Effect of CO in the anode fuel on the performance of PEM fuel cell cathode

Even trace amounts of CO in the fuel for a proton-exchange membrane fuel cell (PEMFC) could poison not only the anode, which is directly exposed to the fuel, but also the cathode, which is separated from the fuel by a proton-exchange membrane; and the performance decline of the cathode is sometimes more than that of the anode. Adsorption of CO on the cathode catalyst has been detected electrochemically, and this indicates that CO can pass through the membrane to reach the cathode. To reduce such a poisoning effect, fuel cell operation conditions (e.g. level of membrane humidification, gas pressure difference between cathode and anode), membrane and catalyst layer structures, and CO-tolerant cathode catalysts should be further explored.     

Uncertainty analysis and robust control of fuel delivery systems considering nitrogen crossover phenomenon

In this paper, the fuel delivery subsystem (FDS) with hydrogen recirculation and anode bleeding is applied in proton exchange membrane fuel cell (PEMFC) system, which is utilized to supply hydrogen to the anode of stack and recirculate fuel back to the supply line. As the diffusion of nitrogen from cathode to anode is inevitable in a real PEMFC during long-term operation. To prevent system performance decline due to nitrogen accumulation. Therefore, this paper firstly develops a control-oriented nonlinear dynamic FDS model involving gas diffusion. Additionally, the FDS is very sensitive to operating environment, uncontrolled operation conditions may cause stack degradation. Specifically, a method based on Monte Carlo simulation is proposed to identify the key parameter boundaries. Then the gas distribution in FDS due to nitrogen crossover is analyzed in detail. After this, a hybrid robust methodology based on sliding mode algorithm is also proposed to maintain adequate hydrogen pressure supply, suitable hydrogen and nitrogen content in the system in presence of nitrogen crossover and renewed uncertainties. Finally, the performance of the presented controller is compared with nonlinear PID (NPID) control and nonlinear multi-input-multi-output (NMIMO) control through a hardware-in-the-loop test bench. Experimental results show that the hybrid controller is accurate and suitable for control purpose, the nitrogen content is restricted to the given range and the variation of output voltage is limited to the desired boundaries, the feasibility and effectiveness are validated.     

High-potential control for durability improvement of the vehicle fuel cell system based on oxygen partial pressure regulation under low-load conditions

In the state-of-the-art high-power self-humidifying proton exchange membrane fuel cell (PEMFC) systems for vehicles, the high potential and low water production at idle or low load conditions strongly cause corrosion and decay of key materials and thus reduce durability. Therefore, the control technology of system-level durability requires an innovative design. Cathode recirculation is beneficial in alleviating the above unfavorable factors from the perspective of regulating oxygen and vapor partial pressure. This paper presents a pioneering study on the dynamics and control of cathode recirculation in vehicle high-power self-humidifying PEMFC system under low load conditions. First, a control-oriented dynamic model of the vehicle PEMFC system with a cathode recirculation loop is developed and the steady-state and dynamic performance is verified with experimental data from a 120 kW system. Active control of the intake component is achieved by re-feeding the reacted cathode gas to the air compressor outlet through a recirculation pump. On this basis, a high-potential controller based on oxygen partial pressure regulation is designed in combination with the dynamics of cathode recirculation. Results show that the designed dynamic fuzzy logic segmented proportional integral derivative controller with feedforward compensation achieves the optimal high-potential control effect by managing the oxygen partial pressure under variable low load conditions. It not only has excellent anti-disturbance ability but also effectively reduces the dynamic response time, transient overshoot, and steady-state error to satisfy the rapid and stable voltage output. Finally, the concomitant effect of humidification brought by the implementation of the optimal high-potential controller is analyzed, and the results show that the proton membrane is completely humidified.     

Dynamic modeling and adaptive control of voltage in proton exchange membrane fuel cell using water management

Maintaining a constant voltage in polymer electrolyte membrane fuel cells (PEMFCs) has always attracted the attention of many researchers, and many articles have been published on this issue. Furthermore, water management in PEMFC has become an important challenge because it can improve cell efficiency and lifetime. This paper will develop a one‐dimensional dynamic model for a single PEMFC, which correlates changes in the cell voltage to changes in the cell current density and humidification rate. Subsequently, a recurrent neural network controller based on the approximation of nonlinear autoregressive moving average model is proposed. The controller manipulates the anode and the cathode water mole fractions in order to fix cell voltage and preserve cell water content within a satisfactory interval regardless of the varying cell current. The model and the controller are simulated in matlab /Simulink (Mathworks Inc., Natick, MA) software, and the results are compared with a PID controller from different viewpoints such as current disturbance and plant parameter variation. Copyright © 2011 John Wiley & Sons, Ltd.     

