A model for hydrogen sulfide poisoning in proton exchange membrane fuel cells

A polymer-electrolyte fuel cell model that incorporates the effects of hydrogen sulfide contaminant on performance is developed. The model is transient, fully two-phase and non-isothermal and includes a complex kinetic mechanism to describe the electrode reactions. Comparisons between the simulation results and data in the literature demonstrate that known trends are well captured. The effects of temperature and relative humidity variations in the anode stream are investigated, with further comparisons to experimental data and a proposed explanation for the nonlinear behaviour observed in the experiments of Mohtadi et al. [R. Mohatadi, W.-K. Lee, J. van Zee, Appl. Catal. B 56 (2005) 37–42)]. Extensions to the model and future work are discussed.     

Enhancement of efficiency and power output of hydrogen fuelled proton exchange membrane (PEM) fuel cell using oxygen enriched air

This paper deals with the effects of the oxygen-enriched air (up to 50% oxygen by mass) along with other operating parameters (hydrogen flow rate, temperature, and relative humidity) on the performance of hydrogen-fuelled proton exchange membrane (PEM) fuel cell. The active area of a fuel cell considered was 50 cm² with three cells in series connections. The air was supplied with O₂ enriched from 23% to 50% at the cathode. The voltage obtained with the respective enriched air was 2.52 and 2.80 V respectively. The optimum oxygen enrichment was found as 45%. The stack temperature plays a significant role on performance improvement and the optimum temperature was found as 50 °C. The voltage efficiency and power output were improved by 9% and 33% with 45% oxygen-enriched air. Electrochemical impedance spectroscopy was used to analyze the impedance behavior of the fuel cell with the variable current demand. The bode plot indicates current dominates voltage at low oxygen-enriched air (25%) and vice-versa at high-enriched air. The inductive effect was dominating at the low frequency and overtaken by the capacitive effects at the higher frequency. These results would be useful to develop a dedicated fuel cell with the oxygen-enriched air.     

Diagnosis of hydrogen crossover and emission in proton exchange membrane fuel cells

When hydrogen leaks through holes or cracks in membrane-electrode assemblies (MEAs) in Proton Exchange Membrane (PEM) fuel cells, it recombines directly with air. This recombination results in a reduction in oxygen concentration on the cathode side of the MEA. In this paper, the signatures of electrochemical impedance spectroscopy (EIS) are analyzed in different multi-cell stack configurations to show the relation between hydrogen leak rate and reduced oxygen concentrations. The reduction in concentration was made by mixing oxygen with nitrogen at different rates, and the increase in hydrogen leak rate was made by controlling the differential pressure (dP) between anode and cathode. To analyze the impedance signatures, we fit the data of oxygen concentration and dP with the parameters of a Randles circuit. The correlation between the parameters of the two data sets allows us to understand the change in impedance signatures with respect to reduction of oxygen in the cathode side. To have a better insight on the effect of insufficient oxygen at the cathode, a model that establishes a relationship between impedance and voltage was considered. Using this model along with the impedance signatures we were able to detect the reduction of oxygen concentrations at the cathode with the help of fuzzy rule-base. However, resolution of detection was reduced with the reduction of leak rate and/or increases in the stack cell count.     

Diagnosis of hydrogen crossover and emission in proton exchange membrane fuel cells

When hydrogen leaks through holes in membrane-electrode assemblies (MEAs) in proton exchange membrane (PEM) fuel cells, it recombines directly with air. This recombination results in a reduction in oxygen concentration on the cathode side of the MEA. In this paper, the signatures of electrochemical impedance spectroscopy (EIS) are analyzed in different multi-cell stack configurations to show the relation between hydrogen leak rate and reduced oxygen concentrations. The reduction in concentration was made by mixing oxygen with nitrogen at different rates, and the increase in hydrogen leak rate was made by controlling the differential pressure (dP) between anode and cathode. To analyze the impedance signatures, we fit the data of oxygen concentration and dP with the parameters of a Randles circuit. The correlation between the parameters of the two data sets allows us to understand the change in impedance signatures with respect to reduction of oxygen in the cathode side. To have a better insight on the effect of insufficient oxygen at the cathode, a model that establishes a relationship between impedance and voltage was considered. Using this model along with the impedance signatures we were able to detect the reduction of oxygen concentrations at the cathode with the help of fuzzy rule-base. However, resolution of detection was reduced with the reduction of leak rate and/or increases in the stack cell count.     

