质子交换膜燃料电池膜电极制备方法的研究进展

燃料电池技术作为一种绿色能源技术,在减少能源消耗、环境污染等方面具有巨大潜力。膜电极（MEA）是质子交换膜燃料电池（PEMFC）的核心部件,MEA中电化学反应的顺利进行需要各功能层的协调配合,MEA各功能层涉及的传质、导电、导质子、催化等方面均影响燃料电池的性能。根据制备方法,可以将MEA分为催化剂涂敷基底（CCS）型MEA、催化剂涂敷膜（CCM）型MEA、有序化MEA和一体化MEA。MEA的性能不仅由催化剂本身载量决定,也受其结构设计和制备工艺的影响。本文介绍了MEA制备过程中常见的改进方法,分别从催化剂喷涂、刮涂、模槽挤出涂覆方式,催化剂浆料组成中Nafion含量和溶剂极性选择,催化层梯度化、图案化及界面结构改进,PEM结构增强、图案化、成膜方式等方面的研究进展进行讨论。但是目前对于MEA各功能层界面间的研究较少,应该注意的是催化层/质子交换膜（PEM）界面以及催化层/气体扩散层（GDL）界面设计也将直接影响MEA的性能。     

直接甲醇燃料电池膜电极制备技术进展

简述了直接甲醇燃料电池(DMFC)的核心部件———膜电极(MEA)的结构及制备技术的最新进展,包括传统厚层电极法、薄层电极法、双层电极法、电沉积法和溅射沉积法,分析了各种方法的优缺点。其中电化学沉积法和溅射沉积法制备MEA,具有催化剂利用率高、负载量低、电池性能好等优点,若能实现大规模的工业化生产,将是DMFC最理想的MEA制备技术。为了进一步推广DMFC的商业化应用,降低MEA的制备成本,建议改进MEA组分、优化MEA结构和开发重现性好,同时适合工业化生产的MEA制备技术。     

直接涂膜技术用于质子交换膜燃料电池膜电极制备

引　言质子交换膜燃料电池 (PEMFC)是极具吸引力的电化学能量转换装置 ,是未来电动汽车的主要动力源 ,也是洁净高效的新型化学电源 .对于电动汽车的应用 ,要求PEMFC提供高能量密度、低催化剂负载量 ,以降低系统体积和成本[1] .膜电极(membraneandelectrodeassembly ,简称MEA)是由聚合物电解质膜、电极催化剂和扩散层材料组合而成的三明治式结构组件 ,类似于计算机的芯片 ,是燃料电池的核心部件 ,长期以来大量的研究集中于MEA新材料设计与制备 ,以提高电池的性能 .近年来 ,对MEA的微观结构分析、MEA制备工艺与电池性能的关系研究工作明显增多[2～ 7] .从PEM FC研究实践中发现 ,如何减少电极中Pt催化剂负载量并能继续保持或者提高电池性能的MEA制备技术开发至关重要 .其中超薄Pt层沉积法[8～ 10 ] 是MEA的制备新技术之一 .与传统的基于墨水涂布(based inkprinting)的方法相比 ,喷溅沉积法(sputterdeposit) [9] 制备的MEA提高了电池的性能和催化剂的利用率 ,它是用直接喷溅沉积法 (directlydeposit) [10...     

质子交换膜燃料电池研究进展

质子交换膜燃料电池（proton exchange membrane fuel cell, PEMFC）因具有效率高、功率密度大、排放产物仅为水、低温启动性好等多方面优点,被公认为下一代车用动力的发展方向之一。然而,目前PEMFC在耐久性和成本方面距离商业化的要求还存在一定差距。为攻克上述两大难题,需要燃料电池全产业链的共同努力和进步。本文回顾了近年来质子交换膜燃料电池从催化剂、膜电极组件、电堆到燃料电池发动机全产业链的研究进展和成果,梳理出单原子催化剂、非贵金属催化剂、特殊形貌催化剂、有序化催化层、高温质子交换膜、膜电极层间界面优化、一体化双极板-扩散层、氢气系统循环等研究热点。文章指出,催化层低铂/非铂化、质子交换膜超薄化、膜电极组件梯度化/有序化、燃料电池运行高温化、自增湿化是未来的发展趋势,迫切需要进一步的创新与突破。     

