燃料电池用质子交换膜电渗拖曳的研究进展

质子交换膜的电渗拖曳直接影响燃料电池的水管理和电池系统复杂性。本文对质子交换膜电渗拖曳系数的测量方法进行了综述,并指出了各种方法的优缺点。经比较发现：电渗拖曳池、氢泵、电泳核磁共振法可测量质子交换膜与液态水接触时的电渗拖曳系数,其值一般在2～5;活度梯度法和电泳核磁共振法可测量质子交换膜与气态水接触时的电渗拖曳系数。随着复合质子交换膜的发展,亟需普遍性的测量方法测定复合膜的电渗拖曳系数,为燃料电池模型提供相关的参数,以利于数学模型对质子交换膜的准确描述。     

高温质子交换膜研究进展

高温质子交换膜燃料电池解决了传统质子交换膜燃料电池催化剂易受CO等杂质气体毒化、水热管理复杂等问题,成为当今燃料电池发展的主要方向。高温质子交换膜是实现高温操作的关键部分。本文结合质子传递机理,分析了以水作为质子溶剂、非水质子溶剂质子交换膜以及无机固态质子导体膜的研究现状,认为有机/无机复合膜和非水质子溶剂膜,尤其是其中的磷酸掺杂的PBI膜是高温质子交换膜的发展方向。     

质子交换膜燃料电池水传递模型

提出了用于研究质子交换膜燃料电池膜中水分布、水传递量分布、电流密度分布等的二维数学模型;系统地考察了电池温度、阴阳极压力差、增湿程度、质子膜厚度等条件对水的传递和膜中水分布的影响.计算结果表明:①阳极增湿能够提高气体进口段膜阳极侧水的含量;②使用越薄的质子膜,越能提高膜中水的含量;③阳极增湿程度越大,由阳极向阴极迁移的水量越多.     

质子交换膜燃料电池可视化研究进展

质子交换膜燃料电池(包括氢氧质子交换膜燃料电池和直接甲醇燃料电池)内的两相流动以及相应的水管理、气管理对燃料电池的性能和寿命有很大的影响,而可视化方法是研究流场槽道内两相流动非常重要的方法之一。可视化实验可以真实地展示气泡或液滴在流场槽道内的生成以及发展过程,有利于了解其进化机制,从而进一步优化气管理、水管理并提高电池性能。本文主要综述了质子交换膜燃料电池两极流场内两相流动的可视化研究进展,讨论了扩散层的润湿性以及扩散层内水的传递机理,还介绍了实现可视化的方法,并提出了可视化研究的不足及发展方向。     

PEM燃料电池阴极中的液态水及其影响因素

阴极多孔介质中液态水的含量对PEM燃料电池阴极中的传质及其性能具有极其重要的影响。提出了一个二维、两相、稳态数学模型,研究PEM燃料电池阴极中两相水的传递及其对电池性能的影响。模型耦合了连续方程、动量方程和组分守恒方程,并将质子膜中的净水迁移通量作为边界条件之一来处理。通过实验的方法和数值模拟的方法,研究了电池操作压力和温度对电池性能的影响,同时验证了模型的有效性。模拟发现:提高操作压力和升高阴极加湿温度使电池阴极催化剂层(CTL)和扩散层(GDL)界面上的液态水含量大幅提高;升高阳极加湿温度,电池阴极CTL和GDL界面上的液态水含量变化不明显;而升高燃料电池的操作温度,阴极CTL和GDL界面上液态水的含量降低。     

常规流场和交指型流场的质子交换膜燃料电池传热传质三维模拟

针对常规流场和交指型流场的质子交换膜燃料电池提出了三维非等温数学模型。模型详细考虑了电池内部的传热、传质和电化学反应，重点考察了多孔介质内的组分传递和膜内水的电渗和扩散作用，对氧气传递限制和膜内水迁移对电池性能的影响进行了分析和讨论。结果表明，流道的交指型设计加强了气体在多孔介质内的质量传递，提高了电池的输出性能，但相应地，阴极催化层界面水分的减少也使得膜的水合程度降低，这就需要更有效的水管理来防止膜脱水。     

质子交换膜燃料电池研究现状及发展

质子交换膜燃料电池是一种高效清洁的发电技术,具有反应动力学快、启动温度低等特点。目前质子交换膜燃料电池技术发展迅速,有望得到广泛推广和普及。本文从质子交换膜燃料电池核心组件出发,对近年来质子交换膜燃料电池的发展进行了简要概述。从材料出发,对核心组件进行分类,详细介绍了质子交换膜、催化剂以及气体扩散层的研究现状和技术特点,综述了各组件的研究方法、改进方法以及研究进展,展望了质子交换膜燃料电池的研究方向和未来发展趋势。基于高温环境下的各种优势,具有短侧链、低当量的且适用于高温低湿环境的质子交换膜仍将是重点研究对象。质子交换膜燃料电池将进一步向低Pt甚至无Pt方向发展,同时未来将实现无增湿条件下的水平衡。     

