纺织学报 ›› 2025, Vol. 46 ›› Issue (09): 242-249.doi: 10.13475/j.fzxb.20241205502

• 综合述评 • 上一篇    下一篇

离子交换膜及其在燃料电池中应用的研究进展

苏乙1, 曾鹏瑾1, 孙菲1,2(), 郭玉海1,2   

  1. 1.浙江理工大学 浙江省纤维材料和加工技术研究重点实验室, 浙江 杭州 310018
    2.浙江省现代纺织技术创新中心(鉴湖实验室), 浙江 绍兴 312030
  • 收稿日期:2024-12-25 修回日期:2025-06-13 出版日期:2025-09-15 发布日期:2025-11-12
  • 通讯作者: 孙菲(1992—),女,博士,讲师。主要研究方向为纤维基复合膜在能源与环境中的应用。E-mail: sunfei_92@zstu.edu.cn
  • 作者简介:苏乙(2001—),男,硕士生。研究方向为阳离子交换膜在液流电池中的应用。
  • 基金资助:
    国家重点研发计划项目(2021YFB3801500);浙江省教育厅一般科研项目(Y202457127)

Research progress and application of ion exchange membranes in fuel cells

SU Yi1, ZENG Pengjin1, SUN Fei1,2(), GUO Yuhai1,2   

  1. 1. Zhejiang Provincial Key Laboratory of Fiber Materials and Manufacturing Technology, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Zhejiang Provincial Innovation Center of Advanced Textile Technology (Jianhu Laboratory), Shaoxing, Zhejiang 312030, China
  • Received:2024-12-25 Revised:2025-06-13 Published:2025-09-15 Online:2025-11-12

摘要:

随着全球经济及工业的不断进步与发展,对能源的需求也在快速增长,构建全新、高效、清洁的可持续发展能源体系成为未来研究的主要热点。燃料电池作为集“开源”和“节流”2种功能于一体的优质新能源技术被广泛研究,本文从离子交换膜在燃料电池中的核心作用出发,首先概述了燃料电池用离子交换膜的性能要求,然后介绍了燃料电池用离子交换膜的发展现状,主要包括阳离子交换膜、阴离子交换膜和两性离子交换膜的研究现状及可能面临的问题。通过综合分析离子交换膜的性能和应用场景,总结现阶段研究存在的问题并对未来研究提供可行的解决思路。随着研究的深入和技术的成熟,燃料电池有望在实现“碳达峰、碳中和”目标的过程中发挥关键作用。

关键词: 燃料电池, 离子交换膜, 质子交换膜, 功率密度, 质子传导率

Abstract:

Significance The growing demand for electrical energy, driven by industrial development, urbanization and rising living standards, highlights the urgent need for sustainable alternative energy solutions. Conventional energy sources, primarily fossil fuels, are becoming increasingly unsuitable due to their impact on the environment. In order to address these challenges, fuel cells have received attention as a promising clean energy technology. The core component of fuel cell operation is the ion exchange membrane, which plays a key role in determining the overall efficiency, stability and service life of the fuel cell. Therefore, advancing the performance and cost-effectiveness of fuel cell technology, especially ion exchange membranes, is critical. This study examines in detail the current status of ion exchange membrane technology in fuel cells, highlighting its key role in promoting fuel cells as a mainstream energy source. By increasing the efficiency of these membranes and reducing production costs, fuel cells can be more widely used, supporting the transition to a sustainable, low-carbon energy future.

Progress Significant progress has been made in the development of ion exchange membranes for fuel cells over the past few decades. One of the main challenges in membrane technology is balancing high ionic conductivity, mechanical strength, and chemical stability. These properties are critical to ensuring long-term efficiency and durability of fuel cells under a variety of operating conditions. In order to address these challenges, researchers have developed several types of ion exchange membranes, including proton exchange membranes (PEMs), anion exchange membranes (AEMs), and amphoteric ion exchange membranes (AEMDs). Each type of membrane has unique properties tailored for specific fuel cell applications. For example, PEMs are commonly used in proton exchange fuel cells and have high proton conductivity, but face challenges with temperature stability. AEMs, on the other hand, are more suitable for alkaline fuel cells and have the potential to reduce costs and enhance stability in harsh environments. In addition to developing various membrane types, substantial progress has been made in improving these membranes to enhance their performance. Blending different polymer materials or adding nanoparticles to the membrane are effective strategies to improve mechanical strength and ionic conductivity. These improvements help reduce membrane losses and increase ion transport efficiency, thereby improving the overall performance of the fuel cell. In addition, these advances have helped reduce costs, making fuel cells more commercially viable. The addition of materials such as nanocomposites and conductive polymers has enabled the development of membranes that perform well in both high-temperature and high-humidity conditions, addressing some of the key limitations of earlier designs. These innovations have opened up new avenues for the commercialization of fuel cells, making them a more practical alternative to traditional energy sources in a variety of applications, from automobiles to stationary power generation.

