直接液体甲醇燃料电池流场组织行为研究(Ⅰ) 传统对称流道电池的模型建立

建立了直接甲醇燃料电池垂直流道方向电池单元的二维稳态数学模型,考虑了电化学动力学、多组分传递和甲醇渗透影响.计算了流道布置密度、扩散层、催化层和质子交换膜等组件尺度对电池内物料传质特性、化学反应组织和电池输出性能的影响.研究发现,增加流道布置密度、增加催化层厚度能有效提高电极反应均匀性和电池性能.其中催化层和质子膜的厚度影响最为显著,在该文研究范围内分别可提高电池的平均电流密度131.0%和17.8%.而扩散层和质子交换膜厚度都存在一个最佳值,需要与以上流场板设计尺寸和膜电极尺寸匹配.     

质子交换膜燃料电池内部传热传质三维模拟

针对常规流场质子交换膜燃料电池提出了三维非等温数学模型。模型考虑了电化学反应动力学以及反应气体在流道和多孔介质内的流动和传递过程,详细研究了水在质子膜内的电渗和扩散作用。计算结果表明,反应气体传质的限制和质子膜内的水含量直接决定了电极局部电流密度的分布和电池输出性能;在电流密度大于0.3~0.4A/cm2时开始出现水从阳极到阴极侧的净迁移;高电流密度时膜厚度方向存在很大的温度梯度,这对膜内传递过程有较大影响。     

质子交换膜燃料电池数值分析

建立了一个三维的数学模型来模拟研究质子交换膜燃料电池,以及流道里流体的流动、阳极氢气和阴极氧气各组分的传递、热量传递、电荷传递、和氧化还原的电化学反应动力学,得到了电池内的组分浓度分布情况、温度场分布情况、以及多孔扩散层孔隙率对电池性能的影响.     

PEMFC翅脉流道传质及输出性能分析

为研究流道结构对质子交换膜燃料电池（PEMFC）反应气体质量传输及输出性能的影响,建立翅脉流道、叶脉流道及蛇形流道的三维PEMFC几何模型,并对比3种流道的反应气体浓度分布、压力分布及电流密度分布,最后对翅脉流道结构参数进行优化。结果表明,与蛇形流道、叶脉流道相比,翅脉流道能明显改善流道和扩散层内反应气体浓度分布的均匀性,有利于强化反应气体向催化层的质量传递;翅脉流道能减小气体压力分布梯度,使反应气体扩散更加充分;翅脉流道的平均膜电流密度更大,有利于促进电化学反应稳定进行;翅脉流道能改善PEMFC的输出性能,翅脉流道峰值功率密度比蛇形流道、叶脉流道分别提高7.72%和6.25%;减小翅脉流道的直流道长度或圆弧流道圆心角,可提升翅脉流道输出性能。     

钙离子对质子交换膜燃料电池性能衰减机理研究

采用试验方法,通过向质子交换膜燃料电池(PEMFC)的电极(阳极和阴极)注入2种浓度(200和500 mg/L)的Ca~(2+)溶液,研究Ca~(2+)对PEMFC电化学性能的影响;通过扫描电镜(SEM),能量散射谱仪(EDS)和电子探针(EPMA)对经Ca~(2+)污染20 h后的电池性能的衰减机理进行研究。实验结果表明,经200和500 mg/L Ca~(2+)污染PEMFC阳极20 h后,电池的电化学性能衰减明显,随着Ca~(2+)浓度的增加,电池电化学性能衰减程度增大;SEM和EDS实验结果表明,经500 mg/L Ca~(2+)污染PEMFC阳极20 h后,阴、阳两极的气体扩散层分别与阴、阳两极的催化层剥离,在质子交换膜、阳极催化层、阳极气体扩散层以及阴极气体扩散层均发现Ca元素,在质子交换膜上Ca元素含量高于其他部件上;EPMA实验结果表明,Ca~(2+)污染PEMFC阳极后,Ca元素主要存在于质子交换膜上;研究结果表明,PEMFC电化学性能衰减的机理主要是由于Ca~(2+)与质子交换膜中的质子发生离子交换反应并取代质子交换膜中的磺酸根基团上的质子形成新的磺酸盐结构所致。     