A general model for air-side proton exchange membrane fuel cell contamination

This paper presents a general model for air-side feed stream contamination that has the capability of simulating both transient and steady-state performance of a PEM fuel cell in the presence of air-side feed stream impurities. The model is developed based on the oxygen reduction reaction mechanism, contaminant surface adsorption/desorption, and electrochemical reaction kinetics. The model is then applied to the study of air-side toluene contamination. Experimental data for toluene contamination at four current densities (0.2, 0.5, 0.75 and 1.0 A cm⁻²) and three contamination levels (1, 5 and 10 ppm) were used to validate the model. In addition, it is expected that, with parameter adjustment, this model can also be used to predict performance degradation caused by other air impurities such as nitrogen oxides (NO_x) and sulfur oxides (SO_x).     

Multiple model predictive control for a hybrid proton exchange membrane fuel cell system

This paper presents a hierarchical predictive control strategy to optimize both power utilization and oxygen control simultaneously for a hybrid proton exchange membrane fuel cell/ultracapacitor system. The control employs fuzzy clustering-based modeling, constrained model predictive control, and adaptive switching among multiple models. The strategy has three major advantages. First, by employing multiple piecewise linear models of the nonlinear system, we are able to use linear models in the model predictive control, which significantly simplifies implementation and can handle multiple constraints. Second, the control algorithm is able to perform global optimization for both the power allocation and oxygen control. As a result, we can achieve the optimization from the entire system viewpoint, and a good tradeoff between transient performance of the fuel cell and the ultracapacitor can be obtained. Third, models of the hybrid system are identified using real-world data from the hybrid fuel cell system, and models are updated online. Therefore, the modeling mismatch is minimized and high control accuracy is achieved. Study results demonstrate that the control strategy is able to appropriately split power between fuel cell and ultracapacitor, avoid oxygen starvation, and so enhance the transient performance and extend the operating life of the hybrid system.     

A dynamic model for hydrogen consumption of fuel cell stacks considering the effects of hydrogen purge operation

The actual hydrogen consumption of a fuel cell stack varies with a fixed time delay under the step load change. For each individual stack, the delay time in the step-up load stage is generally shorter than in the step-down stage. Due to the hydrogen purge operation, transient overshoots take place intermittently after the actual hydrogen consumption reaches the steady state, and the duration and peak value of such overshoots are distributed approximately within a fixed range. Based on the performance investigation mentioned above, an improved dynamic model for hydrogen consumption of a fuel cell stack considering the effects of hydrogen purge operation is introduced in this paper. Compared with the previous model, the suggested model indicates a better agreement between test and simulation, especially in the working condition of hydrogen purge operation.     

Two-dimensional simulation of cold start processes for proton exchange membrane fuel cell with different hydrogen flow arrangements

Proton exchange membrane (PEM) fuel cells with an off-gas recirculation anode (ORA) or dead-ended anode (DEA) are widely adopted in engineering. However, those two hydrogen flow arrangements may cause anodic water and nitrogen accumulation in comparison with the flow-through anode (FTA) mode, which causes significant performance degradation. In this paper, a two-dimensional cold-start model is developed with detailed consideration of water phase changes and the nitrogen crossover phenomenon. A simplified electrochemical module is built to calculate the current density distribution in the model. The simulation results are consistent with the experimental data at both subzero temperatures and normal operating temperatures. The effects of hydrogen flow arrangements, flow configurations, and startup strategies are investigated during startup process from subzero to normal operating temperatures. Much less ice is generated in counter-flow cases than in co-flow cases during constant current operation. A relatively lower startup voltage can effectively shorten the cold-start process and enhance the cold-start capacity for the PEM fuel cell. The ORA mode has the best hydrogen flow arrangement due to its general abilities, including higher hydrogen utilization efficiency, higher anodic nitrogen tolerance, better output performance and better startup capability.     