质子交换膜燃料电池阴极催化剂的位置效应

考虑局部几何效应,通过二维稳态数学模型研究了质子交换膜燃料电池阴极催化剂的位置与其表面传质和反应能力的关系。模型方程涉及氧气在催化层气孔的传输,氧气在气相和电解质相界面的分配以及氧气和质子在电解质中的传递和电化学反应过程。计算结果表明,催化剂表面的氧气扩散能力对催化剂的位置变化非常敏感,随催化剂深入电解质内部,其表面的氧气扩散能力经短暂上升后迅速下降。催化剂位置对质子传递阻力的影响与氧气扩散类似,但位置效应要弱些。性能比较确定最优的催化剂位置是恰好处于刚被电解质膜完全覆盖的位置。     

PWA-13X-CS复合质子交换膜的性能研究

用13X分子筛负载无机质子导体-磷钨酸,然后加入壳聚糖(CS)中制备得到PWA-13X-CS复合质子交换膜,对其进行扫描电镜表征,测试了其吸水率、溶胀度、质子导电率、甲醇渗透系数等性质。结果表明PWA-13X-CS复合质子交换膜溶胀度较小,机械性能较好,质子导电率明显高于壳聚糖空白膜,且随温度升高呈上升趋势,其质子导电活化能低于壳聚糖空白膜,甲醇渗透系数小于Nafion117膜。将其与同样添加负载磷钨酸的13X分子筛的聚酰亚胺复合膜及聚乙烯醇复合膜性能进行对比,结果表明PWA-13X-CS复合质子交换膜综合性能较优,在直接甲醇燃料电池中具有较好的应用潜力。     

燃料电池质子交换膜研究进展

质子交换膜作为燃料电池的关键材料之一,得到世界各国学者的广泛关注和深入研究,已先后研发出含氟高分子类、芳香烃聚合物类以及有机/无机杂化材料的质子交换膜.本文对燃料电池工作原理进行简要概述,并针对质子交换膜的应用前景及研究现状进行分析.     

An overview of electro-osmosis in fuel cell polymer electrolytes

Electro-osmosis, the transport of water with protons, in polymer electrolyte fuel cell membranes is important because it effects water management within an operating cell on both a global and local level. The electro-osmotic drag coefficient is the number of water molecules transported per proton and is a quantitative measure of the extent to which electro-osmosis occurs in a given polymer electrolyte. The methods for which electro-osmotic drag coefficients have been determined are reported. An effort is made to report proton electro-osmotic drag coefficients extensively, while a few non-proton cation electro-osmotic drag coefficients have been chosen for illustrative purposes. The results reported have implications for fuel cell performance and in the development and characterization of new polymer electrolyte membranes.     

Non-isothermal effects of single or double serpentine proton exchange membrane fuel cells

Mathematical models on transport processes and reactions in proton exchange membrane (PEM) fuel cell generally assume an isothermal cell behavior for sake of simplicity. This work aims at exploring how a non-isothermal cell body affects the performance of PEM fuel cells with single and double serpentine cathode flow fields, considering the effects of flow channel cross-sectional areas. Low thermal conductivities of porous layers in the cell and low heat transfer coefficients at the surface of current collectors, as commonly adopted in cell design, increase the cell temperature. High cell temperature evaporates fast the liquid water, hence reducing the cathode flooding; however, the yielded low membrane water content reduces proton transport rate, thereby increasing ohmic resistance of membrane. An optimal cell temperature is presented to maximize the cell performance.     

Water transport through a PEM fuel cell: A one-dimensional model with heat transfer effects

Models play an important role in fuel cell design/development. The most critical problems to overcome in the proton exchange membrane (PEM) fuel cell technology are the water and thermal management. In this work, a steady-state, one-dimensional model accounting for coupled heat and mass transfer in a single PEM fuel cell is presented. Special attention is devoted to the water transport through the membrane which is assumed to be a combined effect of diffusion and electro-osmotic drag. The transport of heat through the gas diffusion layers is assumed to be a conduction-predominated process and heat generation or consumption is considered in the catalyst layers. The analytical solutions for concentration and net water transport coefficient are compared with recent published experimental data. The operating conditions considered are various cathode and anode relative humidity (RH) values at and 2 atm. The studied conditions correspond to relatively low values of RH, conditions of special interest, namely, in the automotive applications. Model predictions were successfully compared to experimental and theoretical I-V polarization curves presented by Hung et al. [2007. Operation-relevant modelling of an experimental proton exchange membrane fuel cell. Journal of Power Sources 171, 728-737] and Ju et al. [2005a. A single-phase, non-isothermal model for PEM fuel cells. International Journal of Heat and Mass Transfer 48, 1303-1315]. The developed easy to implement model using low CPU consumption predicts reasonably well the influence of current density and RH on the net water transport coefficient as well as the oxygen, hydrogen and water vapour concentrations at the anode and cathode. The model can provide suitable operating ranges adequate to different applications (namely low humidity operation) for variable MEA structures.     