空气抽吸式甲醇燃料电池传热与传质特性

空气抽吸式直接甲醇燃料电池不仅具有被动式燃料电池的优点,同时又便于将其串联成电堆提高输出电压。建立以阴极为管道抽吸式结构的直接甲醇燃料电池的三维、两相、非等温稳态数值模型,研究了质子交换膜性能、供给甲醇浓度以及电堆规模对电池性能及燃料利用率的影响。对于保温较好的大电堆,采用低甲醇穿透的改性质子交换膜能同时提升燃料利用率和比功率;此类电堆若采用穿透率低的改性膜,则2 mol/L的甲醇浓度就能保证电池在较大的电流密度区间内维持较高的功率与效率。作为影响电池运行温度的重要因素,电堆规模的大小将直接影响质子交换膜种类与甲醇浓度等关键参数的设计与选择。     

质子交换膜燃料电池的膜电极及其湿度特性

质子交换膜燃料电池的膜电极结构与电池性能密切相关，膜的湿度直接影响膜的性能。膜内水的迁移受到多个参数的影响：较大的电流密度使水的净迁移量下降；电池温度的提高将增大电池水平衡的电流密度；提高湿化程度可以减小膜的欧姆损失。膜内的湿度不足以保证燃料电池正常工作，就必须采用湿化方法。水的迁移过程涉及到电池的压降和温度变化。实际的湿度状态是各种因素的综合．电池的工作条件最终决定了它自身的水平衡状态。     

质子交换膜燃料电池阴极传质过程的数值模拟

利用CFD方法对采用交指型流道质子交换膜燃料电池阴极的传质过程进行数值模拟,得到了阴极扩散层内氧气和水蒸汽质量浓度的分布特性,探讨了电池结构参数和操作条件对电池性能的影响。     

气体扩散层结构对PEMFC性能影响二维数值模拟

质子交换膜燃料电池在运行过程中反应物从流道传输至催化层时会经过气体扩散层,气体扩散层即 可用来传输反应气体,又用来排出反应物生成的水,所以探究气体扩散层的结构对参加反应的物质及生成物 传输的影响规律有助于了解其分布情况。通过数值模拟比较了穿孔型、树状型和不规则形状气体扩散层在不 同孔隙率下顺流流动时对电池性能的影响情况。计算结果表明,气体扩散层结构严重影响质子交换膜燃料电 池性能,三种不同形状的气体扩散层对应的电性能随孔隙率的变化规律各不相同,到达催化层表面氧气的含 量受扩散层结构影响比氢气大,气体扩散层结构对阴极侧生成物水含量的影响不可忽略。     

质子交换膜水电解中气-液两相传输的模拟研究

两相传输是影响质子交换膜水电解系统性能的关键因素。为掌握质子交换膜水电解单元中多孔扩散层内气液两相传输规律,基于数值重构的三维多孔扩散层结构,采用格子Boltzmann两相流动模型模拟研究了扩散层内两相传输过程,详细分析了扩散层孔隙率和表面接触角对气泡传输与分布的影响。数值模拟结果表明：孔隙率减小会明显降低气体渗透率,从而导致气泡难以在扩散层内找到有效传输通道。接触角的增大不仅增加了气泡在界面堆积的风险,也减缓了气泡在孔隙内的传输速度。从孔隙尺度水平初步掌握了质子交换膜水电解单元多孔扩散层内两相传输规律,可为高性能水电解系统设计和优化提供理论支撑。     

Three-dimensional transport model of PEM fuel cell with straight flow channels

In this work, an isothermal, steady-state, three-dimensional (3D) multicomponent transport model is developed for proton exchange membrane (PEM) fuel cell with straight gas channels. The model computational domain, includes anode flow channel, membrane electrode assembly (MEA) and cathode flow channel. The catalyst layer within the domain has physical volume without simplification. A comprehensive set of 3D continuity equation, momentum equations and species conservation equations are formulated to describe the flow and species transport of the gas mixture in the coupled gas channels and the electrodes. The electrochemical reaction rate is modified by an agglomerate model to account for the effect of diffusion resistance through catalyst particle. The activation overpotential is predicted locally in the catalyst layer by separately solving electric potential equations of membrane phase and solid phase. The model is validated by comparison of the model prediction with experimental data of Ticianelli et al. The results indicate the detailed distribution characteristics of oxygen concentration, local current density and cathode activation overpotential at different current densities. The distribution patterns are relatively uniform at low average current density and are severely non-uniform at higher current density due to the mass transfer limitation. The local effectiveness factor in the catalyst layer can be obtained with this model, so the mass transport limitation is displayed from another point of view.     

