静电纺丝纳米纤维在燃料电池质子交换膜中应用的研究进展

保护环境,开发环保型能源,对人类和社会具有重要意义。 质子交换膜燃料电池由于具有燃料转化率较高和无污染的优点,备受关注。 静电纺丝纳米纤维具有比表面积大、高孔隙率和三维的相互连通的网状结构等特点,可以在燃料电池质子交换膜中得到广泛应用。 静电纺丝纳米纤维类复合质子交换膜具有较高的质子传导率,较低的燃料渗透率,较好的化学稳定性能、热稳定性能和机械性能。 本文首先介绍了质子交换膜燃料电池,然后从不同的离子型聚合物基质复合质子交换膜的类别出发,介绍了静电纺丝纳米纤维在Nafion、磺化聚酰亚胺(SPI)、聚苯并咪唑(PBI)、磺化聚醚醚酮(SPEEK)等不同种类的离子型聚合物质子交换膜中的研究现状及作用机理,同时对静电纺丝纳米纤维在质子交换膜的应用方面存在的问题及应用前景做了评论和展望。     

杂萘联苯聚芳醚质子交换膜材料的研究

质子交换膜是质子交换膜燃料电池的核心部件之一，其性能的优劣直接关系燃料电池的工作性能。目前质子交换膜燃料电池多采用全氟磺酸离子膜，全氟磺酸膜虽然具有较高的质子传导性和良好的化学稳定性，但是也具有价格昂贵、甲醇渗透高和高温下质子传导性能下降等缺点。为了克服全氟磺酸膜的不足，国内外相继开展了非氟质子交换膜的研究，如磺化聚醚醚酮（SPEEK）、磺化聚醚醚酮酮（SPEEKK）、磺化聚砜（SPSU）和磺化聚酰亚胺（SPI）等。     

质子交换膜燃料电池膜电极耐久性的提升

质子交换膜燃料电池由于具有能量转换效率高、操作温度低、环境友好等优点而备受人们关注。随着2014年丰田发布燃料电池电动汽车Mirai,带来了新一轮燃料电池及燃料电池汽车的产业化热潮。然而,提升质子交换膜燃料电池的寿命,开发新一代长寿命燃料电池膜电极及燃料电池仍然是本领域的挑战性课题。膜电极(MEA)是质子交换膜燃料电池最核心的部件,其耐久性直接决定着燃料电池的寿命。MEA主要由质子交换膜、催化剂层、气体扩散层三部分组成。本文从质子交换膜、催化剂及载体、气体扩散层三个方面介绍了近年来国内外在提升燃料电池膜电极的寿命(耐久性)方面所做的工作,并对未来的相关研究和发展做了述评及展望。     

质子交换膜燃料电池梯度化膜电极

为实现质子交换膜燃料电池的高性能(高功率密度或大电流密度)、低成本(低铂载量)、长寿命发电,人们尝试在燃料电池的核心部件膜电极结构中引入梯度化设计的概念。梯度化膜电极包括膜电极中各组件的梯度化:气体扩散层的PTFE含量与孔隙率的梯度化,催化层的催化剂与Nafion用量的梯度化以及微孔层的疏水性与孔隙率的梯度化。梯度化膜电极中催化剂分布、孔隙率分布、亲/疏水性分布合理,具有良好的三相反应界面以及质子、电子、反应气体、水等多相物质高效传输通道,从而能满足在低铂载量、低加湿以及高电流密度条件下高性能稳定工作。本文整理了近几年来有关燃料电池梯度化膜电极研究的相关文献,梳理了梯度化膜电极研究发展脉络,归纳总结了各种梯度化膜电极的制备方法、性能以及构效关系,并展望了梯度化膜电极下一步研究方向,对高性能、低成本、长寿命的燃料电池开发具有指导意义。     