Discrete ejector control solution design,characterization, and verification in a 5 kW PEMFC system

An ejector primary gas flow control solution based on three solenoid valves is designed, implemented and tested in a 5 kW proton exchange membrane fuel cell (PEMFC) system with ejector-based anode gas recirculation. The robust and cost effective combination of the tested flow control method and a single ejector is shown to achieve adequate anode gas recirculation rate on a wide PEMFC load range.In addition, the effect of anode gas inert content on ejector performance in the 5 kW PEMFC system is studied at varying load and anode pressure levels. Results show that increasing the inert content increases recirculated anode gas mass flow rate but decreases both the molar flow rate and the anode inlet humidity.Finally, the PEMFC power ramp-rate limitations are studied using two fuel supply strategies: 1) advancing fuel supply and venting out extra fuel and 2) not advancing fuel supply but instead using a large anode volume. Results indicate that the power of the present PEMFC system can be ramped from 1 kW to 4.2 kW within few hundred milliseconds using either of these strategies.     

Treatment of low concentration hydrogen by electrochemical pump or proton exchange membrane fuel cell

Proton exchange membrane fuel cell (PEMFC) can produce electricity through electrochemical reaction of hydrogen with oxygen with the use of a membrane and electrode assembly (MEA). In other words, the hydrogen pressure difference between the anode and cathode can produce electricity via an electrochemical process. Conversely, when we supply electricity to MEA from an external power source, we can pump up or separate hydrogen from the low-pressure anode to the high-pressure cathode, according to the principle of “concentration cell”. By the way, PEMFC cannot use the fuel completely, because a cell potential decreases and electrode material may corrode when most of the fuel is consumed. Therefore the fuel released from PEMFC should be treated safely. The depleted hydrogen from PEMFC can be recovered by the electrochemical hydrogen pump, or further can be used as a fuel for the power generation by PEMFC, even though the cell voltage might be low. In this study we preliminarily measured the voltage–current characteristics of hydrogen pump and PEMFC changing the hydrogen concentration from 99.99% to 1%, as another option to platinum catalytic combustion of low concentration hydrogen. Moreover we could successfully treat the low concentration hydrogen by electrochemical pump or PEMFC, for the widely changing hydrogen concentration and mixture flow rate. The gas chromatography confirmed the hydrogen concentration of the treated gas to be 1000 ppm at most.     

Numerical simulation of exchange membrane fuel cells in different operating conditions

A two-dimensional, steady state model for proton exchange membrane fuel cell (PEMFC) is presented. The model is used to describe the effect operation conditions (current density, pressure and water content) on the water transport, ohmic resistance and water distribution in the membrane and performance of PEMFC. This model considers the transport of species and water along the porous media: gas diffusion layers (GDL) anode and cathode, and the membrane of PEMFC fuel cell.     

A fuzzy logic PI control with feedforward compensation for hydrogen pressure in vehicular fuel cell system

In a vehicular fuel cell system, alternative load and frequent purge action can lead to anode pressure varies with the hydrogen mass flow fluctuation. It's crucial to control the pressure difference between anode and cathode within a reasonable range to avoid adverse phenomena such as membrane failure, reactant starvation, or even water management fault. In this paper, an improved proportional integrative (PI) controller by the fuzzy logic technique that considers the engineer experience and knowledge on the hydrogen supply system behavior is proposed for hydrogen pressure control, in which the PI parameters are tuned by a fuzzy decision process. Furthermore, load current and purge action regarded as input disturbances are applied for feedforward compensation to reduce the pressure response hysteresis. A hydrogen supply subsystem based on the proportional valve is modeled, and corresponding parameters are determined by analyzing the response time and steady pressure fluctuation. The performance of the conventional PI controller, the fuzzy logic PI (FLPI) controller and fuzzy logic PI with feedforward (FLPIF) controller is validated. The presented results indicated that the FLPI controller significantly improves the dynamic response of hydrogen pressure compared to the PI controller, and the FLPIF controller can further reduce overshoot caused by disturbance. Finally, the proposed FLPIF controller is implemented on a rapid prototype platform of the hydrogen supply subsystem and an actual fuel cell system, exhibiting satisfactory performance.     

