高阻氢聚氨酯-聚脲质子交换膜的结构设计及其性能研究
作者： 张庚辰1,2， 庞龙2*，  张晓燕1*，  江河清2
单位： 1. 青岛大学 化学化工学院， 青岛 266071； 
2. 中国科学院青岛生物能源与过程研究所， 青岛 266101
关键词： 聚氨酯； 质子交换膜； 氢气阻隔； 质子传导
DOI号： 10.16159/j.cnki.issn1007-8924.2026.03.011
分类号： TQ317
出版年,卷(期):页码： 2026, 46(3):109-119

摘要：

低氢气渗透系数的质子交换膜（PEM）对于确保运行过程中的安全性和高能效至关重要。本研究提出了一种新型磷酸（PA）掺杂的嵌段聚氨酯-聚脲（PUA）质子交换膜，该膜具有优异的质子电导率，同时显著抑制了氢气的渗透。由双酚A（BPA）和二苯基甲烷二异氰酸酯（MDI）共聚而成的刚性嵌段为膜提供了机械强度，而N-氨乙基哌嗪（AEP）与六亚甲基二异氰酸酯（HDI）聚合成的柔性嵌段含有大量的叔胺官能团，其为PA提供了主要的掺杂位点。本研究设计的PUA膜在80 ℃、98%相对湿度下的最大质子电导率达351.4 mS/cm，氢气渗透率仅为1.86 Barrer。进一步通过在PUA膜两侧引入PFSA保护层制备了燃料电池膜电极，其功率密度达到了54.72 mW/cm2。该PUA膜材料的单体成本低、合成路线简便、制膜工艺成熟，为高性能、低成本质子交换膜的工业放大提供了新的设计路线。

Low hydrogen permeability coefficient of proton exchange membrane (PEM) is critical for ensuring operational safety and high energy efficiency. This paper proposed a novel phosphoric acid (PA)-doped block polyurethane-polyurea (PUA) proton exchange membrane, which exhibited excellent proton conductivity while significantly suppressing hydrogen permeation. The rigid block, copolymerized from bisphenol A (BPA) and methylene diphenyl diisocyanate (MDI), provided mechanical strength to the membrane, whereas the flexible block, polymerized from N-aminoethylpiperazine (AEP) and hexamethylene diisocyanate (HDI), contained  abundant tertiary amine functional groups serving as the primary doping sites for PA. The proposed PUA membrane achieved a maximum proton conductivity of 351.4 mS/cm  at 80 ℃ and 98% relative humidity,and a hydrogen permeability coeffcient of only 1.86 Barrer. Furthermore, fuel cell membrane electrode assemblies were fabricated by introducing PFSA protective layers on both sides of the PUA membrane, achieving a power density of 54.72 mW/cm2. Owing to the low monomer cost, facile synthesis route, and mature membrane fabrication process of this PUA material, this study offers a new design pathway for the industrial scale-up of high-performance, low-cost proton exchange membranes. 

基金项目：

山东省重点研发计划资助(2023CXGC010417); 国家自然科学基金(22308365)

作者简介：
第一作者简介： 张庚辰（2000-），男，山东威海人，主要研究方向为质子交换膜.*通讯作者，庞龙，E-mail：panglong@qibebt.ac.cn；张晓燕，E-mail：xyzhang@qdu.edu.cn

