Characteristics of subzero startup and water/ice formation on the catalyst layer in a polymer electrolyte fuel cell

This work experimentally explores the fundamental characteristics of a polymer electrolyte fuel cell (PEFC) during subzero startup, which encompasses gas purge, cool down, startup from a subfreezing temperature, and finally warm up. In addition to the temperature, high-frequency resistance (HFR) and voltage measurements, direct observations of water or ice formation on the catalyst layer (CL) surface have been carried out for the key steps of cold start using carbon paper punched with microholes and a transparent cell fixture. It is found that purge time significantly influences water content of the membrane after purge and subsequently cold-start performance. Gas purge for less than 30 s appears to be insufficient, and that between 90 and 120 s is most useful. After gas purge, however, the cell HFR relaxation occurs for longer than 30 min due to water redistribution in the membrane-electrode assembly (MEA). Cold-start performance following gas purge and cool down strongly depends on the purge time and startup temperature. The cumulative product water measuring the isothermal cold-start performance increases dramatically with the startup temperature. The state of water on the CL surface has been studied during startup from ambient temperatures ranging from −20 to −1 °C. It is found that the freezing-point depression of water in the cathode CL is 1.0 ± 0.5 °C and its effect on PEFC cold start under automotive conditions is negligible.     

Experimental Studies on the Influence of Operational Parameters on the Cold Start of a 2 kW Fuel Cell

In this paper, experimental investigations on the influence of operational parameters on PEM fuel cell cold start are presented. The effect of current density, stack impedance at 1 kHz prior to start, as well as gas flow rate, gas pressure, coolant flow rate and surrounding subfreezing temperature are studied. The experimental apparatus is briefly described. It includes a main unit at room temperature and a smaller separate unit in a climatic chamber. Low current density, high impedance prior to start, moderate subfreezing temperature (–5 °C), high gas flow rate, low gas pressure and low coolant flow rate are found to have a positive impact on the cold start performance. Combining these parameters, self start‐up of the fuel cell without additional energy is achieved at –5 °C in 30 min. The whole set of observations leads to the following hypotheses on freeze mechanism: in the first phase, dry membranes and low current lead to a transient phase of membrane humidification. Then, in the second phase, ice clogging of the active layers occurs. In the third phase, a variable quantity of the produced water reaches the gas diffusion layers and channels.     

PEMFC冷却剂循环条件下冷启动数值模拟

质子交换膜燃料电池(PEMFC)具有高能量比、环境友好、工作温度低等优点，可用作未来新能源汽车的能量来源，具有很好的发展前景。然而零下温度启动时，电池内水结冰堵塞通道，严重影响电池启动性能及寿命。提出了PEMFC冷启动三维多物理场数值模型，考虑了冷却剂流动与传热的影响，对冷启动过程组分浓度、电势、温度、含冰量等参数进行了可视化分析。数值模拟结果与试验吻合良好，表明模型可用于预测电池冷启动性能并用于机理研究。     

Ice formation and distribution in the catalyst layer during freeze-start process - CRYO-SEM investigation

Ice distribution in the catalyst layer and gas distribution layer (GDL) of proton exchange membrane (PEM) fuel cells under isothermal constant voltage (ICV) operation at a subzero temperature was determined using a field emission scanning electron microscope with a cryogenic stage and sample preparation unit (CRYO-FESEM). The analysis method was designed to ensure that the entire experiment, from sample preparation to CRYO-FESEM characterization, are carried out under subzero (°C) conditions so that the water is always kept in a frozen state without thawing.Under a moderately wet shutdown, the porosity of the cathode catalyst layer decreased from an initial dry porosity of 65% to 15.9% for the frozen-only sample and to 8.2% for the sample which was operated at subzero temperatures (ICV). After the completion of the ICV, the catalyst surface was completely covered with ice and the gas was not able to reach the active sites and the reaction ceased. Two distinct regions with different porosities in the catalyst layer were observed at the half ICV state, which indicates that ice in the catalyst layer melted at the beginning of ICV operation.     

Design of a reference electrode for high-temperature PEM fuel cells

In this work, we present the design of an external reference electrode for high-temperature PEM fuel cells. The connection between the reference electrode with one of the fuel cell electrodes is realized by an ionic connector. Using the same material for the ionic connection as for the fuel cell membrane gives us the advantage to reach temperatures above 100 °C without destroying the reference electrode. This configuration allows for the separation of the anode and cathode overpotential in a working fuel cell system. In addition to the electrode overpotentials in normal hydrogen/air operation, the influence of CO and CO + H₂O in the anode feed on the fuel cell potentials was investigated. When CO poisons the anode catalyst, not only the anode potential increased, but also the cathode overpotential, due to fewer protons reaching the cathode. By the use of synthetic reformate containing hydrogen, carbon monoxide and water on the anode, fuel cell voltage oscillations were observed at high constant current densities. The reference electrode measurements showed that the fuel cell oscillations were only related to reactions on the anode side influencing the anode overpotential. The cathode potential, in contrast, was only negligibly affected by the oscillations under the applied conditions.     

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.     

Steady-state operation of a compressor for a proton exchange membrane fuel cell system

The performance of a system consisting of a proton exchange membrane (PEM) fuel cell coupled to a centrifugal air compressor is simulated. Two modes of operation of the system are investigated: one in which the speed of the compressor is constant, and the other in which the compressor speed is varied with the electric load on the fuel cell stack. The operating characteristics of the compressor and the PEM fuel cell stack and their influence on the system efficiency are analyzed for a step change in the stack current. The effects of the fuel cell stack back-pressure and the electric load on the compressor power consumption and the system efficiency are studied. It is found that the system efficiency is higher when the fuel cell stack is operated at a constant oxygen gas stoichiometry by varying the compressor speed instead of at a constant compressor speed. The system model can be used to determine the rotation speed of the compressor for various electric loads.     

