高温质子交换膜燃料电池的研究进展(英文)

Due to the need for clean energy, the development of an efficient fuel cell technology for electricity generation has received considerable attention. Much of the current research efforts have investi-gated the materials for and process development of fuel cells, including the optimization and simpli-fication of the fuel cell components, and the modeling of the fuel cell systems to reduce their cost and improve their performance, durability and reliability to enable them to compete with the con-ventional combustion engine. A high temperature proton exchange membrane fuel cell(HT-PEMFC) is an interesting alternative to conventional PEMFCs as it is able to mitigate CO poisoning and water management problems. Although the HT-PEMFC has many attractive features, it also possesses many limitations and presents several challenges to its widespread commercialization. In this re-view, the trends of HT-PEMFC research and development with respect to electrochemistry, mem-brane, modeling, fuel options, and system design were presented.     

静电纺丝制备质子交换膜燃料电池催化剂层综述

质子交换膜燃料电池催化剂层在成本、耐久性以及性能上的局限是制约燃料电池汽车商业化的瓶颈. 已有文献证明静电纺丝技术制备的纳米纤维催化剂层能提高催化剂利用率、增加三相界面和三相通道以及提高耐久性. 作者结合所在课题组的工作综述了静电纺丝技术制备质子交换膜燃料电池催化剂层的研究进展. 首先,介绍了质子交换膜燃料电池催化剂层的发展历程,并从制备方式和结构两个方面对其进行分类和总结;接下来,从静电纺丝纳米纤维催化剂层的制备、物理特性表征、电化学性能分析及耐久性表征等方面进行了总结;最后,从三相界面、三相通道以及量产适用性的视点比较了三种结构的催化剂层,介绍了质子交换膜燃料电池催化剂层的发展趋势,并梳理了静电纺丝法制备质子交换膜燃料电池催化剂层领域待研的问题.     

低维纳米材料在质子交换膜燃料电池电催化反应中的应用

在聚合物膜燃料电池中,电催化剂决定了电池的运行寿命及性能。本文按照材料维数的不同,分别介绍了近年来零维、一维和二维材料在聚合物膜燃料电池电极反应中应用的最新研究进展;并对各类聚合物膜燃料电池电催化反应的机理和研究侧重点进行了详细的介绍。     

Carbon‐Nanotube‐Supported Bio‐Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells

A biomimetic nickel bis‐diphosphine complex incorporating the amino acid arginine in the outer coordination sphere was immobilized on modified carbon nanotubes (CNTs) through electrostatic interactions. The functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H₂/2 H⁺ interconversion from pH 0 to 9, with catalytic preference for H₂ oxidation at all pH values. The high activity of the complex over a wide pH range allows us to integrate this bio‐inspired nanomaterial either in an enzymatic fuel cell together with a multicopper oxidase at the cathode, or in a proton exchange membrane fuel cell (PEMFC) using Pt/C at the cathode. The Ni‐based PEMFC reaches 14 mW cm⁻², only six‐times‐less as compared to full‐Pt conventional PEMFC. The Pt‐free enzyme‐based fuel cell delivers ≈2 mW cm⁻², a new efficiency record for a hydrogen biofuel cell with base metal catalysts.     

车用燃料电池启停工况性能衰减

车用燃料电池(质子交换膜燃料电池)技术经过二十余年的持续研发和不断突破,使得燃料电池汽车性能基本满足了商业化指标,并成为当前备受瞩目的新能源汽车。然而,质子交换膜燃料电池伴随实际车况变化会经历燃料供应、湿度、温度、电流、电压等复杂循环过程,造成燃料电池的关键材料衰减加速,并且车用燃料电池的耐久性问题棘手且涉及面广。本文针对车用燃料电池的启停工况,归纳分析了启停工况下燃料电池的研究过程、衰减机理、实验论证、建模分析,并从燃料电池系统管理角度分析了启停衰减的缓解策略。通过对已有启停工况下质子交换膜燃料电池性能衰减失效的梳理,提出了本文的观点、分析和解释。     

Estimation of MEA parameters and prediction of PEM fuel cells electrical performances using numerical modelling

In this paper, a coupled model of transfer phenomena within Proton Exchange Membrane Fuel Cell (PEMFC) developed from Stefan-Maxwell (in the diffusion and active layers), Butler-Volmer (in the active layer), and water mass transport (in the electrolyte membrane) equations is presented. This modeling allows interpreting experimental results, prediction of PEMFC electrical performances and guiding perspective investigations on optimization of PEMFC. The model helps the research of dominating sensitivity parameters, as well as the estimation of some badly known MEA (Membrane Electrode Assembly) parameters using fuel cell tests.     