氧化石墨烯/聚合物复合质子交换膜研究进展

氧化石墨烯/聚合物复合质子交换膜(GO/Polymer blend PEM)是一种新型的质子交换膜,广泛应用于直接甲醇燃料电池(DMFC)中,已成为质子交换膜研究的热点之一。氧化石墨烯/聚合物复合质子交换膜具有较高的传导质子率、力学性能、阻醇性能和电池性能。本文综述了氧化石墨烯(GO)处理方法、氧化石墨烯/聚合物复合质子交换膜制备方法,氧化石墨烯/聚合物复合质子交换膜的质子传导、阻醇、离子交换容量和电池的性能,氧化石墨烯/聚合物复合质子交换膜质子传递机理及阻醇机理。     

低温质子交换膜燃料电池自增湿膜电极研究进展

具有自增湿能力的低温质子交换膜燃料电池膜电极是实现自增湿燃料电池的重要途径,对于燃料电池的商业化具有十分重要的意义,它不仅可以大幅度减小燃料电池系统的体积,提升燃料电池系统的输出功率密度,还可以有效降低燃料电池的制造成本. 目前,低温质子交换膜燃料电池自增湿膜电极的研究主要是集中在构建具有自增湿能力的质子交换膜、自增湿催化层和复合自增湿层三个方面. 本文主要从这三个方面系统介绍近年来国内外低温质子交换膜燃料电池自增湿膜电极方面的研究进展和发展趋势.     

燃料电池用高温质子交换膜

与传统质子交换膜燃料电池相比,高温质子交换膜燃料电池(HT-PEMFCs)不仅可以提高催化剂对CO的耐受能力,还能简化水热管理,提高能量转化效率。高温质子交换膜是实现高温操作的关键部件之一。掺杂无机磷酸的高温质子交换膜因为在高温度(100~200 ℃)和低相对湿度下具有较高的质子传导率,以及较长使用寿命而成为研究的热点。高的磷酸掺杂量有助于质子传导率的提升,但也会牺牲膜的机械强度,因此已有大量致力于提升膜综合性能的改性研究。本文对目前基于磷酸基的聚苯并咪唑类、聚芳醚类等高温质子交换膜的改性策略进行评述,并梳理总结了包括 MOFs、COFs 在内的新型多孔材料在质子交换膜领域的应用,最后指出了高温质子交换膜当前面临的挑战。     

燃料电池用跨温区质子交换膜材料研究进展

质子交换膜燃料电池(PEMFC)是一种电化学能量转换器件，能将燃料中的化学能转换为电能，具有高效、清洁、寿命长等优点，可应用于动力电池、固定式和便携式电源等领域。质子交换膜(PEM)是其中的关键部件，主要用于隔离阴阳两极和传递质子等。但当前质子交换膜燃料电池的发展面临着成本高、寿命不足等挑战。本文结合近年的研究热点，从质子传输机制出发将质子交换膜燃料电池分为磺酸功能化PEM和磷酸掺杂型PEM两大类，从主链结构的差异以及改性方法等方面综述近年来的研究进展，详细介绍了材料的化学结构、膜材料性能、电化学性能等，并针对现存的一些问题和不足对质子交换膜燃料电池今后的发展方向进行了展望。     

燃料电池质子交换膜研究进展与展望

质子交换膜燃料电池(PEMFC)作为一种清洁高效的能量转换装置,具有比功率高、稳定性好、易于启动等优点,是未来可移动动力源的理想候选。成本和寿命是阻碍PEMFC商业化的主要原因,寻找新型材料是解决这两大问题的必然选择,也是近年来质子交换膜研究的热点和重点。本文介绍了几种质子交换膜材料的研究进展,主要包括聚合物型、陶瓷型和有机-无机复合型,讨论了各种膜材料的特点,并对其未来的发展加以展望。     

直接甲醇燃料电池质子膜研究进展

本文对直接甲醇燃料电池(DMFC)质子交换膜的要求及目前的研究状况作了简要的概述,特别是从基膜材料结构角度进行分类,较详细地介绍分析以Nafion膜为代表的全氟磺酸膜的各种改性研究及以PBI、PEEK、PSU等基膜材料为代表的聚芳环系列的DMFC质子交换膜的研究情况.总结了质子交换膜的一些研究方法,对直接甲醇燃料电池质子交换膜的发展前景进行了探讨。     