Conclusion and Prospect Despite the encouraging progress in the development of ion exchange membranes for fuel cells, several challenges still exist that hinder their widespread commercialization. The most important of these issues is the low ionic conductivity of many ion exchange membranes at high temperatures, which reduces the overall efficiency of fuel cells in practical applications. In addition, the stability of these membranes under harsh operating conditions remains a key challenge. In addition, while advances in membrane materials and manufacturing technologies have brought about improved performance, the cost-effectiveness of these technologies remains a barrier to large-scale adoption. In order to address these challenges, future research must focus on exploring new materials that provide better ionic conductivity and stability at higher temperatures. Novel polymers, hybrid materials, and nanomaterials are currently the mainstream research directions. In addition, optimizing the structure and composition of ion exchange membranes can further improve their performance, especially by improving their resistance to chemical degradation and enhancing their thermal stability. With the continuous progress in materials science, manufacturing technology, and system integration, fuel cells and their ion exchange membranes are expected to play a key role in achieving global carbon reduction goals. As the technology matures and becomes more cost-effective, fuel cells are likely to make a significant contribution to meeting the world's energy needs in a sustainable and environmentally friendly manner. This shift will not only transform the energy industry, but also pave the way for a more sustainable, cleaner energy future.

Key words: fuel cell, ion exchange membrane, proton exchange membrane, power density, proton conductivity

中图分类号: 

  • TM911.48

图1

常见离子交换膜及其离子交换基团"

表1

阳离子交换膜交换基团及性能对比"

交换基团 样品名称 原料 制备方法 质子传导率/
(mS·cm-1)
峰值功率密度/
(mW·cm-2)
参考
文献
—SO3H Nafion PFSA 挤出或浇筑 12.1 82.0 [7]
Nafion-SPEEK-GO Nafion、SPEEK、GO 共混、浇筑 322.2 621.2 [27]
SPAES-X SPAES 共混、浇筑 203.1 468.0 [19]
—COOH
—PO4H2
OPBI-xPI-COOH PI-COOH、OPBI 共混、流延 89.0 463.0 [22]
SPEEK/PAPOP PAPOP、SPEEK 流延 417.0 120.5 [21]

表2

阴离子交换膜交换基团及性能对比"

交换基团 样品名称 原料 制备方法 离子传导率/
(mS·cm-1)
峰值功率密度/
(mW·cm-2)
离子交换容量值/
(meq·g-1)
参考
文献
—NH4 x-PP-DMHDA-
20
PP、TMA、
DMHDA
热压、交联 56.5 122.0 1.8 [32]
PVA/qPPO PE、PPO 交联、浇筑 151.0 - 3.0 [27]
QPE PPE、FO 浇筑 144.0 297.0 1.9 [34]
—C5H11N2
(咪唑基团)
PyPBI-BuI PBI、Alk-I 浇筑 128.6 - 3.4 [37]
FB-OPBI-6-
HQA-x
OPBI、FB、TDAP 浇筑 92.2 - 3.0 [29]
—C5H11N
(哌啶基团)
b-PTP-2.5 BPA-P 浇筑 145.0 2 300.0 2.8 [38]

表3

常见两性离子交换膜交换基团及性能对比"