直接甲酸燃料电池的研究进展

近年来,直接甲酸燃料电池(DFAFC)的研发取得了很大的进展,已有报道用Pd作阳极催化剂的DFAFC的最大能量密度为0.25 W/cm²,很接近于以氢为燃料的质子交换膜燃料电池(PEMFC),表明DFAFC有很好的发展前景。 综述了DFAFC的研究进展、甲酸电氧化机理、阳极复合催化剂性能提高的原因和机理。DFAFC存在的主要问题,并对其发展进行了展望。     

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     

钯基氧还原和乙醇氧化反应电催化剂:关于结构和机理研究的一些近期见解

质子交换膜燃料电池和直接乙醇燃料电池已成为可持续性清洁能源研究的一个聚焦点。在燃料电池中,氧还原反应和乙醇氧化反应是两个重要的反应,其相关高活性、高稳定性并且廉价的催化剂的研发仍然存在很多问题,极大地制约了燃料电池的大规模商业化应用。其中的挑战主要来自于对纳米催化剂结构和反应机理的有限认识。由于实验表征理论计算的结合,对钯基合金纳米材料电催化剂的研究得到了很大的进展。本文从实验和理论计算两个方面出发,重点讨论了应用于氧还原反应和乙醇氧化反应的钯和钯基电催化剂的结构和反应机理方面的近期研究的一些见解。这些见解对未来催化剂的设计与优化有一定的启发意义。     

The use of 1H NMR microscopy to study proton-exchange membrane fuel cells.

To understand proton-exchange membrane fuel cells (PEMFCs) better, researchers have used several techniques to visualize their internal operation. This Concept outlines the advantages of using 1H NMR microscopy, that is, magnetic resonance imaging, to monitor the distribution of water in a working PEMFC. We describe what a PEMFC is, how it operates, and why monitoring water distribution in a fuel cell is important. We will focus on our experience in constructing PEMFCs, and demonstrate how 1H NMR microscopy is used to observe the water distribution throughout an operating hydrogen PEMFC. Research in this area is briefly reviewed, followed by some comments regarding challenges and anticipated future developments.     

质子交换膜燃料电池铂电催化剂稳定策略

质子交换膜燃料电池使用寿命低是制约其商业化应用的主要瓶颈. 其中,影响质子交换膜燃料电池寿命的一个主要因素是其所广泛使用的贵金属铂基电催化剂在燃料电池苛刻的运行环境下（如可变电压、强酸性、气液两相流等）容易发生降解,导致电催化剂性能衰减,从而降低了质子交换膜燃料电池的使用寿命. 因此,如何保持铂基电催化剂的电化学稳定性已成为质子交换膜燃料电池稳定性研究中的重大科学问题. 本论文基于作者在该领域的长期研究成果,评述了应用于质子交换膜燃料电池的铂电催化剂稳定性的研究进展. 重点关注了能够大幅改善铂催化剂电化学稳定性的策略,包括聚合物稳定策略、多孔碳封装/限域稳定策略以及载体稳定策略,并对这些铂催化剂稳定策略所面临的挑战进行了展望.     

Performance improvement of air-breathing proton exchange membrane fuel cell (PEMFC) with a condensing-tower-like curved flow field

Air-breathing proton exchange membrane fuel cells (PEMFCs) are very promising portable energy with many advantages. However, its power density is low and many additional supporting parts affect its specific power. In this paper, we aim to improve the air diffusion and fuel cell performance by employing a novel condensing-tower-like curved flow field rather than an additional fan, making the fuel cell more compact and has less internal power consumption. Polarization curve test and galvanostatic discharge test are carried out and proved that curved flow field can strengthen the air diffusion into the PEMFC and improve its performance. With appropriate curved flow field, the fuel cell peak power can be 55.2% higher than that of planar flow field in our study. A four-layer stack with curved cathode flow field is fabricated and has a peak power of 2.35 W (120 W/kg).     

Application of electrospinning for the fabrication of proton-exchange membrane fuel cell electrodes

Electrospun materials have been gaining great interest in the energy sector. Their tunability and robustness make them highly attractive, particularly for proton-exchange membrane fuel cell (PEMFC) electrodes. Conventional PEMFC electrodes, prepared by either spraying, painting, or slot-die coating, have not yet met the needs of large-scale PEMFC use. Electrospinning of fibrous materials has already shown great promise as an alternative methodology for electrode fabrication. Electrospinning has been used in fuel cell electrodes through two primary means: (1) segmented carbon or inorganic fibers to serve as precious metal catalyst support, and (2) high aspect ratio polymer/particle fibers to serve directly as the electrode. The use of electrospun fibrous electrodes has led to improved PEMFC durability and increased power output at low catalyst loadings, both of which are of paramount importance to large-scale commercialization of PEMFC electric vehicles.     