Composition and performance modelling of catalyst layer in a proton exchange membrane fuel cell

The composition and performance optimisation of cathode catalyst platinum and catalyst layer structure in a proton exchange membrane fuel cell has been investigated by including both electrochemical reaction and mass transport process. It is found that electrochemical reactions occur in a thin layer within a few micrometers thick, indicating ineffective catalyst utilization for the present catalyst layer design. The effective use of platinum catalyst decreases with increasing current density, hence lower loadings of platinum are feasible for higher current densities of practical interest without adverse effect on cell performance. The optimal void fraction for the catalyst layer is about 60% and fairly independent of current density, and a 40% supported platinum catalyst yields the best performance amongst various supported catalysts investigated. An optimal amount of membrane content in the void region of the catalyst layer exists for minimum cathode voltage losses due to competition between proton migration through the membrane and oxygen transfer in the void region. The present results will be useful for practical fuel cell designs.     

Simulation of species transport and water management in PEM fuel cells

A single phase computational fuel cells model is presented to elucidate three-dimensional interactions between mass transport and electrochemical kinetics in proton exchange membrane (PEM) fuel cells with straight gas channels. The governing differential equations are solved over a single computational domain, which consists of a gas channel, gas diffusion layer, and catalyst layer for both the anode and cathode sides of the cell as well as the solid polymer membrane. Emphasis is placed on obtaining a basic understanding of how three-dimensional flow and transport phenomena in the air cathode impact the electrochemical process in the flow field. The complete cell model has been validated against experimentally measured polarization curve, showing good accuracy in reproducing cell performance over moderate current density interval. Fully three-dimensional results of the flow structure and species profiles are presented for cathode flow field. The effects of pressure on oxygen transport and water removal are illustrated through main axis of the flow structure. The model results indicate that oxygen concentration in reaction sites is significantly affected by pressure increase which leads to rising fuel cells power.     

Numerical investigation of the optimal Nafion ionomer content in cathode catalyst layer: An agglomerate two-phase flow modelling

A two dimensional, across the channel, isothermal, two-phase flow model for a proton exchange membrane fuel cell is presented. Reactant transport in porous media, water phase transfer and water transport through the membrane are included. The catalyst layer is modelled as a spherical agglomerate structure. Liquid water occupies the secondary pores of the cathode catalyst layer to form a liquid water coating surrounding the agglomerate. The thickness is calculated by coupling the two-phase flow model with the agglomerate model. Ionomer swelling is associated with the non-uniform distribution of water in the ionomer determined from several processes occurring simultaneously, namely (1) water phase transfer between the vapour, dissolved and liquid water; (2) membrane/ionomer water content depending on the water vapour pressure; (3) a water film covering the catalyst agglomerate; (4) water transport through the membrane via electro-osmotic drag, back diffusion and hydraulic permeation. The model optimises the initial dry ionomer content in the cathode catalyst layer. The simulation results indicate that, to achieve the best fuel cell performance, the initial dry ionomer volume fraction should be controlled around 10%, corresponding to 0.3 mg cm⁻². By considering the effect of ionomer swelling on the reduction in CCL porosity and the increase in oxygen mass transport resistance, the accuracy of the model prediction is improved, especially at higher current densities.     

Parametric study of a novel cathode catalyst layer in proton exchange membrane fuel cells

A steady-state mathematical model for the ordered cathode of proton exchange membrane fuel cells is developed to investigate the dependence of the cathode performance on the structural parameters of the catalyst layer. The model is based on the governing equations for oxygen concentration and potentials of the membrane and the solid phase, coupled by Tafel relation for the oxygen reduction reaction kinetics. The cathode current density optimization at a given electrode potential is presented with respect to nano-thread radius, porosity, platinum mass percentage, thickness, Nafion volume fraction and platinum loading of the catalyst layer. The simulation results suggest that small nano-thread radius is preferred. Except for quite low values as well as thin catalyst layers, porosity and platinum mass percentage have minor effects on cathode optimization. The cathode performance depends strongly on the catalyst layer thickness and additional attention should be paid to a thinner catalyst layer. The cathode can be efficiently optimized by increasing the highly sensitive parameters, Nafion volume fraction and platinum loading, to a suitable value which must avoid significant loss of oxygen transport.     

