Zhongju Wang , Tengda Guo , Hui Liu , Zhonghui Wang , Jianbo Zhang , Qiang Liu , Zixi Wang
{"title":"紫外/过氧化氢深度氧化膜电极组件自由基降解机理研究","authors":"Zhongju Wang , Tengda Guo , Hui Liu , Zhonghui Wang , Jianbo Zhang , Qiang Liu , Zixi Wang","doi":"10.1016/j.ijhydene.2025.150362","DOIUrl":null,"url":null,"abstract":"<div><div>The main challenges in the commercialization of proton exchange membrane fuel cells (PEMFCs) are their high cost and poor durability; one of the key factors limiting their lifetime is the attack of free radicals (•OH) on membrane electrode assemblies. In this study, a quantitative free-radical aging device is built based on an ultraviolet (UV)/hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) Advanced Oxidation Process, which precisely regulates the generation rate of hydroxyl radicals. The results show that free-radical attack leads to polymer backbone and side-chain breakage, as well as the loss of sulfonic acid groups. The tensile strength and water absorption properties of the catalyst-coated membrane (CCM) are significantly reduced, while the gas permeability remains stable. The catalyst layer (CL) thickness decreases, and the mass loss rate increased. The hydrophobicity of the microporous layer (MPL) surface decreases continuously with the free-radical attack, the first 10 h, rapid defluorination and initial oxidation lead to a decrease in hydrophobicity. From 10 to 40 h, the defluorination rate slows, but oxidation continues, further diminishing the hydrophobicity. This study provides an in-depth understanding of the aging mechanisms of free radicals in fuel cells and offers an important theoretical basis for designing durable membrane electrode assembly (MEA) materials.</div></div>","PeriodicalId":337,"journal":{"name":"International Journal of Hydrogen Energy","volume":"158 ","pages":"Article 150362"},"PeriodicalIF":8.1000,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Study of free radical degradation mechanisms of membrane electrode assembly based on ultraviolet/hydrogen peroxide advanced oxidation process\",\"authors\":\"Zhongju Wang , Tengda Guo , Hui Liu , Zhonghui Wang , Jianbo Zhang , Qiang Liu , Zixi Wang\",\"doi\":\"10.1016/j.ijhydene.2025.150362\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The main challenges in the commercialization of proton exchange membrane fuel cells (PEMFCs) are their high cost and poor durability; one of the key factors limiting their lifetime is the attack of free radicals (•OH) on membrane electrode assemblies. In this study, a quantitative free-radical aging device is built based on an ultraviolet (UV)/hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) Advanced Oxidation Process, which precisely regulates the generation rate of hydroxyl radicals. The results show that free-radical attack leads to polymer backbone and side-chain breakage, as well as the loss of sulfonic acid groups. The tensile strength and water absorption properties of the catalyst-coated membrane (CCM) are significantly reduced, while the gas permeability remains stable. The catalyst layer (CL) thickness decreases, and the mass loss rate increased. The hydrophobicity of the microporous layer (MPL) surface decreases continuously with the free-radical attack, the first 10 h, rapid defluorination and initial oxidation lead to a decrease in hydrophobicity. From 10 to 40 h, the defluorination rate slows, but oxidation continues, further diminishing the hydrophobicity. This study provides an in-depth understanding of the aging mechanisms of free radicals in fuel cells and offers an important theoretical basis for designing durable membrane electrode assembly (MEA) materials.</div></div>\",\"PeriodicalId\":337,\"journal\":{\"name\":\"International Journal of Hydrogen Energy\",\"volume\":\"158 \",\"pages\":\"Article 150362\"},\"PeriodicalIF\":8.1000,\"publicationDate\":\"2025-07-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"International Journal of Hydrogen Energy\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0360319925033609\",\"RegionNum\":2,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Hydrogen Energy","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0360319925033609","RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Study of free radical degradation mechanisms of membrane electrode assembly based on ultraviolet/hydrogen peroxide advanced oxidation process
The main challenges in the commercialization of proton exchange membrane fuel cells (PEMFCs) are their high cost and poor durability; one of the key factors limiting their lifetime is the attack of free radicals (•OH) on membrane electrode assemblies. In this study, a quantitative free-radical aging device is built based on an ultraviolet (UV)/hydrogen peroxide (H2O2) Advanced Oxidation Process, which precisely regulates the generation rate of hydroxyl radicals. The results show that free-radical attack leads to polymer backbone and side-chain breakage, as well as the loss of sulfonic acid groups. The tensile strength and water absorption properties of the catalyst-coated membrane (CCM) are significantly reduced, while the gas permeability remains stable. The catalyst layer (CL) thickness decreases, and the mass loss rate increased. The hydrophobicity of the microporous layer (MPL) surface decreases continuously with the free-radical attack, the first 10 h, rapid defluorination and initial oxidation lead to a decrease in hydrophobicity. From 10 to 40 h, the defluorination rate slows, but oxidation continues, further diminishing the hydrophobicity. This study provides an in-depth understanding of the aging mechanisms of free radicals in fuel cells and offers an important theoretical basis for designing durable membrane electrode assembly (MEA) materials.
期刊介绍:
The objective of the International Journal of Hydrogen Energy is to facilitate the exchange of new ideas, technological advancements, and research findings in the field of Hydrogen Energy among scientists and engineers worldwide. This journal showcases original research, both analytical and experimental, covering various aspects of Hydrogen Energy. These include production, storage, transmission, utilization, enabling technologies, environmental impact, economic considerations, and global perspectives on hydrogen and its carriers such as NH3, CH4, alcohols, etc.
The utilization aspect encompasses various methods such as thermochemical (combustion), photochemical, electrochemical (fuel cells), and nuclear conversion of hydrogen, hydrogen isotopes, and hydrogen carriers into thermal, mechanical, and electrical energies. The applications of these energies can be found in transportation (including aerospace), industrial, commercial, and residential sectors.