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自由基湮灭剂含量调控对质子交换膜耐久性的影响研究

作者：杨大伟1,2, 韩敏芳1*, 高启秀2, 周守勇3

单位： 1. 清华大学能源与动力工程系，新型电力系统运行与控制全国重点实验室，北京 100084;
2. 苏州科润新材料股份有限公司，苏州 215200; 3. 淮阴师范学院化学化工学院，淮安 223300

关键词：燃料电池；质子交换膜；自由基湮灭剂；耐久性；工业级

DOI号： 10.16159/j.cnki.issn1007-8924.2026.03.010

分类号： TM911.4; TB383.2

出版年,卷(期):页码： 2026, 46(3):100-108

摘要：

燃料电池用质子交换膜通过加入可抵御强氧化性自由基攻击的自由基湮灭剂来提高电池膜的耐久性，但同时会降低膜的电学性能。本研究旨在探寻工业级质子交换膜中自由基湮灭剂的最佳添加量，实现其化学耐久性与电池性能的综合平衡。通过将不同质量分数（0~0.6%）的碳酸铈湮灭剂直接添加到全氟磺酸树脂制膜液中，经分散混合后，再与膨体聚四氟乙烯微孔膜充分浸润、覆合，成功制备出厚度为12 μm、不同湮灭剂含量的质子交换膜，并系统测试了复合膜的各项基础性能、燃料电池的电化学性能和开路电压加速耐久性。测试结果表明，随着湮灭剂含量的增加，复合膜组装成的燃料电池的电化学性能降低越明显，但是添加剂含量对膜的基础性能影响较小；当碳酸铈添加量为0.3%时，复合膜在燃料电池测试时保有较高电学性能的同时，其开路电压加速测试寿命达到1 150 h，实现了耐久性与电学性能的最佳综合平衡。将自由基湮灭剂直接加入到全氟磺酸树脂制膜液中，进行机械混合搅拌分散，操作简单、易于实施，加入量有效可控。该制备方法为工业应用提供了兼顾长寿命与高性能的膜材料配方。

The durability of proton exchange membranes (PEMs) for fuel cells is typically enhanced by incorporating radical scavengers that mitigate oxidative degradation caused by highly reactive free radicals. However, this strategy often compromises the electrical properties of the membrane. This study aims to determine the optimal loading of radical scavengers in industrial-grade PEMs to achieve a balanced trade-off between chemical durability and electrochemical performance. Cerium carbonate, employed as a radical quencher, was directly added to a perfluorosulfonic acid resin solution at concentrations ranging from 0 to 0.6%. Following dispersion and mixing, the solution was used to impregnate an expanded polytetrafluoroethylene (ePTFE) microporous membrane and subsequently laminated to fabricate composite membranes with a uniform thickness of 12 μm. The resulting membranes were systematically characterized in terms of fundamental physicochemical properties, fuel cell performance, and durability under accelerated open-circuit voltage (OCV) conditions. Results demonstrated that while higher quencher loadings led to a progressive decline in electrochemical performance, their impact on the membrane’s fundamental properties remained minimal. At a cerium carbonate content of 0.3%, the composite membrane exhibited a favorable combination of high fuel cell performance and an extended accelerated OCV durability of 1 150 hours, representing an optimal balance between durability and electrical output. The direct incorporation of the radical quencher into the resin solution via mechanical mixing offered a simple, scalable, and precisely controllable approach for membrane fabrication. This method thus provides a viable formulation strategy for the industrial production of proton exchange membranes that achieve both long operational lifetime and high performance.

基金项目：

2024年度江苏省制造强省建设专项资金项目(“1650”产业体系协同攻关类)

作者简介：

第一作者简介：杨大伟（1984-），男，江苏淮安人，主要研究方向为能源与动力. *通讯作者，E-mail:hanminfang@mail.tsinghua.edu.cn

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