交换基团 样品名称 原料 制备方法 离子传导率/
(mS·cm-1)
离子交换容量值/
(meq·g-1)
参考
文献
—SO3H和—NH4 SPES/TEOS/TPABS-70 SPES、TEOS、TPABS 溶胶-凝胶法交联 72.4 1.4 [44]
SPES/TEOS/TPABS SPES、TEOS、TPABS 溶胶-凝胶法交联 72.4 2.0 [41]
—PO4H2
—C3H5N2
PBI-B3-9% PBI、OBBA、DAB 浇筑 43.0 - [42]
[1] GALLAGHER J. Costing out fuel cells[J]. Nature Energy, 2023, 8(9): 907-907.
doi: 10.1038/s41560-023-01366-w
[2] ABBASI R, SETZLER B P, YAN Y. Material and system development needs for widespread deployment of hydroxide exchange membrane fuel cells in light-duty vehicles[J]. Energy & Environmental Science, 2023, 16(10): 4404-4422.
[3] CHEN R, XU W, DENG S, et al. Towards the Carnot efficiency with a novel electrochemical heat engine based on the Carnot cycle: thermodynamic considera-tions[J]. Energy, 2023, 284:128577.
doi: 10.1016/j.energy.2023.128577
[4] MUSTAIN W E, CHATENET M, PAGE M, et al. Durability challenges of anion exchange membrane fuel cells[J]. Energy & Environmental Science, 2020, 13(9): 2805-2538.
[5] 李晓锋. 功能导向的高性能离子交换膜结构设计与性能研究[D]. 合肥: 中国科学技术大学,2023:2-4.
LI Xiaofeng. Function-oriented high-performance ion exchange membrane structure design and performance research[D]. Hefei: University of Science and Technology of China, 2023: 2-4.
[6] 陈志华, 周键, 王三反. 离子交换膜选择透过机理的研究进展[J]. 应用化工, 2021, 50(5): 1366-1371.
CHEN Zhihua, ZHOU Jian, WANG Sanfan. Research progress on the selective permeation mechanism of ion exchange membranes[J]. Applied Chemical Industry, 2021, 50(5): 1366-1371.
[7] YANDRASITS M A, LINDELL M J, HAMROCK S J. New directions in perfluoroalkyl sulfonic acid-based proton-exchange membranes[J]. Current Opinion in Electrochemistry, 2019, 18: 90-98.
doi: 10.1016/j.coelec.2019.10.012
[8] PRYKHODKO Y, FATYEYEVA K, HESPEL L, et al. Progress in hybrid composite Nafion-based membranes for proton exchange fuel cell applic-ation[J]. Chemical Engineering Journal, 2021, 409: 127329.
doi: 10.1016/j.cej.2020.127329
[9] KARIMI M B, MOHAMMADI F, HOOSHYARI K. Recent approaches to improve Nafion performance for fuel cell applications: a review[J]. International Journal of Hydrogen Energy, 2019, 44(54): 28919-28938.
doi: 10.1016/j.ijhydene.2019.09.096
[10] YE H, HUANG J, XU J J, et al. New membranes based on ionic liquids for PEM fuel cells at elevated temperatures[J]. Journal of Power Sources, 2008, 178(2): 651-660.
doi: 10.1016/j.jpowsour.2007.07.074
[11] YAZILI D, MARINI E, SAATKAMP T, et al. Sulfonated poly(phenylene sulfone) blend membranes finding their way into proton exchange membrane fuel cells[J]. Journal of Power Sources, 2023, 563: 232791.
doi: 10.1016/j.jpowsour.2023.232791
[12] DEIVANAYAGAM P, RAMANUJAM RAMAMOORTHY A, JAISANKAR S N. Synthesis and characterization of sulfonated poly(arylene ether sulfone)/silicotungstic acid composite membranes for fuel cells[J]. Polymer Journal, 2013, 45(2): 166-172.
doi: 10.1038/pj.2012.102
[13] ZENG P, SU Y, HUANG B, et al. Sulfonated poly (ether ether ketone) asymmetrical pore-filling PTFE composite membrane with highly selective for vanadium flow batteries[J]. International Journal of Hydrogen Energy, 2025, 120: 365-373.
doi: 10.1016/j.ijhydene.2025.03.311
[14] HUYNH T B N, SONG J, BAE H E, et al. Enhancing proton exchange membrane water electrolysis with a checkered carbon matrix containing Ir-Ru nano-particles[J]. Advanced Energy Materials, 2024, 14(46): 2402179.
doi: 10.1002/aenm.v14.46
[15] HUANG L, GUAN J, SUN X, et al. High free volume crosslinked membranes constructed by stereocrosslinker for high-temperature proton-exchange membrane fuel cells[J]. Journal of Membrane Science, 2024, 709: 123100.
doi: 10.1016/j.memsci.2024.123100
