质子交换膜燃料电池关键技术研究进展

简述了质子交换膜燃料电池(PEMFC)的工作原理及特点;综述了PEMFC关键技术的最新研究进展,包括质子交换膜合成、电催化剂制备、膜电极工艺及水管理和热控制;并简介了我国PEMFC的开发情况。     

质子交换膜燃料电池催化层的有效质子电导率

A numerical model was presented to predict the specific proton conductivity of the catalyst layer in Proton Exchange Membrane Fuel Cells (PEMFC). This model was derived from the random packed spheres with simple cubic, body-centered cubic and face-centered cubic structures. The effects of sphe reradius rs, bulk proton conductivity kb, contact parameter γ and contact angle a on proton transfer within a homogeneous agglomerate sphere consisting of carbon-supported catalyst and electrolyte were analyzed. A correlation equation of specific proton conductivity was obtained by data fitting. The real effective proton conductivity in the catalyst layer was measured by addition to a standard Membrane Electrolyte Assembly of an inactive composite layer in the electrolyte path between the anode and cathode. The model was validated by good agreement between calculations and measured data.     

氢氧质子交换膜燃料电池阴极流道设计模型

为了优化氢氧质子交换膜燃料电池阴极的气体流道,建立了沿流道长度和深度方向的气体流道设计模型.模型考虑了阴极气体在流道中的动量传递、质量传递和电极反应等物理过程.将二维问题经积分均化后转化为较简单的一维问题,偏微分方程组转变为常微分方程组,使计算过程得以简化.以50 cm长的流道为例,计算了沿流道方向的浓度、流速以及电流密度的分布.还利用此模型分析了各操作与设计参数如入口流速、流道深度、交换电流密度等对浓度、流速和电流密度分布的影响.     

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.     

质子交换膜燃料电池加氢反应器

简述了燃料电池反应器的研究现状,根据膜反应器的设计思想,提出质了交换膜燃料电池加氢反应器的新概念,阐述了质子交换膜燃料电池作为加氢反应器的原理、可行性及应用前景。     

质子交换膜燃料电池的研究进展

质子交换膜燃料电池（PEMFC）是一种高效节能、工作稳定、环境友好的理想发电装置。质子交换膜是PEMFC的核心组成,是一种选择透过性膜,主要起传导质子、分割氧化剂与还原剂的作用。PEMFC用电催化剂主要为铂系电催化剂,为降低成本,提高铂的利用率和开发非铂系催化剂是今后催化剂研究的主要方向之一。对PEMFC电极的工作原理,关键组件及电池的水管理、热管理方法等作了综述。     

乙烷质子交换膜燃料电池的研究

研究了以乙烷作为燃料、全氟磺酸高分子膜(Nafion膜)作为质子交换膜、Pt或Pt-Ru作为电极催化剂主要组分、并通过掺杂Nafion膜作为电极内的离子导体构成的燃料电池电化学性能.研究了两种电极催化剂:Pt与Pt-Ru复合催化剂的制备及构成的单电池在不同温度及运行时间下的电化学性能.温度增加,电池性能变好;运行时间增加,电池性能下降,在相同的温度与运行时间下,Pt-Ru复合催化剂构成的电池比Pt催化剂构成的电池极化小.通过分析电极反应产物,探讨了乙烷电极及电池的反应机理.结构为C2H6,( Pt-Ru+膜材料复合阳极)/Nafion膜/(Pt+膜材料复合阴极),O2 的质子交换膜燃料电池,在150℃时,电池的最大输出电流和功率密度分别高达70 mA·cm-2和22 mW·cm-2.     

直接甲醇燃料电池质子交换膜的发展现状

直接甲醇燃料电池(DMFC)是20世纪90年代兴起的第六代燃料电池,以其诸多的优点引起人们的广泛关注和研究。其中聚合物电解质膜是DMFC的关键技术,起着隔离阴阳极、质子传输、绝缘电子的作用。它的作用决定着DMFC的输出功率、电池效率、成本及应用前景。本文介绍了已商品化的全氟磺酸膜(Nafion膜)的结构及性能、以及替代膜的国内外发展现状,指出DMFC用膜的研究是21世纪能源研究的重点。     

质子交换膜燃料电池的发展现状

简要叙述了质子交换膜燃料电池的发展历史,介绍了高效、新型电催化剂、新型质子交换膜、新型双极板与流场的研究、应用、开发等关键技术,并对质子交换膜燃料电池的发展前景进行了展望。     

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.     