Modeling of the Ballard-Mark-V proton exchange membrane fuel cell with power converters for applications in autonomous underwater vehicles

This paper studies the transient response of the output voltages of a Ballard-Mark-V 35-cell 5 kW proton exchange membrane fuel cell (PEMFC) stack with power conversion for applications in autonomous underwater vehicles (AUVs) under load changes. Four types of pulse-width modulated (PWM) dc-dc power converters are employed to connect to the studied fuel cell in series for converting the unregulated fuel cell stack voltage into the desired voltage levels. The fuel cell model in this paper consists of the double-layer charging effect, gases diffusion in the electrodes, and the thermodynamic characteristic; PWM dc-dc converters are assumed to operate in continuous-conduction mode with a voltage-mode control compensator. The models of the study's fuel cell and PWM dc-dc converters have been implemented in a Matlab/SIMULINKTM environment. The results show that the output voltages of the studied PEMFC connected with PWM dc-dc converters during a load change are stable. Moreover, the model can predict the transient response of hydrogen/oxygen out flow rates and cathode and anode channel temperatures/pressures under sudden change in load current.     

Anode bleeding experiments to improve the performance and durability of proton exchange membrane fuel cells

Cost, durability, efficiency and fuel utilization are important issues that remain to be resolved for commercialization of proton exchange membrane fuel cells (PEMFC). Anode flow mode, which includes recirculation, dead-ended and exit bleeding operation, plays an important role in fuel utilization, durability, performance and the overall cost of the fuel cell system. Depending on the flow mode, water and nitrogen accumulation in the anode leads to voltage transients and local fuel starvation, which causes cell potential reversal and carbon corrosion in the cathode catalyst layers. Controlled anode exit bleeding can avoid the accumulation of nitrogen and water and improve fuel utilization. In this study, we present a method to control the bleed rate with high precision in experiments and demonstrate that hydrogen utilization as high as 0.9988 for a 25 cm² single cell and 0.9974 for an 8.17 cm² single cell can be achieved without significant performance loss. In the experiments, anode pressure is kept at 1 bar higher than the cathode pressure to decrease nitrogen crossover from the cathode, decreasing the crossover from the cathode. Moreover, four load cycle profiles are applied to observe the cumulative loss in the electrochemical surface area (ECSA), which are acquired from cyclic voltammetry (CV) analysis. Experiments confirm that the ECSA loss and severe voltage transients are indicative of fuel starvation induced by prolonged dead-ended or low exit-bleed operation modes whereas bleed rates that are larger than the predicted crossover rate are sufficient to operate the fuel cell without voltage transients and detrimental ECSA loss.     

Numerical analysis on the effects of manifold design on flow uniformity in a large proton exchange membrane fuel cell stack

The size and configuration of manifold can affect the flow characteristics and uniformity in proton exchange membrane fuel cell (PEMFC) stack; then its efficiency and service life. Based on the simulation results of a single fuel cell considering electrochemical reaction, a stack model with 300 porous media is established to numerically investigate the performances of a large commercial PEMFC stack. The effects of manifold width and configuration type on the pressure drop and species concentration are studied by computational fluid dynamics (CFD). The results show that the uniformity for most cases of U-type configuration is better than those of Z-type configuration. For U-type configuration, a very good uniformity can be obtained by selecting anode inlet manifold width of 20 mm and anode outlet manifold in range from 25 to 30 mm; the uniformity is bad for all cathode inlet manifold width, relatively better uniformity can be achieved by adjusting cathode outlet manifold width. For Z-type configuration, bad uniformity is found for cathode inlet and outlet manifold with all width; a relatively good uniformity can be obtained with suitable anode manifold width of 35 mm. The research can provide some references to improve gas distribution uniformity in large PEMFC stacks.     

Oxygen excess ratio control of PEM fuel cells using observer-based nonlinear triple-step controller

This paper proposes a novel observer-based nonlinear triple-step controller for the air supply system of polymer electrolyte membrane (PEM) fuel cell. The control objective is adjusting the oxygen excess ratio to its reference value under fast current transitions, so as to avoid the oxygen starvation and obtain the maximum net power. Considering that the cathode pressure cannot be measured directly, we design a disturbance observer to estimate the cathode pressure based on the developed third-order nonlinear model of air supply system. Next, a triple-step nonlinear method is applied to derive an oxygen excess ratio tracking controller, wherein the stability of closed-loop system is guaranteed by Lyapunov-based technique. Subsequently, several key issues of controller in practical implementation are explained, and then the robustness analysis against the considered lumped disturbance is carried out. Finally, the performance of the proposed control scheme is validated through a series of comparative simulations, and the simulation results demonstrate the effectiveness and robustness of the proposed approach under different load variations and parameter uncertainties.     