[16] ELWAN H A, MAMLOUK M, SCOTT K. A review of proton exchange membranes based on protic ionic liquid/polymer blends for polymer electrolyte membrane fuel cells[J]. Journal of Power Sources, 2021, 484: 229197.
doi: 10.1016/j.jpowsour.2020.229197
[17] HARAGIRIMANA A, INGABIRE P B, LIU Y, et al. An effective strategy to enhance the performance of the proton exchange membranes based on sulfonated poly(ether ether ketone)s[J]. International Journal of Hydrogen Energy, 2020, 45(16): 10017-10029.
doi: 10.1016/j.ijhydene.2020.01.180
[18] DÖNMEZ G, OKUTAN M, DELIGÖZ H. Blend membranes of sulfonated poly (ether ether ketone) and thermoplastic poly (urethane) for fuel cells[J]. Journal of Polymer Research, 2019, 26(6):133.
doi: 10.1007/s10965-019-1792-7
[19] HARAGIRIMANA A, INGABIRE P B, ZHU Y, et al. Four-polymer blend proton exchange membranes derived from sulfonated poly(aryl ether sulfone)s with various sulfonation degrees for application in fuel cells[J]. Journal of Membrane Science, 2019, 583: 209-219.
doi: 10.1016/j.memsci.2019.04.014
[20] LIU F, KINGSBURY R S, RECH J J, et al. Effect of osmotic ballast properties on the performance of a concentration gradient battery[J]. Water Res, 2022, 212: 118076.
doi: 10.1016/j.watres.2022.118076
[21] WANG S, ZHU T, SHI B, et al. Porous organic polymer with high-density phosphoric acid groups as filler for hybrid proton exchange membranes[J]. Journal of Membrane Science, 2023, 666: 121147.
doi: 10.1016/j.memsci.2022.121147
[22] QU E, CHENG G, XIAO M, et al. Composite membranes consisting of acidic carboxyl-containing polyimide and basic polybenzimidazole for high-temperature proton exchange membrane fuel cells[J]. Journal of Materials Chemistry A, 2023, 11(24): 12885-12895.
doi: 10.1039/D2TA08904A
[23] LIU N, BI S, ZHANG Y, et al. Nanofiber-based polymer electrolyte membranes for fuel cells[J]. Carbon Energy, 2025: e677.
[24] YUZER B, SELCUK H, CHEHADE G, et al. Evaluation of hydrogen production via electrolysis with ion exchange membranes[J]. Energy, 2020, 190: 116420.
doi: 10.1016/j.energy.2019.116420
[25] LIANG Z, YANG W, YIN Z, et al. Chlor-alkali membrane cell process for industrial waste salt utilization: fundamentals and challenges[J]. Desalination, 2024, 587: 117921.
doi: 10.1016/j.desal.2024.117921
[26] THAKUR A K, MALMALI M. Advances in polymeric cation exchange membranes for electrodialysis: an overview[J]. Journal of Environmental Chemical Engineering, 2022, 10(5): 108295.
doi: 10.1016/j.jece.2022.108295
[27] MISHRA A K, KIM N H, JUNG D, et al. Enhanced mechanical properties and proton conductivity of Nafion-SPEEK-GO composite membranes for fuel cell applications[J]. Journal of Membrane Science, 2014, 458: 128-135.
doi: 10.1016/j.memsci.2014.01.073
[28] LIU L, LI Q, DAI J, et al. A facile strategy for the synthesis of guanidinium-functionalized polymer as alkaline anion exchange membrane with improved alkaline stability[J]. Journal of Membrane Science, 2014, 453: 52-60.
doi: 10.1016/j.memsci.2013.10.054
[29] 李金晟. 基于聚苯并咪唑和聚芳醚酮阴离子交换膜的制备及其性能研究[D]. 长春: 长春工业大学, 2020:10-11.
Li Jinsheng. Preparation and performance study of anion exchange membrane based on polybenzimidazole and polyaryletherketone[D]. Changchun: Changchun University of Technology, 2020:10-11.
[30] HUANG J, YU Z, TANG J, et al. A review on anion exchange membranes for fuel cells: anion-exchange polyelectrolytes and synthesis strategies[J]. International Journal of Hydrogen Energy, 2022, 47(65): 27800-27820.
doi: 10.1016/j.ijhydene.2022.06.140