Performance prediction of proton exchange membrane fuel cells using a three-dimensional model

In this study a steady-state three-dimensional computational fluid dynamics (CFD) model of a proton exchange membrane fuel cell is developed and presented for a single cell. A complete set of conservation equations of mass, momentum, species, energy transport, and charge is considered with proper account of electrochemical kinetics based on Butler–Volmer equation. The catalyst layer structure is considered to be agglomerate. This model enables us to investigate the flow field, current distribution, and cell voltage over the fuel cell which includes the anode and cathode collector plates, gas channels, catalyst layers, gas diffusion layers, and the membrane. The numerical solution is based on a finite-volume method in a single solution domain. In this investigation a CFD code was used as the core solver for the transport equations, while mathematical models for the main physical and electrochemical phenomena were devised into the solver using user-developed subroutines. Three-dimensional results of the flow structure, species concentrations and current distribution are presented for bipolar plates with square cross section of straight flow channels. A polarization curve is obtained for the fuel cell under consideration. A comparison between the polarization curves obtained from the current study and the corresponding available experimental data is presented and a reasonable agreement is obtained. Such CFD model can be used as a tool in the development and optimization of PEM fuel cells.     

A general model of proton exchange membrane fuel cell

In this study, a general model of proton exchange membrane fuel cell (PEMFC) was constructed, implemented and employed to simulate the fluid flow, heat transfer, species transport, electrochemical reaction, and current density distribution, especially focusing on liquid water effects on PEMFC performance. The model is a three-dimensional and unsteady one with detailed thermo-electrochemistry, multi-species, and two-phase interaction with explicit gas–liquid interface tracking by using the volume-of-fluid (VOF) method. The general model was implemented into the commercial computational fluid dynamics (CFD) software package FLUENT^® v6.2, with its user-defined functions (UDFs). A complete PEMFC was considered, including membrane, gas diffusion layers (GDLs), catalyst layers, gas flow channels, and current collectors. The effects of liquid water on PEMFC with serpentine channels were investigated. The results showed that this general model of PEMFC can be a very useful tool for the optimization of practical engineering designs of PEMFC.     

Dynamic characteristics and mitigations of hydrogen starvations in proton exchange membrane fuel cells during start-ups

Hydrogen starvation during a start-up process in proton exchange membrane (PEM) fuel cells could result in drastic local current density variations, reverse cell voltage and irreversible cell damages. In this work, variations of local current densities and temperatures are measured in situ under both potentiostatic and galvanostatic modes. Experimental results show that when the cell starts up under potentiostatic mode with hydrogen starvation, current density undershoots occur in the downstream; while under the galvanostatic mode, local current density in the downstream almost drops to zero, but the current density near the outlet remains almost constant. The phenomenon of near constant current density near the outlet leads to a novel approach to alleviate hydrogen starvations - a hydrogen reservoir is added at the anode outlet. Experimental results show that the exit hydrogen reservoir can significantly reduce the zero current region and alleviate hydrogen starvations. A non-dimensional current-density variation coefficient is proposed to measure the magnitude of local current density changes during starvations. Experimental results show that the exit hydrogen reservoir can significantly reduce the current-density variations coefficient over the entire flow channel, indicating that adding an exit reservoir is an effective approach in mitigating hydrogen starvations.     

New theoretical model for convergent nozzle ejector in the proton exchange membrane fuel cell system

A new theoretical model for the convergent nozzle ejector in the anode recirculation line of the polymer electrolyte membrane (PEM) fuel cell system is established in this paper. A velocity function for analyzing the flow characteristics of the PEM ejector is proposed by employing a two-dimensional (2D) concave exponential curve. This treatment of velocity is an improvement compared to the conventional 1D “constant area mixing” or “constant pressure mixing” ejector theories. The computational fluid dynamics (CFD) technique together with the data regression and parameter identification methods are applied in the determination of the velocity function's exponent. Based on the model, the anode recirculation performances of a hybrid PEM system are studied under various stack currents. Results show that the model is capable of evaluating the performance of ejector in both the critical mode and subcritical mode.     