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.     

质子交换膜燃料电池动态过程的数值模拟

为描述质子交换膜燃料电池的动态过程,发展了一个基于计算流体动力学的非稳态、非等温的三维两相流数学模型.应用模型对一蛇形流道结构的质子交换膜燃料电池单体进行了数值计算,得到了电池启动过程中电池阴极侧膜表面温度和电流密度等特征参数的动态过程变化曲线.最后,分析了阴极入口速度、湿度和电池电压阶跃变化后电池特性的动态响应特性.结果表明：电池的启动时间和阶跃响应时间均为秒的数量级,与大多数模型模拟的结果相一致.     

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     

Review: Durability and Degradation Issues of PEM Fuel Cell Components

Besides cost reduction, durability is the most important issue to be solved before commercialisation of PEM Fuel Cells can be successful. For a fuel cell operating under constant load conditions, at a relative humidity close to 100% and at a temperature of maximum 75 °C, using optimal stack and flow design, the voltage degradation can be as low as 1–2 μV·h. However, the degradation rates can increase by orders of magnitude when conditions include some of the following, i.e. load cycling, start–stop cycles, low humidification or humidification cycling, temperatures of 90 °C or higher and fuel starvation. This review paper aims at assessing the degradation mechanisms of membranes, electrodes, bipolar plates and seals. By collecting long‐term experiments as well, the relative importance of these degradation mechanisms and the operating conditions become apparent.     

Empirical Model Equations for the Direct Methanol Fuel Cell DMFCs

Empirical model equations, proposed for polymer electrolyte fuel cells, are used to predict the cell voltage vs. current density response of a liquid feed direct methanol fuel cell. The model equations are validated against experimental data for a small-scale fuel cell over a wide range of methanol concentration and temperatures. A new empirical equation is presented which is able to predict the voltage response of liquid feed direct methanol fuel cells over a wide range of operating conditions and even in the case of very low current densities caused by, for example, the use of dilute methanol solutions or low cell temperatures.     

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。     

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.     

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.     

Three-dimensional CFD modelling of PEM fuel cells: An investigation into the effects of water flooding

In this work, a three-dimensional PEM fuel cell model has been developed and is used to investigate the effects of water flooding on cell performance parameters. The presence of liquid water in the cathode gas diffusion layer (GDL) limits the flow of reactants to the cathode catalyst layer, thereby reducing the overall reaction rate and curtailing the maximum power that can be derived from the cell. To characterize the effects of water flooding on gas diffusion, effective diffusivity models that account for the tortuosity and relative water saturation of the porous fuel cell electrodes have been derived from percolation theory and coupled with the CFD model within a single phase flow skeleton. The governing equations of the overall three-dimensional PEM fuel cell model, which are a representative of the coupled CFD and percolation theory based effective diffusivity models, are then solved using the finite volume method. Parametric studies have been conducted to characterize the effects of GDL permeability, inlet humidity and diffusivity of the reactants on the various cell performance parameters such as concentration of reactants/products and cell current densities. It is determined that the GDL permeability has little or no effect on the current densities due to the diffusion dominated nature of the gas flow. However, through the incorporation of percolation theory based effective diffusivity model; a marked reduction in the cell performance is observed which closely resembles published experimental observations. This is a reasonable approximation for effects of water flooding which has been inherently used for further parametric studies.     

多晶硅还原炉低电压启动转高电压启动设备结构改造

目前国内多晶硅生产中,还原炉多采用高电压击穿的方式启动,但国外多晶硅生产中多采用低电压击穿,一些进口还原炉采用了低电压启动的结构设计。现本文将以MSA还原炉为例,分析阐述满足低压启动还原炉改成高压启动条件,对炉体结构的改造方案。     

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     

Comparison of two IT DIR-SOFC models: Impact of variable thermodynamic, physical, and flow properties. Steady-state and dynamic analysis

This paper compares two dynamic, one-dimensional models of a planar anode-supported intermediate temperature (IT) direct internal reforming (DIR) solid oxide fuel cell (SOFC): one where the flow properties (pressure, gas stream densities, heat capacities, thermal conductivities, and viscosity) and gas velocities are taken as constant throughout the system, based on inlet conditions, and one where this assumption is removed to focus on the effect of considering the variation of local flow properties on the prediction of the fuel cell performance. The refined model consists of mass, energy, and momentum balances, and of an electrochemical model that relates the fuel and air gas compositions and temperatures to voltage, current density, and other relevant fuel cell variables. Simulations for steady-state and dynamic conditions have been carried out and the results obtained from the two models compared. For a co-flow SOFC operating on a 10% pre-reformed methane fuel mixture, with 75% fuel utilisation, inlet fuel and air temperatures of 1023 K, average current density of , and an air ratio of 8.5, the results show that, although the error incurred in the prediction of the flow properties in the first model is significant, there is good agreement between both models in terms of the overall cell performance: the maximum difference in the local temperature values is about 7 K and the cell efficiency differs by less than 1%. However, the discrepancies between the two models increase, especially in the fuel channel, when higher current density values are assigned to the cell.     

Novel application of boron-doped diamond and related material to electrochemical generation of functional water

The performances of the electrogeneration of ClO⁻ on the different electrode materials, such as boron-doped diamond (BDD), Pt/BDD and Pt, were investigated at constant voltages of 10, 20 and 30 V as well as constant currents of 25, 50 and 75 mA. The BDD and Pt/BDD electrodes showed superior to platinum electrode for the ClO⁻ generation at both constant voltage and constant current conditions under respective room temperature (RT) and low temperature (LT) (2-5 °C). Both BDD and Pt/BDD electrodes exhibited high stability used under high voltage and current conditions.