侧链磺化聚芳醚质子交换膜的研究进展

燃料电池是以氢气、甲醇等作为燃料的一种新型能量转化装置,其中质子交换膜燃料电池（Proton Exchange Membrane Fuel Cell, PEMFC）凭借其能量功率高、启动速度快和使用寿命长等优点已经在移动电源、潜艇和电动汽车等领域得到了广泛应用。质子交换膜（Proton Exchange Membrane, PEM）对PEMFC的性能影响最大,高效的PEMFC需要PEM具有高的质子电导率、良好的热稳定性和机械性能、低燃料渗透率以及优异的物理化学稳定性等。目前市面上多数使用的均是具有优异质子电导率的Nafion系列膜,但其存在制备困难、成本昂贵、质子电导率严重依赖湿度等缺点,在一定程度上限制了其发展。为了让PEM有更多的选择,科学家一直专注于使用新材料替代Nafion膜。近年来,科学家们模拟Nafion结构,通过合成各种侧链含磺酸基团的聚芳醚结构,使得亲水基团磺酸基和疏水基团之间形成微相分离结构,从而获得了一系列具有优异综合性能的PEM。本文将重点对侧链烷基磺化型、侧链磺化嵌段型、侧链局部密集磺化型、侧链磺化交联型和侧链磺化复合型这几种常见策略的合成方法及性能进行了综述,最后展望了侧链磺化聚芳醚在PEM领域的优势及发展前景。     

燃料电池用质子交换膜的研究进展

质子交换膜燃料电池 (PEMFC)以质子交换膜 (PEM )作为电解质和隔膜 ,其性能强烈地依靠PEM的性质 .本文分析了PEMFC对PEM的要求 ,对全氟化、部分氟化和非氟化的PEM进行了分类介绍 ,着重讨论了膜的结构、制备、性质以及它们在PEMFC中的应用     

Hydrophilicity/porous structure-tuned, SiO2/polyetherimide-coated polyimide nonwoven porous substrates for reinforced composite proton exchange membranes

Porous substrate-reinforced composite proton exchange membranes have drawn considerable attention due to their promising application to polymer electrolyte membrane fuel cells (PEMFCs). In the present study, we develop silica (SiO(2)) nanoparticles/polyetherimide (PEI) binders-coated polyimide (PI) nonwoven porous substrates (referred to as "S-PI substrates") for reinforced composite membranes. The properties of S-PI substrates, which crucially affect the performance of resulting reinforced composite membranes, are significantly improved by controlling the hygroscopic SiO(2) particle size. The 40 nm S-PI substrate (herein, 40 nm SiO(2) particles are employed) shows the stronger hydrophilicity and highly porous structure than the 530 nm S-PI substrate due to the larger specific surface area of 40 nm SiO(2) particles. Based on the comprehensive understanding of the S-PI substrates, the structures and performances of the S-PI substrates-reinforced composite membranes are elucidated. In comparison with the 530 nm S-PI substrate, the hydrophilicity/porous structure-tuned 40 nm S-PI substrate enables the impregnation of a large amount of a perfluorosulfonic acid ionomer (Nafion), which thus contributes to the improved proton conductivity of the reinforced Nafion composite membrane. Meanwhile, the reinforced Nafion composite membranes effectively mitigate the steep decline of proton conductivity with time at low humidity conditions, as compared to the pristine Nafion membrane. This intriguing finding is further discussed by considering the unusual features of the S-PI substrates and the state of water in the reinforced Nafion composite membranes.     

Non-Fluorinated Polymer Composite Proton Exchange Membranes for Fuel Cell Applications – A Review

The critical component of a proton exchange membrane fuel cell (PEMFC) system is the proton exchange membrane (PEM). Perfluorosulfonic acid membranes such as Nafion are currently used for PEMFCs in industry, despite suffering from reduced proton conductivity due to dehydration at higher temperatures. However, operating at temperatures below 100 °C leads to cathode flooding, catalyst poisoning by CO, and complex system design with higher cost. Research has concentrated on the membrane material and on preparation methods to achieve high proton conductivity, thermal, mechanical and chemical stability, low fuel crossover and lower cost at high temperatures. Non-fluorinated polymers are a promising alternative. However, improving the efficiency at higher temperatures has necessitated modifications and the inclusion of inorganic materials in a polymer matrix to form a composite membrane can be an approach to reach the target performance, while still reducing costs. This review focuses on recent research in composite PEMs based on non-fluorinated polymers. Various inorganic fillers incorporated in the PEM structure are reviewed in terms of their properties and the effect on PEM fuel cell performance. The most reliable polymers and fillers with potential for high temperature proton exchange membranes (HTPEMs) are also discussed.     