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.     

Modelling of performance of PEM fuel cells with conventional and interdigitated flow fields

A simple mathematical model is developed to investigate the superiority of the interdigitated flow field design over the conventional one, especially in terms of maximum power density. Darcy's equation for porous media and the standard diffusion equation with effective diffusivity are used in the gas diffuser, and a coupled boundary condition given by the Butler–Volmer equation is used at the catalyst layer interface. The performance of PEM fuel cells with a conventional flow field and an interdigitated flow field is studied with other appropriate boundary conditions. The theoretical results show that the limiting current density of a fuel cell with an interdigitated flow field is about three times the current density of a fuel cell with a conventional flow field. The results also demonstrate that the interdigitated flow field design can double the maximum power density of a PEM fuel cell. The modelling results compared well with experimental data in the literature.     

Numerical optimization of bipolar plates and gas diffusion layers for PEM fuel cells

This paper is devoted to the numerical optimization of the dimensions of channels and current transfer ribs of bipolar plates as well as the thickness and porosity of gas diffusion layers. A mathematical model of the transfer processes in a PEM fuel cell has been developed for this purpose. The results are compared with experimental data. Recommendations of the values of operating parameters and some design requirements to increase PEM fuel cell efficiency are suggested.This paper was originally Presented at the CHISA Congress, Prague, August 2004.An erratum to this article can be found at     

Measurements of proton conductivity in the active layer of PEM fuel cell gas diffusion electrodes

This paper reports further studies to understand and optimize the Membrane and Electrode Assembly (MEA) structure in Polymer Electrolyte Membrane Fuel Cells (PEMFCs). The effective proton conductivity in the active catalyst layer was measured as a function of its composition, which consisted of platinum catalyst on carbon support (E-Tek) and Nafion® polymer electrolyte (DuPont de Nemours). The conductivity was calculated from the resistance added to a standard MEA by the addition of an inactive composite layer in the electrolyte path between the anode and cathode. The specific conductivity of the active layer was found to be proportional to the volume fraction of Nafion® in the composite mixture, following the relationship κ^eff_H⁺≈0.078_Nafion+0.004 S cm⁻¹. Modeling studies showed that this ionic conductivity limits the utilized active layer thickness to 20–25 μm.     

Two-dimensional analysis of PEM fuel cells

This study reports a two-dimensional numerical simulation of a steady, isothermal, fully humidified polymer electrolyte membrane (PEM) fuel cell, with particular attention to phenomena occurring in the catalyst layers. Conservation equations are developed for reactant species, electrons and protons, and the rate of electrochemical reactions is determined from the Butler–Volmer equation. Finite volume method is used along with the alternating direction implicit algorithm and tridiagonal solver. The results show that the cathode catalyst layer exhibits more pronounced changes in potential, reaction rate and current density generation than the anode catalyst layer counterparts, due to the large cathode activation overpotential and the relatively low diffusion coefficient of oxygen. It is shown that the catalyst layers are two-dimensional in nature, particularly in areas of low reactant concentrations. The two-dimensional distribution of the reactant concentration, current density distribution, and overpotential is determined, which suggests that multi-dimensional simulation is necessary to understand the transport and reaction processes occurring in a PEM fuel cell.     

Measurement of in-plane effective thermal conductivity in PEM fuel cell diffusion media

Gas diffusion media used in polymer electrolyte membrane (PEM) fuel cells are highly anisotropic with significantly different transport property values in the through- and in-plane directions. In this study, experimental measurements of the in-plane effective thermal conductivity k for gas diffusion media used in PEM fuel cells have been carried out using a parallel thermal conductance technique. Conductivity values are measured at a mean sample temperature of 70 °C for six different material types and two different orientations in order to quantify the effect of PTFE content on thermal conductivity and to reveal any anisotropic behavior. The results vary from a minimum of k = 3.54 W/(m °C) to a maximum value of 15.1 W/(m °C) for various samples and configurations tested in this study, with an uncertainty between 1% and 2% for all the cases investigated.     