质子交换膜燃料电池膜电极结构与设计研究进展

膜电极（MEA）为质子交换膜燃料电池（PEMFC）提供了电子、质子、反应气体和产物水等多相物质传递和电化学反应的重要场所。设计和制备具有优异特性的MEA对提高PEMFC的性能,降低制造成本,加快其商业化应用是至关重要的。本文首先对PEMFC的反应机理进行了分析,接着从气体扩散层（GDL）、催化层（CL）、质子交换膜构造（PEM）3个方面阐述各部件在MEA中的作用,归纳总结了各部件的制备方法、传热传质方式、仿真模型、构效关系以及优缺点,最后对影响MEA的各种因素进行了总结,并且结合目前涌现出的许多新兴技术对PEMFC的发展进行了展望。本综述对未来高性能、长寿命和低成本的MEA开发具有指导意义。     

多孔纳米碳纤维作为质子交换膜燃料电池微孔层的性能

质子交换膜燃料电池膜电极中的微孔层结构对改善体系的水管理能力,提升膜电极的整体性能发挥重要作用。本文通过静电纺丝和后续热处理的方法制备了多孔纳米碳纤维（PCNF）,并以此构建膜电极的微孔层。与炭黑颗粒作为微孔层呈现出紧密堆积结构不同,由PCNF搭建的微孔层结构疏松呈现三维贯通状。膜电极的发电测试表明,以多孔纳米碳纤维作为微孔层（MPL-PCNF）的膜电极其最大功率密度达70.0mW/cm²,远高于炭黑颗粒为微孔层（MPL-CB）的膜电极（58.1mW/cm²）,而没有微孔层（Ref）结构的膜电极最大功率密度仅为27.7mW/cm²,显示出PCNF作为微孔层材料的明显优势。     

直接甲醇燃料电池用三维网络结构膜电极的制备方法

本发明公开了一种直接甲醇燃料电池用膜电极的制备方法,属于直接甲醇燃料电池高效膜电极组件结构和制造技术领域。采用控温超声喷涂工艺制备膜电极中的催化层,以实现催化层的三维网络结构,增加催化剂暴露于三相界面的活性位点数量,为气液传输提供通道,再以憎水处理的碳布为扩散层、Nafion膜为质子交换膜、Pt黑和PtRu黑     

质子交换膜燃料电池用催化剂及其电极的研究进展

膜电极(MEA)是质子交换膜燃料电池(PEMFC)的核心技术。膜电极包含的催化剂层、材料和结构等对PEMFC的性能影响很大。催化剂面层上供三相(质子、电子、气体)用的通道对于电池使用时的催化作用是必不可少的。介绍了近几年催化剂的研究进展,看重对三相通道进行了详细叙述。也回顾了一些用于改善催化剂活性的其他方法,如阴极催化、合金催化剂,根据这些进展,对今后的研究方向提出了建议。     

聚合物电解质膜燃料电池气体扩散层上新型双层微孔层的制备和性能

聚合物电解质膜燃料电池（PEMFC）的微孔层对电池性能有重要影响。首次使用多壁碳纳米管（MWCNTs）在碳纸上先制备1层微孔层,再用碳黑（CB）在其上制备第2层微孔层,形成双层微孔层。从不同尺度上观察了微孔层（MPL）的形貌和结构,测量了气体扩散层（GDL）垂直向电阻,并测试了电池性能。结果表明,双层微孔层的平整程度与单独使用碳黑制备的微孔层相似,比单独使用MWCNTs制备的微孔层更加平整;双层微孔层的GDL垂直向的电阻比单层微孔层的GDL更小;使用双层微孔层制备的膜电极比相同碳载量下的单层微孔层制备的膜电极性能更好。     

PEMFC膜电极组成及其性能

质子交换膜燃料电池(PEMFC)的膜电极(MEA)由质子交换膜、催化层、水管理层(WML)和扩散层组成。研究了WML的厚度和聚四氟乙烯(PTFE)的含量对膜电极性能的影响,并采用了两种新型造孔剂(碳酸氢铵和硫酸铵)优化WML的孔结构。采用环境扫描电镜(ESEM)表征了膜电极的表面形貌和孔结构;采用单体PEMFC的电流密度-电压曲线评价了膜电极在外增湿和自增湿方式下的极化特性,结果表明,WML的建立提高了膜电极的水管理能力,使膜电极在自增湿方式下具有良好的极化特性。     