Novel dynamic semiempirical proton exchange membrane fuel cell model incorporating component voltages

This paper introduces a novel dynamic semiempirical model for the proton exchange membrane fuel cell (PEMFC). The proposed model not only considers the stack output voltage but also provides valid waveforms of component voltages, such as the no‐load, activation, ohmic, and concentration voltages of the PEMFC stack system. Experiments under no‐load, ramping load, and dynamic load conditions are performed to obtain various voltage components. According to experimental results, model parameters are optimised using the lightning search algorithm by providing valid theoretical ranges of parameters to the lightning search algorithm code. In addition, the correlation between the vapour and water pressures of the PEMFC is obtained to model the component voltages. Finally, all component voltages and the stack output voltage are validated by using the experimental/theoretical waveforms mentioned in previous research. The proposed model is also compared with a recently developed semiempirical model of PEMFC through particle swarm optimisation. The proposed dynamic model may be used in future in‐depth studies on PEMFC behaviour and in dynamic applications for health monitoring and fault diagnosis.     

Low power proton exchange membrane fuel cell system identification and adaptive control

This paper proposes a systematic method of system identification and control of a proton exchange membrane (PEM) fuel cell. This fuel cell can be used for low-power communication devices involving complex electrochemical reactions of nonlinear and time-varying dynamic properties. From a system point of view, the dynamic model of PEM fuel cell is reduced to a configuration of two inputs, hydrogen and air flow rates, and two outputs, cell voltage and current. The corresponding transfer functions describe linearized subsystem dynamics with finite orders and time-varying parameters, which are expressed as discrete-time auto-regression moving-average with auxiliary input models for system identification by the recursive least square algorithm. In the experiments, a pseudo-random binary sequence of hydrogen or air flow rate is fed to a single fuel cell device to excite its dynamics. By measuring the corresponding output signals, each subsystem transfer function of reduced order is identified, while the unmodeled, higher-order dynamics and disturbances are described by the auxiliary input term. This provides a basis of adaptive control strategy to improve the fuel cell performance in terms of efficiency, as well as transient and steady state specifications. Simulation shows that adaptive controller is robust to the variation of fuel cell system dynamics, and it has proved promising from the experimental results.     

Investigation and analysis of proton exchange membrane fuel cell dynamic response characteristics on hydrogen consumption of fuel cell vehicle

The number of working points and response speed are two essential characteristics of proton exchange membrane fuel cell (PEMFC). The improper setting of the number of working points and response speed may reduce the life of PEMFC and increase the hydrogen consumption of the vehicle. This paper explores the impact of the response speed as well as the working points of the PEMFC on the hydrogen consumption in the real-system level. In this paper a dynamic model of the PEMFC system is established and verified by experiments. The model is able to reflect the dynamic response process of PEMFC under a series different number of working points and different response speed. Based on the proposed model, the influence of working points and the response speed of PEMFC on the hydrogen consumption in the vehicle under different driving cycles is analyzed and summarized, for the first time, in the open literature. The results highlight that the hydrogen consumption will decreases in both cases that with the increase of working point number and increase of response speed. However, the reduction range of hydrogen consumption trends to smaller and may reach to an optimal level considering the trade-off between the hydrogen saving and the other costs, for example the control cost. Also, with a more complex driving cycle, the working points and response speed have a greater the impact on the hydrogen consumption in the vehicle applications.     