磺化嵌段型共聚物在质子交换膜燃料电池中的应用*

燃料电池是以碳氢化合物为燃料的一种新型、清洁的发电装置,而其中的质子交换膜燃料电池由于具有可快速启动的优点而可应用于机动车等领域。所用的质子交换膜需要具有高的质子传导性、低的甲醇/水渗透性、好的机械和热稳定性以及合适的价格等特点,但目前已经工业化的Nafion膜并未能全部满足上述要求。为了解决这些问题,目前已经开发了多种新的质子交换膜。本文对其中的磺化嵌段型聚醚砜、磺化嵌段型聚酰亚胺和苯乙烯基嵌段共聚物在质子交换膜燃料电池中的应用进行了综述,并与Nafion膜和相应的无规共聚物的性能进行了比较。最后展望了嵌段共聚物在质子交换膜领域的发展趋势。     

A numerical multiphase CFD simulation for PEMFC with parallel sinusoidal flow fields

Journal of Thermal Analysis and Calorimetry - Flow field design has an important role in proton exchange membrane fuel cell (PEMFC) due to its effect on the distribution of pressure, current...     

Synthesis and characterization of novel sulfonated polyimide containing phthalazinone moieties as PEM for PEMFC

A novel sulfonated diamine monomer,1,2-dihydro-2-(3-sulfonic-4-aminophenyl)-4-[4-(4-aminophenoxy)-phenyl]phthalazin- 1-one(S-DHPZDA),was successfully synthesized by direct sulfonation of diamine 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4- aminophenoxy)-phenyl]-phthalazin-1-one(DHPZDA).A series of sulfonated polyimides(SPIs),which can be used as the material of the proton exchange membrane(PEM)for the proton exchange membrane fuel cell(PEMFC),were prepared from 1,4,5,8- naphthalenetetracarboxylic dianhydride(NTDA),S-DHPZDA,and nonsulfonated diamines DHPZDA.The structure of the monomer and polymers were characterized by FT-IR and~1H NMR.The solubility of the S-DHPZDA-based SPIs has been improved due to the induction of the phthalazione moiety.The SPIs membranes have high thermo-stability,predominant swelling resistance with high ion exchange capacity.     

Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability

The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006     

燃料电池用质子交换膜的研究进展

质子交换膜是燃料电池的重要组成部分。本文介绍了全氟磺酸膜的优缺点,对其进行改进的方法以及新型质子交换膜的发展情况,重点讨论了各类质子交换膜的制备、结构、性质以及它们在质子交换膜燃料电池(PEMFC)或直接甲醇燃料电池(DMFC)的应用,最后提出质子交换膜的发展趋势。     

Hybrid Organic/Inorganic Sol-Gel Materials for Proton Conducting Membranes

One important application of hybrid organic-inorganic materials with nano-sized interfaces is the preparation of membranes for Proton Exchange Membrane Fuel Cells (PEMFC) operating at high temperature. Poly (styrene-co-methacrylate)--silica covalent hybrid membranes have been synthesised by copolymerization of monomers (styrene and 2-hydroxyethyl methacrylate), with formation of covalent bonds between hydroxyl group of HEMA and pre-hydrolysed tetraethoxysilane (TEOS). Sulfonation of benzyl groups was applied to endow the membranes of proton conductivity. The incorporation of an inorganic component to a polymeric one modifies properties like thermal, chemical and mechanical stability, and proton conductivity. A compromise between these properties has to be achieved to produce adequate proton conducting membranes with application in PEMFC. The hybrid membrane with 25% SiO₂ combines these properties being a promising candidate for application in PEMFC.