Comparison of catalyst-coated membranes and catalyst-coated substrate for PEMFC membrane electrode assembly:A review

Catalyst-coated membranes (CCMs) have gained popularity among membrane electrode assembly (MEA) fabri-cators for their abilities and advantages compared with those of other methods, such as catalyst-coated sub-strates (CCSs). CCMs show a profound new analysis for reducing platinum (Pt) catalyst loading. In addition, they increase the total number of reactions that occur on the MEA because of their active area amplification, which leads to an improved catalyst-utilization efficiency rate. Moreover, several characteristics are involved in the MEA fabrication methods. Material-manufacturing effects with regard to catalyst inks and analysis of the overall performance of MEAs prepared by the CCM and CCS methods are deliberated. This deliberation empha-sizes the practical approaches in minimizing performance deterioration during the fabrication of MEAs using the CCM method and converses the commercialization of the CCM fabrication method toward developing an end product. Novel research is required for MEA fabrication using the CCM methods to ensure that the fuel cell performance is improved. Therefore, this review is focusing on the pros and cons of both distinguished methods, that is, CCM and CCS fabrication, for better comparison.     

Effect of MEA fabrication techniques on the cell performance of Pt–Pd/C electrocatalyst for oxygen reduction in PEM fuel cell

The effect of three different membrane electrode assembly (MEA) fabrication techniques, catalyst-coated substrate by direct spray (CCS) and catalyst-coated membrane by direct spray (CCM-DS) or decal transfer (CCM-DT), on the performance of oxygen reduction in a proton exchange membrane (PEM) fuel cell was carried out under identical conditions of Pt–Pd/C electrocatalyst loading. The results indicated that the fabrication technique had only a very slight effect on the ohmic resistance of the PEM fuel cell but it significantly affected the charge transfer resistance and open circuit voltage (OCV). The cells prepared by the CCM method, and particularly by decal transfer, exhibited a significantly higher OCV but a lower ohmic and charge transfer resistance compared with the other investigated fabrication techniques. By using cyclic voltammetry with H₂ adsorption, it was found that the electrochemical active area of the electrocatalyst prepared by CCM-DT was higher than those prepared by CCS and CCM-DS by around 1.76- and 1.05-fold, respectively. Under a H₂/O₂ system at 0.6 V, the cells with MEA made by CCM-DT provided the highest cell performance of around 350 mA/cm², significantly greater than those prepared by the CCS and CCM-DS (149 and 42 mA/cm², respectively).     

Performance improvement of ultra-low Pt proton exchange membrane fuel cell by catalyst layer structure optimization

Reducing the loading of noble Pt-based catalyst is vital for the commercialization of proton exchange membrane fuel cell (PEMFC).However,severe mass transfer polarization loss resulting in fuel cell perfor-mance decline will be encountered in ultra-low Pt PEMFC.In this work,mild oxidized multiwalled carbon nanotubes (mMWCNT) were adopted to construct the catalyst layer,and by varying the loading of carbon nanotubes,the catalyst layer structure was optimized.A high peak power density of 1.23 W·cm 2 for the MEA with mMWCNT was obtained at an ultra-low loading of 120 μg·cm-2 Pt/PtRu (both cathode and anode),which was 44.7％ higher than that of MEA without mMWCNT.Better catalyst dispersion,low charge transfer resistance,more porous structure and high hydrophobicity of catalyst layer were ascribed for the reasons of the performance improvement.     

Performance of direct methanol fuel cells prepared by hot-pressed MEA and catalyst-coated membrane (CCM)

The effect of the fabrication methods of the conventional hot-pressed membrane-electrode-assembly (hot-pressed MEA) and catalyst-coated membrane (CCM) on the utilization efficiency of Pt electrocatalysts, methanol crossover and performance of direct methanol fuel cells (DMFCs) is studied under the condition of the same Pt electrocatalysts loading. Cyclic voltammetric and electrochemical impedance studies showed that the cell with CCM exhibited significantly higher electrochemical surface area and lower electrode polarization resistance for the methanol oxidation reaction, in comparison to that with the hot-pressed MEA. Compared with the hot-pressed MEA, the methanol crossover of the cell with CCM is decreased by 55% and the power density of DMFC is enhanced by 36%. The improvement of the DMFCs with CCM is probably due to the significantly higher electrochemical reaction sites and the increased three-phase boundaries through the reduction in the loss of the Pt electrocatalysts in the gas diffusion layers and enhanced electrode/membrane interface.     

