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。     

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.     

Analysis of coupled proton and water transport in a PEM fuel cell using the binary friction membrane model

Transport of liquid water within a polymer electrolyte membrane (PEM) is critical to the operation of a PEM fuel cell, due to the strong dependence of the membrane transport coefficients on water content. In addition, enhanced predictive abilities are particularly significant in the context of passive air breathing fuel cell designs where lower water contents will prevail in the membrane. We investigate and analyze the numerical predictions of a recently proposed rational model for transport of protons and water in a PEM, when compared to a widely used empirical model. While the performance is similar for a saturated membrane, for PEMs with low water content, the difference in computed current density and membrane water crossover can be substantial. The effects of coupling partially saturated gas diffusion electrodes (GDLs) with the membrane are studied in both a 1D and 2D context. In addition, a simplified 1D analytical membrane water transport model is validated against the complete 1D model predictions. Our numerical results predict a higher current density and more uniform membrane hydration using a dry cathode instead of a dry anode, and illustrate that the strongest 2D effects are for water vapor transport.     

Mathematical Model of Proton Exchange Membrane Fuel Cell with Consideration of Water Management

One‐dimensional model on the membrane electrode assembly (MEA) of proton exchange membrane fuel cell is proposed, where the membrane hydration/dehydration and the possible water flooding of the respective cathode and anode gas diffusion layers are considered. A novel approach of phase‐equilibrium approximation is proposed to trace the water front and the detailed saturation profile once water emerges in either anode or cathode gas diffusion layer. The approach is validated by a semi‐analytical method published earlier. The novel approach is applicable to the polarization regime from open circuit voltage to the limiting current density under practical operation conditions. Oxygen diffusion is limited by water accumulation in the cathode gas diffusion layer as current increases, caused by excessive water generation at the cathode catalyst layer and the electro‐osmotic drag across the membrane. The existence of liquid water in the anode gas diffusion layer is predicted at low current densities if high degrees of humidification in both anode and cathode feeds are employed. The influences of inlet relative humidity, imposed pressure drop, and cell temperature are correlated well with the cell performance. In addition, the overpotentials attributed from individual components of the MEA are delineated against the cell current densities.     

On the modeling of water transport in polymer electrolyte membrane fuel cells

Water management is a critical issue in polymer electrolyte membrane (PEM) fuel cells, and water transport through the membrane, catalyst layer and gas diffusion layer has significant impact on the cell performance and durability. In this study, the mechanism of water transport processes in PEM fuel cells has been analyzed through 3-D unsteady non-isothermal simulations, along with a comprehensive examination of various modeling approaches in literature. It is shown that the finite rates of sorption/desorption of water in membrane affect the cell current output and the cell response time. Water dissolved in the membrane should be taken as the proper mechanism of water formation in the cathode of practical PEM fuel cells. Capillary pressure and relative permeability have significant impact on the distribution of liquid water saturation and transport, implying a need for their determination under specific PEM fuel cell conditions.     

Improvement of the Ohmic Loss Process Model of the Proton Exchange Membrane Fuel Cell

The impedance characteristics of the ohmic overpotential of the proton exchange membrane (PEM) fuel cells are studied analytically using the process modeling approach. The water transport in the membrane, the cathode catalyst layer, and gas diffusion layer are analyzed. The analytical relation of the impedance of the ohmic loss is determined and is converted to an equivalent circuit. Then, the impedance of a PEM fuel cell is measured experimentally in different current densities, operating temperatures and the anode and cathode relative humidities. The measured impedances are compared with the predicted ones from the analytical model. It is shown that the predicted impedance characteristics are in great agreement with the measured ones in all different operating conditions.     

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.     

A three-dimensional numerical simulation of the transport phenomena in the cathodic side of a PEMFC

A three-dimensional numerical model is developed to simulate the transport phenomena on the cathodic side of a polymer electrolyte membrane fuel cell (PEMFC) that is in contact with parallel and interdigitated gas distributors. The computational domain consists of a flow channel together with a gas diffusion layer on the cathode of a PEMFC. The effective diffusivities according to the Bruggman correlation and Darcy's law for porous media are used for the gas diffusion layer. In addition, the Tafel equation is used to describe the oxygen reduction reaction (ORR) on the catalyst layer surface. Three-dimensional transport equations for the channel flow and the gas diffusion layer are solved numerically using a finite-volume-based numerical technique. The nature of the multi-dimensional transport in the cathode side of a PEMFC is illustrated by the fluid flow, mass fraction and current density distribution. The interdigitated gas distributor gives a higher average current density on the catalyst layer surface than that with the parallel gas distributor under the same mass flow rate and cathode overpotential. Moreover, the limiting current density increased by 40% by using the interdigitated flow field design instead of the parallel one.     

Oxygen mass transport limitations at the cathode of polymer electrolyte membrane fuel cells

Oxygen transport across the cathode gas diffusion layer (GDL) in polymer electrolyte membrane (PEM) fuel cells was examined by varying the O₂/N₂ ratio and by varying the area of the GDL extending laterally from the gas flow channel under the bipolar plate (under the land). As the cathode is depleted of oxygen, the current density becomes limited by oxygen transport across the GDL. Oxygen depletion from O₂/N₂ mixtures limits catalyst utilization, especially under the land.The local current density with air fed PEM fuel cells falls to practically zero at lateral distances under the land more than 3 times the GDL thickness; on the other hand, catalyst utilization was not limited when the fuel cell cathode was fed with 100% oxygen. The ratio of GDL thickness to the extent of the land is thus critical to the effective utilization of the catalyst in an air fed PEM fuel cell. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

采用常规条形流场的质子交换膜燃料电池阴极数值模拟(Ⅰ)模型建立

对采用常规条形流场的H₂-Air PEMFCs阴极建立了二维数学模型,模型的控制方程耦合了连续性方程、Darcy方程、电传导方程以及O₂和H₂O的对流-扩散方程,对氧的电化学还原反应过程采用Butler-Volmer方程描述.利用模型计算了阴极扩散层中电流密度、O₂和H₂O浓度、催化层界面上局部电流密度的分布,分析了采用常规条形流场时气体在阴极扩散层中的传递机制及各组分浓度分布的特点.     