CO/H_2燃料气的质子交换膜燃料电池性能研究

质子交换膜燃料电池的燃料气多来自于重整气 ,而重整气中所含的CO对电催化剂有毒化作用 ,使电池性能大幅度衰减 .本文就CO对燃料电池的性能影响作了系统的实验研究 ,结果证明 :随CO通入时间的延长 ,电池性能剧烈衰减 ,然后趋于稳定 ,但仍有振荡 ;同时CO浓度越高 ,中毒现象越严重 ;温度升高 ,CO的毒化作用减轻 ;CO在催化剂表面的吸附是可逆的 ;PtRu/C较Pt/C的抗CO中毒能力强 .本文所制的PtRu/C催化剂的抗CO性能已与商品催化剂接近     

PEMFC催化剂的研究：自制Pt/C电催化剂的性质

研究了一种用于质子交换膜燃料电池(PEMFC)的自制Pt/C电催化剂(标记为THYT-1)的物理化学和电化学性质.将THYT-1电催化剂与E-TEK公司的同类电催化剂的组成、形态及电催化性能进行了比较.单电池测试结果显示, THYT-1的电催化性能优于E-TEK电催化剂. CV测试结果表明CO在这两种电催化剂上的电氧化性能相近；TEM分析表明两种催化剂上Pt晶粒在炭载体上呈均匀分布，平均粒径均为2～3 nm； XPS和XRD测试结果表明两种催化剂中Pt主要以金属态存在.这些数据表明THYT-1催化剂的物理化学性质与E-TEK公司的相类似.     

质子交换膜燃料电池零下冷启动研究

在零下启动过程中,质子交换膜燃料电池阴极中氧气还原反应生成的水会在催化剂层内部结冰,因而阻碍氧气传输,覆盖催化剂层反应活性位点,降低电化学活性面积,影响燃料电池发电性能,甚至会导致零下启动失败;同时,结冰/融化循环还会破坏膜电极结构,影响燃料电池寿命。因此,质子交换膜燃料电池零下启动技术的研究对促进燃料电池汽车的推广应用有重要意义。本文针对质子交换膜燃料电池的零下启动过程,从实验研究、机理解释、模型分析及策略开发等角度对文献内容进行了梳理,并对涉及质子交换膜燃料电池零下启动过程的专利技术进行了总结。     

电化学阻抗谱在质子交换膜燃料电池动态的先导应用

通过分析电化学阻抗（EIS）在质子交换膜燃料电池（PEMFC）动态应用,本文指出制约EIS 工具发展的瓶颈问题. EIS 高频电阻确定电池内阻已成普遍方法,但仅在小电流电池可以应用;低频分析因涉及物质传输仍是难点和重点;EIS 改进型Randles 等效电路分析已初步建立,并深入至物质传输-反应、电池操作/衰减、高温电池研究;EIS 正发展为电堆分析工具、电动汽车控制核心. 然而多学科交叉的暂态EIS 发展,仍是前沿突破难点.     

L'hydrogene pour le transport sur route : réalisations et développements

Hydrogen for road transportation : achievements and developments. At the beginning of this millenium, hydrogen appears as a potential energy carrier for the future. Thus, it could serve as a storage medium for renewable energy forms, which should play an increasing part in the world energy supply. In a closer future, hydrogen could also become a fuel for prospective fuel-cell and internal-combustion vehicles. We present here an inventory of the various technologies related to the use of hydrogen in road transportation : propulsion type (fuel cell and electric motor, or internal combustion engine), hydrogen production, on-board storage, infrastructure. Safety, standardization and regulation aspects will also be addressed. Presently, the majority of hydrogen buses are equipped with polymer membrane fuel cells (PEMFC), directly supplied with hydrogen from pressurized vessels (300 bars). On the other hand, car manufacturers are developing various types of experimental vehicles : internal-combustion engine cars with liquid hydrogen storage, fuel cell (PEMFC) cars with storage of hydrogen (liquid, gaseous, hydride) or of methanol. The type of required infrastructured will depend on the type of fuel chosen by the car makers and on the requirements of the oil companies. Several hydrogen supply stations, of different technologies, have already been set up. They deliver gaseous or liquid hydrogen produced by reforming of natural gas or by electrolysis. The building of a hydrogen-based fueling system requires the development of specific means of production, transportation, storage and delivery. Public acceptance will have to be won by guaranteeing safety, reliability, performance and competitivity. Presently, research and development work is mainly carried out on : on-board storage of hydrogen ; on-board systems for the production of hydrogen from methanol and petrol ; standardization and regulation.     

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。     

Stabilization Strategies of Pt Catalysts for Proton Exchange Membrane Fuel Cells北大核心CSCD

The low service lifetime of proton exchange membrane fuel cells (PEMFCs) is the main bottleneck for their commercial applications.One of the main factors is that the expensive metal Pt catalyst is easy to degradation under the harsh working environment of PEMFC (such as variable voltage, strong acidity, gas-liquid two-phase flow), which leads to the inevitable decay of the catalytic performance, thus, seriously restricting the lifetime of PEMFC.Therefore, the electrochemical stability of Pt-based electrocatalysts has become an important and hot topic to improve the PEMFC lifetime.In this paper, we review the recent development in enhancing the stability of Pt electrocatalysts for PEMFC, mainly focusing on the achievements obtained by our group, especially, the polymer stabilization strategy, carbon encapsulation/confinement stabilization strategy, and support stabilization strategy.In addition, the challenges in these Pt catalyst stabilization strategies are summarized, and the corresponding measures and future research trends in facing these challenges are suggested.,,,,. © 2018 Chinese Chemical Society. All rights reserved.