质子交换膜燃料电池两维、两相流动模型

提出了考虑电池内部两相流动的质子交换膜燃料电池数学模型,模拟了阳极、阴极两侧的流道和扩散层中同时发生两相流动时电池内部的各种传递特性,并用实验数据验证了该模型的准确性。模拟结果显示,当电池阴极扩散层中有液态水存在时会大大降低膜中的局部电流密度;质子交换膜中水的净通量方向可正、可负,因此电池的增湿策略应根据不同的运行工况而不断变化。     

DCMFC两腔液量变化与产电性能的关系

随着DCMFC产电周期的增加,阴阳极间的液位差明显增加。为解析此现象,从蒸发、渗透压、生物代谢及电场角度考察了质子和水的传递行为,研究了产水与电池性能的关系。结果表明：360 h内蒸发、渗透压引起的液量变化少于0.50 ml（液面降低0.5 mm）;断路312 h,阳极代谢气体使PEM形变凸向阴极,阳极液减少6.20 ml（下降6.5 mm）,阴极液增加10.75 ml（上升11.2 mm）,两腔液位差达17.7 mm;通路下,除膜的形变,水合质子被电渗透到阴极并还原成水,312 h内阳极液减少10.70 ml（下降11.1 mm）,阴极液增加17.00 ml（上升17.7 mm）,两腔液位差达28.8 mm,且产水量随电压的增大而增加。研究表明,生物代谢及电渗透对两腔液量影响较大,产水量可表征质子传递率。经计算该系统质子传递率大于54%,为评判产电效率提供了简便依据。     

采用不同流场的质子交换膜燃料电池内部传递现象模拟

A numerical model for proton exchange membrane (PEM) fuel cell is developed, which can simulate such basic transport phenomena as gas-liquid two-phase flow in a working fuel cell. Boundary conditions for both the conventional and the interdigitated modes of flow are presented on a three-dimensional basis. Numerical techniques for this model are discussed in detail. Validation shows good agreement between simulating results and experimental data. Furthermore, internal transport phenomena are discussed and compared for PEM fuel cells with conventional and interdigitated flows. It is found that the dead-ended structure of an interdigitated flow does increase the oxygen mass fraction and decrease the liquid water saturation in the gas diffusion layer as compared to the conventional mode of flow. However, the cathode humidification is important for an interdigitated flow to acquire better performance than a conventional flow fuel cell.     

Three-dimensional numerical simulation of straight channel PEM fuel cells

The need to model three-dimensional flow in polymer electrolyte membrane (PEM) fuel cells is discussed by developing an integrated flow and current density model to predict current density distributions in two dimensions on the membrane in a straight channel PEM fuel cell. The geometrical model includes diffusion layers on both the anode and cathode sides and the numerical model solves the same primary flow related variables in the main flow channel and the diffusion layer. A control volume approach is used and source terms for transport equations are presented to facilitate their incorporation in commercial flow solvers. Predictions reveal that the inclusion of a diffusion layer creates a lower and more uniform current density compared to cases without diffusion layers. The results also show that the membrane thickness and cell voltage have a significant effect on the axial distribution of the current density and net rate of water transport. The predictions of the water transport between cathode and anode across the width of the flow channel show the delicate balance of diffusion and electroosmosis and their effect on the current distribution along channel.     

Organic-inorganic nanocomposite polymer electrolyte membranes for fuel cell applications

Organic-inorganic nanocomposite polymer electrolyte membrane (PEM) contains nano-sized inorganic building blocks in organic polymer by molecular level of hybridization. This architecture has opened the possibility to combine in a single solid both the attractive properties of a mechanically and thermally stable inorganic backbone and the specific chemical reactivity, dielectric, ductility, flexibility, and processability of the organic polymer. The state-of-the-art of polymer electrolyte membrane fuel cell technology is based on perfluoro sulfonic acid membranes, which have some key issues and shortcomings such as: water management, CO poisoning, hydrogen reformate and fuel crossover. Organic-inorganic nanocomposite PEM show excellent potential for solving these problems and have attracted a lot of attention during the last ten years. Disparate characteristics (e.g., solubility and thermal stability) of the two components, provide potential barriers towards convenient membrane preparation strategies, but recent research demonstrates relatively simple processes for developing highly efficient nanocomposite PEMs. Objectives for the development of organic-inorganic nanocomposite PEM reported in the literature include several modifications: (1) improving the self-humidification of the membrane; (2) reducing the electro-osmotic drag and fuel crossover; (3) improving the mechanical and thermal strengths without deteriorating proton conductivity; (4) enhancing the proton conductivity by introducing solid inorganic proton conductors; and (5) achieving slow drying PEMs with high water retention capability. Research carried out during the last decade on this topic can be divided into four categories: (i) doping inorganic proton conductors in PEMs; (ii) nanocomposites by sol-gel method; (iii) covalently bonded inorganic segments with organic polymer chains; and (iv) acid-base PEM nanocomposites. The purpose here is to summarize the state-of-the-art in the development of organic-inorganic nanocomposite PEMs for fuel cell applications.