A distributed dynamic model for chronoamperometry, chronopotentiometry and gas starvation studies in PEM fuel cell cathode

Electrochemical systems differ significantly from conventional chemical systems. The response of voltage to changes in current and that of current to changes in voltage is much faster compared to typical transients observed in transport variables. In this work, the transient characteristics of various transport and electrochemical phenomena are studied in the PEM fuel cell cathode using a dynamic model. Model-based chronoamperometry and chronopotentiometry studies are performed to investigate the interactions among the various phenomena and the limiting mechanisms under various operating modes. The dynamic response of current to changes in voltage under chronoamperometry and that of voltage to changes in current under chronopotentiometry are found to be significantly different. Moreover, it is also observed through simulations that the dynamics in the output variables are strongly influenced by the operating cell voltage. Results from chronoamperometry studies are used to highlight the problem of oxygen starvation, which is also reflected by the magnitude of oxygen excess ratio or stoichiometric ratio. Results from step tests in chronopotentiometry studies are used to study nonlinearities in the response of voltage to changes in inputs such as, current and air flow rate.     

Development of gas diffusion layer using water based carbon slurry for proton exchange membrane fuel cells

The micro-porous layer of gas diffusion layers (GDLs) was fabricated with the carbon slurry dispersed in water containing sodium dodecyl sulfate (SDS), by wire rod coating process. The aqueous carbon slurry with micelle-encapsulation was highly consistent and stable without losing any homogeneity even after adding polytetrafluoroethylene (PTFE) binder for hundreds of hours. The surface morphology, contact angle and pore size distribution of the GDLs were examined using SEM, Goniometer and Hg Porosimeter, respectively. GDLs fabricated with various SDS concentrations were assembled into MEAs and evaluated in a single cell PEMFC under diverse operating relative humidity (RH) conditions using H₂/O₂ and H₂/air as reactants. The peak power density of the single cell using the GDLs with optimum SDS concentration was 1400 and 500 mW cm⁻² with H₂/O₂ and H₂/air at 90% RH, respectively. GDLs were also fabricated with isopropyl alcohol (IPA) based carbon slurry for fuel cell performance comparison. It was found that the composition of the carbon slurry, specifically SDS concentration played a critical role in controlling the pore diameter as well as the corresponding pore volumes of the GDLs.     

A novel design of distribution zone in scaled-up PEM fuel cells based on active control of transverse flow

The flow distribution is of significance to the fuel cell performance and durability, which has been studied from a theoretical and practical level in this work. The transverse-flow-control-based mechanism behind flow distribution processes is revealed. The core lies in the reasonable generation and distribution of transverse flow, which are the prerequisite and co-requisite for flow homogeneity. For the dual purpose, a novel design of combined-mesh-type distribution zone is proposed incorporating central horizontal meshes and lateral vertical meshes. The design philosophy and methodology are clarified. Under these guidelines, the novel distributor design is applied to different flow field plate geometries including the shorter distribution zone, higher expansion ratio, and scaled-up fuel cell. Through organized and detailed simulations, two key geometrical parameters (porosities of central and lateral meshes) are quantified and the superior effect on flow distribution is validated.     

A high-throughput study of PtNiZr catalysts for application in PEM fuel cells

The effects of adding Zr to PtNi oxygen reduction reaction (ORR) electrocatalyst alloys were examined in a study aimed at probing the possibility of creating catalysts with enhanced resistance to corrosion in a PEM fuel cell environment. Samples consisting of pure Pt or PtNiZr alloys with a range of compositions (not exceeding 11 at.% Zr) were fabricated using co-sputter deposition. A high-throughput fabrication approach was used wherein 18 distinct thin film catalyst alloy samples with varying compositions were deposited onto a large-area substrate with individual Au current collector structures. A multi-channel pseudo-potentiostat allowed for the simultaneous quantitative study of catalytic activity for all 18 electrodes in a single test bath, a first for the study of ORR electrocatalysts. A properly stirred oxygenated 1 M H₂SO₄ electrolyte solution was used to provide each electrode with a steady-state flow of reactants during electrochemical evaluation. The onset potentials, absolute current density values, and Tafel analysis data obtained using this technique were compared with literature reports. The analyses showed that most PtNiZr alloys tested offered improvements over pure Pt, however those surfaces with a high mole fraction (>4 at.%) of Zr exhibited reduced activity that was roughly inversely correlated to the amount of Zr present. Film composition, morphology, and crystallographic properties were examined using X-ray energy dispersive spectroscopy (XEDS), X-ray photoelectron spectroscopy (XPS), SEM, and synchrotron X-ray diffraction. These data were then correlated with electrochemical data to elucidate the relationships between composition, structure, and relative performance for this ternary system.