Numerical investigation of transport component design effect on a proton exchange membrane fuel cell

A numerical investigation of the transport phenomena and performance of a proton exchange membrane fuel cell (PEMFC) with various design parameters of the transport component is presented. A three-dimensional fuel cell model, incorporating conservations of species, momentum, as well as current transport, is used. The Bulter–Volmer equation that describes the electrochemical reaction in the catalyst layer is introduced; the activation overpotential connects the solid phase potential field to that of the electrolyte phase. Through cell performance simulation with various channel aspect ratios and gas diffusion layer (GDL) thicknesses, a slender channel is found suitable for cells operating at moderate reaction rate, and a flat channel produces more current at low cell voltage. Plots of transverse oxygen concentration and phase potential variation indicate that these oppositely affect the local current density pattern. The relative strengths of these two factors depend on the transport component position and geometry, as well as on the cell operating conditions. Consequently, the curves of cell output current density demonstrate that the optimal GDL thickness increases as the cell voltage decreases. However, at the lowest considered cell voltage of 0.14 V, optimal thickness decreases as that of a thick GDL. The oxygen deficiency caused by long traveling length and clogging effect of liquid water reverses this relationship.     

Modeling and simulation of a direct methanol fuel cell anode

A mathematical model for the anode of a direct methanol fuel cell (DMFC) is presented. This model considers the mass transport in the whole anode compartment and the proton exchange membrane (PEM), together with the kinetic and ohmic resistance effects through the catalyst layer. The influence of key parameters on methanol crossover and anode performance is investigated. Our results indicate that, at low current density and high methanol concentration, the methanol crossover poses a serious problem for a DMFC. The anodic overpotential and reaction-rate distributions throughout the catalyst layer are more sensitive to the protonic conductivity than to the diffusion coefficient of methanol. Increasing the protonic conductivity can effectively enhance the performance of a DMFC.     

Pore network modeling of cathode catalyst layer of proton exchange membrane fuel cell

In this paper, a pore network model is developed to investigate the coupled transport and reaction processes in the cathode catalyst layer (CCL) of proton exchange membrane fuel cell (PEMFC). The developed model is validated by comparing the predicted polarization curve with the experimental data, and the parametric studies are carried out to elucidate the effects of CCL design parameters. With the decrease of the CCL thickness and the Nafion content, the cell voltage reduces at the low current density but increases when the current density is higher. The cell performance is also improved by increasing the proton conductivity of the Nafion film in the CCL. As compared to the CCL of uniformly distributed Nafion, the CCL with the Nafion volume decreasing along the thickness direction exhibits better performance at the high current density.     

Effect of primary parameters on the performance of PEM fuel cell

A one-dimensional, steady-state and isothermal model for a proton exchange membrane (PEM) fuel cell has been developed to investigate the effects of various parameters such as the molar fraction of nitrogen gas, relative humidity, temperature, pressure, membrane thickness, anode and cathode stoichiometric flow ratio and the distribution of oxygen in the cathode catalyst while water transfer in membrane is produced by diffusion, pressure gradient and electro-osmotic drag. The most critical problems to overcome in the proton exchange membrane (PEM) fuel cell technology are the water and thermal management. The results show that the cell performance increases as operating pressure and temperature are increased. The performance of cell can decrease by decreasing the relative humidity of inlet gases and increasing the membrane thickness. Increasing the anode and cathode stoichiometric flow ratio can also improve the cell performance. As the oxygen concentration becomes zero in about 8 percent depth of cathode catalyst layer, the thickness of cathode catalyst layer can be reduced 92 percent without any potential loss in output voltage. The cathode activation loss also becomes high by increasing the molar fraction of nitrogen gas. The modeling results agree very well with experimental results.