[31] DAS G, CHOI J-H, NGUYEN P K T, et al. Anion exchange membranes for fuel cell application: a review[J]. Polymers, 2022, 14(6): 1197.
doi: 10.3390/polym14061197
[32] 张国良, 于泽, 张秋根, 等. 侧链型氟掺杂聚 (对三联苯哌啶) 阴离子交换膜的制备[J]. 膜科学与技术, 2024, 44(6):6-8.
ZHANG Guoliang, YU Ze, ZHANG Qiugen, et al. Preparation of side chain fluorine-doped poly (p-terphenylpiperidine) anion exchange membrane[J]. Membrane Science & Technology, 2024, 44(6):6-8.
[33] ZHANG M, LIU J, WANG Y, et al. Highly stable anion exchange membranes based on quaternized polypropylene[J]. Journal of Materials Chemistry A, 2015, 3(23): 12284-12296.
doi: 10.1039/C5TA01420D
[34] DONG J, LI H, REN X, et al. Anion exchange membranes of bis-imidazolium cation crosslinked poly(2,6-dimethyl-1,4-phenylene oxide) with enhanced alkaline stability[J]. International Journal of Hydrogen Energy, 2019, 44(39): 22137-22145.
doi: 10.1016/j.ijhydene.2019.06.130
[35] PELTIER C R, YOU W, FACKOVIC VOLCANJK D, et al. Quaternary ammonium-functionalized polyethylene-based anion exchange membranes: balancing performance and stability[J]. ACS Energy Letters, 2023, 8(5): 2365-2372.
doi: 10.1021/acsenergylett.3c00319
[36] GONG S, BAI L, LI L, et al. Block copolymer anion exchange membrane containing polymer of intrinsic microporosity for fuel cell application[J]. International Journal of Hydrogen Energy, 2021, 46(2): 2269-2281.
doi: 10.1016/j.ijhydene.2020.10.068
[37] SANA B, DAS A, SHARMA M, et al. Alkaline anion exchange membrane from alkylated polybenzimid-azole[J]. ACS Applied Energy Materials, 2021, 4(9): 9792-9805.
doi: 10.1021/acsaem.1c01862
[38] LEE K H, CHU J Y, KIM A R, et al. Fabrication of high-alkaline stable quaternized poly(arylene ether ketone)/graphene oxide derivative including zwitterion for alkaline fuel cells[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(26): 8824-8834.
[39] OGIHARA N, NAGAYA K, YAMAGUCHI H, et al. Direct capacity regeneration for spent Li-ion batteries[J]. Joule, 2024, 8(5): 1364-1379.
doi: 10.1016/j.joule.2024.02.010
[40] KU A Y, ALONSO E, EGGERT R, et al. Grand challenges in anticipating and responding to critical materials supply risks[J]. Joule, 2024, 8(5): 1208-1223.
doi: 10.1016/j.joule.2024.03.001
[41] 孙丽娜. 两性离子磺化聚醚砜复合质子交换膜的制备与性能研究[D]. 南昌: 南昌大学, 2012:27-28.
SUN Lina. Preparation and performance study of zwitterionic sulfonated polyethersulfone composite proton exchange membrane[D]. Nanchang: Nanchang University, 2012:27-28.
[42] NI J, HU M, LIU D, et al. Synthesis and properties of highly branched polybenzimidazoles as proton exchange membranes for high-temperature fuel cells[J]. Journal of Materials Chemistry C, 2016, 4(21): 4814-4821.
doi: 10.1039/C6TC00862C
[43] 徐涛. 有机-无机杂化质子交换膜质子传递特性仿生强化的研究[D]. 天津: 天津大学, 2012:18-22.
XU Tao. Research on biomimetic enhancement of proton transfer characteristics of organic-inorganic hybrid proton exchange membrane[D]. Tianjin: Tianjin University, 2012:18-22.
[44] CHEN L, SUN L, ZENG R, et al. Cross-linked zwitterionic polyelectrolytes based on sulfonated poly(ether sulfone) with high proton conductivity for direct methanol fuel cells[J]. Journal of Power Sources, 2012, 212: 13-21.
doi: 10.1016/j.jpowsour.2012.04.008
[1] 张鑫伟, 李港华, 李林蔚, 刘红, 田明伟, 王航. 基于聚偏氟乙烯/聚多巴胺/UiO-66纳米纤维的复合质子交换膜制备及其性能[J]. 纺织学报, 2025, 46(02): 35-42.
[2] 王利媛, 康卫民, 庄旭品, 鞠敬鸽, 程博闻. 磺化聚醚砜纳米纤维复合质子交换膜的制备及其性能[J]. 纺织学报, 2020, 41(11): 19-26.
[3] 王树博, 秦湘普, 石磊, 庄旭品, 李振环. 氧化石墨烯量子点/聚丙烯腈纳米纤维复合质子交换膜的制备及其性能[J]. 纺织学报, 2020, 41(06): 8-13.
[4] 王栋 卿星 蒋海青 钟卫兵 李沐芳. 纤维材料与可穿戴技术的融合与创新[J]. 纺织学报, 2018, 39(05): 150-154.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
No Suggested Reading articles found!