常规流场下各向异性扩散层对质子交换膜燃料电池(PEMFC)性能影响

为了研究扩散层各向异性对电池性能的影响,以XD=Di,j ^y/Di,j ^x 为各向异性的表征,建立了使用常规流场的质子交换膜燃料电池二维传质模型.考虑了阴阳极内物质的对流和扩散、水和质子在膜内传递以及催化层的电化学反应.利用有限差分法对控制方程进行离散,采用逐次超松驰法求解得到了阴阳极反应气体和水的浓度分布以及催化层电流密度、膜中水含量、膜中电势和电流密度的分布.分析结果表明：在1≤XD≤4时增大XD有利于提高电池性能,但随着XD增大其对电池性能的影响逐渐减小;并且XD对电池性能的影响主要体现在对阴极和膜性能的影响上,其对阳极性能的影响甚微.     

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。     

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.     

Investigation of phosphoric acid and water transport in the high temperature proton exchange membrane fuel cells using a multiphase model

A three-dimensional, nonisothermal, and multiphase model of high temperature proton exchange membrane fuel cells is built to investigate water and phosphoric acid transportation, in which a spherical agglomerate model considering catalyst layer structure and liquid saturation is applied to determine the electrochemical kinetics in the cathode catalyst layer. Experimental polarization curve, water proportion in the anode outlet gas, and phosphoric acid distribution are selected for validation. It is found that the simulated results can represent the experimental data with reasonable accuracy. Based on the model, the effects of current density and stoichiometry on the variable distributions are analyzed. The results show that water in anode is mainly from cathode by concentration diffusion of liquid water, and the proportion of anode outlet water to the total produced water decreases slightly with the increase of current density. A higher current density leads to a greater electromigration of phosphoric acid from cathode to anode and a higher liquid phase fraction in anode, while a lower phosphoric acid concentration in the fuel cells.     

Calculation of reversible electrode heats in the proton exchange membrane fuel cell from calorimetric measurements

A calorimeter was used to measure the heat production in polymer electrolyte membrane (PEM) fuel cells operated on hydrogen and oxygen at 50 °C and 1 bar. Two cells were examined, one using a 35 μm thick Nafion membrane and a catalyst loading of 0.6/0.4 mg Pt cm⁻², for the cathode and anode layer, respectively, the other using a 180 μm thick Nafion membrane and loading of 0.4/0.4 mg Pt cm⁻². The cells investigated thus had different membranes and catalyst layers, but identical porous transport layers and micro-porous layers. The calorimeter is unique in that it provides the heat fluxes out of the cell, separately for the anode and the cathode sides. The corresponding cell potential differences, ohmic cell resistance and current densities are also reported. The heat fluxes through the current collector plates were decomposed by a thermal model to give the contributions from the ohmic and the Tafel heats to the total heat fluxes. Thus, the contributions from the reversible heat (the Peltier heats) to the current collectors were determined. The analysis suggests that the Peltier heat of the anode of these fuel cell materials is small, and that it is the cathode reaction which generates the main fraction of the total heat in a PEM fuel cell. The entropy change of the anode reaction appears to be close to zero, while the corresponding value for the cathode is near −80 J K⁻¹ mol⁻¹.     

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.     

Modelling the Effect of Inhomogeneous Compression of GDL on Local Transport Phenomena in a PEM Fuel Cell

The effects of inhomogeneous compression of gas diffusion layers (GDLs) on local transport phenomena within a polymer electrolyte membrane (PEM) fuel cell were studied theoretically. The inhomogeneous compression induced by the rib/channel structure of the flow field plate causes partial deformation of the GDLs and significantly affects component parameters. The results suggest that inhomogeneous compression does not significantly affect the polarisation behaviour or gas–phase mass transport. However, the effect of inhomogeneous compression on the current density distribution is evident. Local current density under the channel was substantially smaller than that under the rib when inhomogeneous compression was taken into account, while the current density distribution was fairly uniform for the model which excluded the effect of inhomogeneous compression. This is caused by the changes in the selective current path, which is determined by the combination of conductivities of components and contact resistance between them. Despite the highly uneven current distribution and variation in material parametres as a function of GDL thickness, the temperature profile was relatively even over the active area for both the modelled cases, contrary to predictions in previous studies. However, an abnormally high current density significantly accelerates deterioration of the membrane and is critical in terms of cell durability. Therefore, fuel cells should be carefully designed to minimise the harmful effects of inhomogeneous compression.     

Mass transport in the cathode of a free-breathing polymer electrolyte membrane fuel cell

In small fuel cell applications, it is desirable to take care of the management of reactants, water and heat by passive means in order to minimize parasitic losses. A polymer electrolyte membrane fuel cell, in which air flow on the cathode was driven by free convection, was studied by experimental and modelling methods. The cathode side of the cell had straight vertical channels with their ends open to the ambient air. A two-dimensional, isothermal and steady state model was developed for the cathode side to identify the limiting processes of mass transport. The modelled domain consists of the cathode gas channel and the gas diffusion layer. Experimental data from current distribution measurements were used to provide boundary conditions for oxygen consumption and water production. The model results indicate that at the cell temperature of 40 °C the performance of the cell was limited by water removal. At the cell temperature of 60 °C, the current distribution was determined by the partial pressure of oxygen.