piperidinium) ion-conducting networks via hydrogen-bonding for anion exchange membrane fuel cells[J]. Journal of Membrane Science, 2025, 736: 124623.
[21]	Lu X L, Zhang Y, Ma X Q, et al. Hydrogen Bond Network Assisted Ultrafast Ion Transport of Anion Exchange Membrane Grafting with Covalent Organic Frameworks for Hydrogen Conversion[J]. Angewandte Chemie International Edition, 2025, 137(21): e202503372.
[22]	Yuan C L, Ma X Q, Shen Z D, et al. Sandwich-Like Free-Standing Covalent Organic Framework Anion Exchange Membranes for Water Electrolysis[J]. Angewandte Chemie International Edition, 2025, 64(48): e202513244.
[23]	Wang X Y, Shi B B, Yang H, et al. Assembling covalent organic framework membranes with superior ion exchange capacity[J]. Nature Communications, 2022, 13: 1020.
[24]	Ma H P, Liu B L, Li B, et al. Cationic Covalent Organic Frameworks: A Simple Platform of Anionic Exchange for Porosity Tuning and Proton Conduction[J]. Journal of the American Chemical Society, 2016, 138(18): 5897-5903.
[25]	Chen W T, Liu Q, Pang B, et al. De Novo Design of Aminopropyl Quaternary Ammonium-Functionalized Covalent Organic Frameworks for Enhanced Polybenzimidazole Anion Exchange Membranes[J]. Small, 2025, 21(1): 2407260.
[26]	Li Z L, Li H, Guan X Y, et al. Three-Dimensional Ionic Covalent Organic Frameworks for Rapid, Reversible, and Selective Ion Exchange[J]. Journal of the American Chemical Society, 2017, 139(49): 17771-17774.
[27]	Liu Y J, Gao W T, Zhu A M, et al. High-performance di-piperidinium-crosslinked poly(p-terphenyl piperidinium) anion exchange membranes[J]. Journal of Membrane Science, 2023, 687: 122045.
[28]	Ma X Q, Lu X L, Liang S M, et al. Achieving ultra-low oxygen transport resistance of fuel cells by microporous covalent organic framework ionomers[J]. Chemical Science, 2025, 16(46): 22111-22118.
[29]	Fan C Y, Wu H, Guan J Y, et al. Scalable Fabrication of Crystalline COF Membranes from Amorphous Polymeric Membranes[J]. Angewandte Chemie International Edition, 2021, 60(33): 18051-18058.
[30]	Gao W T, Gao X L, Zhang Q G, et al. Durable poly(binaphthyl-co-p-terphenyl piperidinium)-based anion exchange membranes with dual side chains[J]. Journal of Energy Chemistry, 2024, 89: 324-335.
[31]	Li Q H, Hu M X, Ge C X, et al. Ionomer degradation in catalyst layers of anion exchange membrane fuel cells[J]. Chemical Science, 2023, 14(38): 10429-10434.
[32]	Zhang K Y, Yu W S, Ge X L, et al. DFT insight of hydroxide degradation pathways for heterocyclic quaternary ammonium cations in anion exchange membranes[J]. Journal of Membrane Science, 2023, 678: 121672.
[33]	Luo X Y, Rojas-Carbonell S, Yan Y S, et al. Structure-transport relationships of poly(aryl piperidinium) anion-exchange membranes: Eeffect of anions and hydration[J]. Journal of Membrane Science, 2020, 598: 117680.