Graphene as catalyst support: The influences of carbon additives and catalyst preparation methods on the performance of PEM fuel cells

The reduction of the platinum amount for efficient PEM (polymer electrolyte membrane) fuel cells was achieved by the use of graphene/carbon composites as catalyst support. The influences of the carbon support type and also of the catalyst preparation method on the fuel cell performance were investigated with electrochemical, spectroscopic and microscopic techniques. Using pure graphene supports the final catalyst layer consists of a dense and well orientated roof tile structure which causes strong mass transport limitations for fuels and products. Thus the catalysts efficiency and finally the fuel cell performance were reduced. The addition of different carbon additives like carbon black particles or multi-walled carbon nanotubes (MWCNT) destroys this structure and forms a porous layer which is very efficient for the mass transport. The network structure of the catalyst layer and therefore the performance depends on the amount and on the morphology of the carbon additives. Due to optimizing these parameters the platinum amount could be reduced by 37% compared to a commercial standard system.     

Comparative studies of configurations and preparation methods for direct methanol fuel cell electrodes

Catalyst-coated membrane (CCM) and catalyzed diffusion medium (CDM) prepared either by brush painting method or by spraying method were compared for direct methanol fuel cell (DMFC) anode and cathode. The pore structure and the morphology of the electrodes were characterized by mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). Internal resistance corrected polarization curves were employed to separate the contribution of each compartment of the membrane electrode assembly (MEA) to the overall polarization. It was shown that the increased mass transport resistance in the anode diffusion layer made the anode in CDM form act as the methanol barrier. The CCM configuration and the increased pores in micron scales in the catalyst layer were in favor of improving the performance of both anode and cathode. Accounting for the effect of methanol permeation, the combination of the anode in CDM form prepared by brush painting method and the cathode in CCM form prepared by spraying method was finally selected as the optimized configuration for MEA, which had the highest DMFC performance under near-ambient conditions.     

Realising a reference electrode in a polymer electrolyte fuel cell by laser ablation

This work presents a new concept for realising a reference electrode configuration in a PEM fuel cell by means of laser ablation. The laser beam is used to evaporate a small part of the electrode of a catalyst-coated membrane (CCM) to isolate the reference electrode from the active catalyst layer. This method enables the simultaneous ablation of the electrodes on both sides of the CCM because the membrane is transparent for the laser beam. Therefore, a smooth electrode edge without electrode misalignment can be realised. A test fuel cell was constructed which together with the ablated CCM enables the separation of the total cell losses during operation into the cathode, anode and membrane overpotentials in PEFC as well as in DMFC mode. The methanol tolerance of a selenium-modified ruthenium-based catalyst (RuSe _x ) was investigated under real fuel cell conditions by measuring polarisation curves, electrochemical impedance spectroscopy (EIS) and current interrupt measurements (CI).     

Sub-freezing endurance of PEM fuel cells with different catalyst-coated membranes

The sub-freezing endurance of proton exchange membrane (PEM) fuel cells with hydrophobic and hydrophilic catalyst-coated membranes (CCMs) was investigated. The polarization curves, electrochemical characteristics and physical structures of the CCMs were measured. The cells were frozen at −20 °C with saturated residual water after operating at 60 °C. After eight freeze/thaw cycles, no evident negative effect on the performance of the cell with a hydrophobic CCM was observed, while the cell with a hydrophilic CCM degraded severely. By analyzing the polarization curves, it was concluded that the mass transport limitation was the main reason for the performance loss of the hydrophilic cell. The electrochemical active surface area (ECA) results suggest that the hydrophobicity of the catalyst layer (CL) has an apparent impact on the residual water distribution of the membrane electrode assembly (MEA). A larger water content in the hydrophilic CL has a negative effect on the subzero endurance. From the polarization resistance obtained from electrochemical impedance spectroscopy (EIS) the origin of degradation was further clarified. Mercury intrusion porosimetry showed that the pore size of the hydrophilic catalyst layer changed significantly after freezing; the mean pore size increased from 5.68 to 6.71 nm. However, with a water removal method, namely, gas purging, it was possible to prevent degradation effectively.