参考文献：

［1］Guan P, Jiang M, Li W, et al. Strategies for lowering hydrogen permeation in membranes for proton exchange membrane water electrolyzers and fuel cells［J］. Adv Mater, 2026, 38(4): e08400.
［2］Carmo M, Fritz D L, Mergel J, et al. A comprehensive review on PEM water electrolysis［J］. Int J Hydrog Energy, 2013, 38(12): 4901-4934.
［3］Peighambardoust S J, Rowshanzamir S, Amjadi M. Review of the proton exchange membranes for fuel cell applications［J］. Int J Hydrog Energy, 2010, 35(17): 9349-9384.
［4］Li T, Song X, Zhang Y, et al. Tailoring long-range ordered nanochannels in Nafion intercalated GO membrane for improved proton conduction［J］. J Membr Sci, 2025, 724: 123946.
［5］Shiva Kumar S, Himabindu V. Hydrogen production by PEM water electrolysis - A review［J］. Mater Sci Energy Technol, 2019, 2(3): 442-454.
［6］Kusoglu A, Weber A Z. New insights into perfluorinated sulfonic-acid ionomers［J］. Chem Rev, 2017, 117(3): 987-1104.
［7］Cohen L A, Weimer M S, Yim K, et al. How low can you go? nanoscale membranes for efficient water electrolysis［J］. ACS Energy Lett, 2024(9): 1624-1632.
［8］Schuler T, Weber C C, Wrubel J A, et al. Ultrathin microporous transport layers: implications for low catalyst loadings, thin membranes, and high current density operation for proton exchange membrane electrolysis［J］. Adv Energy Mater, 2024, 14(7): 2302786.
［9］Liu F, Miyatake K, Kim I S, et al. Universal fluorine-free proton exchange polymers for high-performance and durable fuel cells operable under severe conditions［J］. Adv Mater, 2026, 38(14): e20137.
［10］Wang W, Tai G, Li Y, et al. Highly elastic, healable, and durable anhydrous high-temperature proton exchange membranes cross-linked with highly dense hydrogen bonds［J］. Macromol Rapid Commun, 2023, 44(8): e2300007.
［11］Sun H, Bao J, Pan G, et al. Preparation and properties of polybenzimidazole proton exchange membranes with hydrogen bond-rich networks formed by branches［J］. Int J Hydrog Energy, 2024, 81: 1192-1197.
［12］Che Q, Feng F, Liu L, et al. Preparation of the multicomponent high temperature proton exchange membranes with layer by layer self-assembly technique［J］. Fibers Polym, 2018, 19(8): 1585-1595.
［13］Jia T, Shen S, Xiao L, et al. Constructing multilayered membranes with layer-by-layer self-assembly technique based on graphene oxide for anhydrous proton exchange membranes［J］. Eur Polym J, 2020, 122: 109362.
［14］Che Q, Fan H, Duan X, et al. Layer by layer self-assembly fabrication of high temperature proton exchange membrane based on ionic liquids and polymers［J］. J Mol Liq, 2018, 269: 666-674.
［15］Akindoyo J O, Beg M D H, Ghazali S, et al. Polyurethane types, synthesis and applications - A review［J］. RSC Advances, 2016, 6(115): 114453-114482.
［16］Wang P, Peng J, Yin B, et al. Phosphoric acid-doped polybenzimidazole with a leaf-like three-layer porous structure as a high-temperature proton exchange membrane for fuel cells［J］. J Mater Chem A, 2021, 9(46): 26345-26353.
［17］Li W, Liu W, Zhang J, et al. Porous proton exchange membrane with high stability and low hydrogen permeability realized by dense double skin layers constructed with amino tris (methylene phosphonic acid)［J］. Adv Funct Mater, 2023, 33(6): 2210036.
［18］Wang X, Wang D, Wang S, et al. High-performance proton exchange membranes based on block polybenzimidazole and organic-inorganic fillers with a low acid doping level［J］. ACS Appl Energy Mater, 2022, 5(2): 2553-2563.
［19］李甜甜. 基于氧化石墨烯与全氟磺酸纳米纤维的复合质子交换膜构筑及性能研究 ［D］.青岛:青岛大学, 2025.
［20］Zhang X, Jiao C, Li X, et al. Zn ion-modulated polyamide membrane with enhanced facilitated transport effect for CO2 separation［J］. Sep Purif Technol, 2022, 292: 121051.
［21］Aili D, Henkensmeier D, Martin S, et al. Polybenzimidazole-based high-temperature polymer electrolyte membrane fuel cells: New insights and recent progress［J］. Electrochem Energy Rev, 2020, 3(4): 793-845.
［22］Freeman B D. Basis of permeability/selectivity tradeoff relations in polymeric gas separation membranes［J］. Macromolecules, 1999, 32(2): 375-380.
［23］Wu X, He G, Li X, et al. Improving proton conductivity of sulfonated poly(ether ether ketone) proton exchange membranes at low humidity by semi-interpenetrating polymer networks preparation［J］. J Power Sources, 2014, 246: 482-490.
［24］Wang S, Zhang D, Ma X, et al. Modifying ionic membranes with carbon dots enables direct production of high-purity hydrogen through water electrolysis［J］. ACS Appl Mater Interfaces, 2021, 13(33): 39304-39310.
［25］Du L, Yan X, He G, et al. SPEEK proton exchange membranes modified with silica sulfuric acid nanoparticles［J］. Int J Hydrog Energy, 2012, 37(16): 11853-11861.
［26］Kim T, Sihn Y, Yoon I H, et al. Monolayer hexagonal boron nitride nanosheets as proton-conductive gas barriers for polymer electrolyte membrane water electrolysis［J］. ACS Appl Nano Mater, 2021, 4(9): 9104-9112.
［27］Goo B H, Al Munsyr A Z, Choi O, et al. Sulfonated poly(ether sulfone)-coated and -blended nafion membranes with enhanced conductivity and reduced hydrogen permeability［J］. ACS Appl Energy Mater, 2020, 3(11): 11418-11433.
［28］Gao Z, Yin Z, Kong Y, et al. Robust and highly proton conductive COF composite membranes for fuel cell and electrochemical hydrogen compression［J］. Chem Eng J, 2024, 490: 151368.
［29］Al Munsur A Z, Goo B H, Kim Y, et al. Nafion-based proton-exchange membranes built on cross-linked semi-interpenetrating polymer networks between poly(acrylic acid) and poly(vinyl alcohol)［J］. ACS Appl Mater Interfaces, 2021, 13(24): 28188-28200.
［30］Min K, Al Munsur A Z, Paek S Y, et al. Development of high-performance polymer electrolyte membranes through the application of quantum dot coatings to nafion membranes［J］. ACS Appl Mater Interfaces, 2023, 15(12): 15616-15624.
［31］Non  Y S, Jeong H Y, Yoon S J, et al. Multilayered hydrocarbon ionomer/PTFE composite electrolytes with enhanced performance for energy conversion devices［J］. Int J Hydrogen Energy, 2023, 48(13): 5288-5300.
［32］Ahn S M, Park J E, Jang G Y, et al. Highly sulfonated aromatic graft polymer with very high proton conductivity and low hydrogen permeability for water electrolysis［J］. ACS Energy Lett, 2022, 7(12): 4427-4435.

服务与反馈：
【Download】【加入收藏】

《膜科学与技术》编辑部 地址：北京市朝阳区北三环东路19号蓝星大厦 邮政编码：100029 电话：010-80492417/010-80485372 传真：010-80485372邮箱：mkxyjs@163.com

京公网安备11011302000819号