A simple electric circuit model for proton exchange membrane fuel cells

A simple and novel dynamic circuit model for a proton exchange membrane (PEM) fuel cell suitable for the analysis and design of power systems is presented. The model takes into account phenomena like activation polarization, ohmic polarization, and mass transport effect present in a PEM fuel cell. The proposed circuit model includes three resistors to approach adequately these phenomena; however, since for the PEM dynamic performance connection or disconnection of an additional load is of crucial importance, the proposed model uses two saturable inductors accompanied by an ideal transformer to simulate the double layer charging effect during load step changes. To evaluate the effectiveness of the proposed model its dynamic performance under load step changes is simulated. Experimental results coming from a commercial PEM fuel cell module that uses hydrogen from a pressurized cylinder at the anode and atmospheric oxygen at the cathode, clearly verify the simulation results.     

Transport phenomena within the porous cathode for a proton exchange membrane fuel cell

A two-phase, one-dimensional steady model is developed to analyze the coupled phenomena of cathode flooding and mass-transport limiting for the porous cathode electrode of a proton exchange membrane fuel cell. In the model, the catalyst layer is treated not as an interface between the membrane and gas diffusion layer, but as a separate computational domain with finite thickness and pseudo-homogenous structure. Furthermore, the liquid water transport across the porous electrode is driven by the capillary force based on Darcy's law. And the gas transport is driven by the concentration gradient based on Fick's law. Additionally, through Tafel kinetics, the transport processes of gas and liquid water are coupled. From the numerical results, it is found that although the catalyst layer is thin, it is very crucial to better understand and more correctly predict the concurrent phenomena inside the electrode, particularly, the flooding phenomena. More importantly, the saturation jump at the interface of the gas diffusion layer and catalyst layers is captured, when the continuity of the capillary pressure is imposed on the interface. Elsewise, the results show further that the flooding phenomenon in the CL is much more serious than that in the GDL, which has a significant influence on the mass transport of the reactants. Moreover, the saturation level inside the cathode is determined, to a great extent, by the surface overpotential, the absolute permeability of the porous electrode, and the boundary value of saturation at the gas diffusion layer-gas channel interface. In order to prevent effectively flooding, it should remove firstly the liquid water accumulating inside the CL and keep the boundary value of liquid saturation as low as possible.     

An improved model for predicting electrical contact resistance between bipolar plate and gas diffusion layer in proton exchange membrane fuel cells

Electrical contact resistance between bipolar plates (BPPs) and gas diffusion layers (GDLs) in PEM fuel cells has attracted much attention since it is one significant part of the total contact resistance which plays an important role in fuel cell performance. This paper extends a previous model by Zhou et al. [Y. Zhou, G. Lin, A.J. Shih, S.J. Hu, J. Power Sources 163 (2007) 777–783] on the prediction of electrical contact resistance within PEM fuel cells. The original microscale numerical model was based on the Hertz solution for individual elastic contacts, assuming that contact bodies, GDL carbon fibers and BPP asperities are isotropic elastic half-spaces. The new model features a more practical contact by taking into account the bending behavior of carbon fibers as well as their anisotropic properties. The microscale single contact process is solved numerically using the finite element method (FEM). The relationship between the contact pressure and the electrical resistance at the GDL/BPP interface is derived by multiple regression models. Comparisons of the original model by Zhou et al. and the new model with experimental data show that the original model slightly overestimates the electrical contact resistance, whereas a better agreement with experimental data is observed using the new model.     

A mini-type hydrogen generator from aluminum for proton exchange membrane fuel cells

A safe and simple hydrogen generator, which produced hydrogen by chemical reaction of aluminum and sodium hydroxide solution, was proposed for proton exchange membrane fuel cells. The effects of concentration, dropping rate and initial temperature of sodium hydroxide solution on hydrogen generation rate were investigated. The results showed that about 38 ml min⁻¹ of hydrogen generation rate was obtained with 25 wt.% concentration and 0.01 ml s⁻¹ dropping rate of sodium hydroxide solution. The cell fueled by hydrogen from the generator exhibited performance improvement at low current densities, which was mainly due to the humidified hydrogen reduced the protonic resistivity of the proton exchange membrane. The hydrogen generator could stably operate a single cell under 500 mA for nearly 5 h with about 77% hydrogen utilization ratio.