Real-time AC voltage control and power-following of a combined proton exchange membrane fuel cell,and ultracapacitor bank with nonlinear loads

The nonlinear loads create a wide range of current harmonics in the system. Such loads can make distortions on the output voltage profile, influence on the fuel cell (FC) performance, and endanger safe operation of the FC unit. In this paper, new strategies for power-following and AC voltage control have been developed. The proposed system consists of the ultracapacitor (UC) bank and proton exchange membrane fuel cell (PEMFC) supplying nonlinear AC loads. The power tracking strategy is based on the Fourier analysis of total load demand. The Fourier analysis is used as an effective tool to eliminate destructive effect of current harmonics on the PEMFC output current. To supply the nonlinear AC loads under sinusoidal voltage with the fast response, a dynamic model for the inverter control loop is also presented. This model is used to enhance the input reference tracking and reject input/output disturbances. The simulation outcomes confirm the desirable PEMFC performance against nonlinear load disturbances. In addition, the output AC voltage is kept sinusoidal and has low deviations under nonlinear load variations.     

Simultaneous direct visualisation of liquid water in the cathode and anode serpentine flow channels of proton exchange membrane (PEM) fuel cells

Water flooding is detrimental to the performance of the proton exchange membrane fuel cell (PEMFC) and therefore it has to be addressed. To better understand how liquid water affects the fuel cell performance, direct visualisation of liquid water in the flow channels of a transparent PEMFC is performed under different operating conditions. Two high-resolution digital cameras were simultaneously used for recording and capturing the images at the anode and cathode flow channels. A new parameter extracted from the captured images, namely the wetted bend ratio, has been introduced as an indicator of the amount of liquid water present at the flow channel. This parameter, along with another previously used parameter (wetted area ratio), has been used to explain the variation in the fuel cell performance as the operating conditions of flow rates, operating pressure and relative humidity change. The results have shown that, except for hydrogen flow rate, the wetted bend ratio strongly linked to the operating condition of the fuel cell; namely: the wetted bend ratio was found to increase with decreasing air flow rate, increasing operating pressure and increasing relative humidity. Also, the status of liquid water at the anode was found to be similar to that at the cathode for most of the cases and therefore the water dynamics at the anode side can also be used to explain the relationships between the fuel cell performance and the investigated operating conditions.     

A new dynamic model for predicting transient phenomena in a PEM fuel cell system

In this paper, a mathematical model is developed to simulate the transient phenomena in a polymer electrolyte membrane fuel cell (PEMFC) system. At present many electrochemical models are available to the fuel cell designers to capture steady state behavior by estimating the equilibrium voltage for a particular set of operating conditions, but models capable of describing transient phenomena are scanty. In practical applications such as powertrains of land-based vehicles or submarines, the output power from the fuel cell system undergoes large variations especially during acceleration and deceleration. During such processes, many transient dynamic mechanisms become significant, while simple empirical models are unable to represent the transient dynamics caused by such as diffusion effect and double layer capacitance at the interface between the electrodes and the electrolyte. Hence, a novel dynamic fuel cell model is developed in this paper which incorporates the effects of charge double layer capacitance, the dynamics of flow and pressure in the anode and cathode channels and mass/heat transfer transient features in the fuel cell body. This dynamic model can predict the transient response of cell voltage, temperature of the cell, hydrogen/oxygen out flow rates and cathode and anode channel temperatures/pressures under sudden change in load current. The proposed model is implemented in SIMULINK environment. The simulation results are analyzed and compared to benchmark results. Lab tests are carried out at Connecticut Global Fuel Cell Center and a good agreement is found between tests and simulations. This model will be very useful for the optimal design and real-time control of PEM fuel cell systems.     

An adaptive sliding mode observer based near-optimal OER tracking control approach for PEMFC under dynamic operation condition

Tracking control of oxygen excess ratio (OER) is crucial for dynamic performance and operating efficiency of the proton exchange membrane fuel cell (PEMFC). OER tracking errors and overshoots under dynamic load limit the PEMFC output power performance, and also could lead oxygen starvation which seriously affect the life of PEMFC. To solve this problem, an adaptive sliding mode observer based near-optimal OER tracking control approach is proposed in this paper. According to real time load demand, a dynamic OER optimization strategy is designed to obtain an optimal OER. A nonlinear system model based near-optimal controller is designed to minimize the OER tracking error under variable operation condition of PEMFC. An adaptive sliding mode observer is utilized to estimate the uncertain parameters of the PEMFC air supply system and update parameters in near-optimal controller. The proposed control approach is implemented in OER tracking experiments based on air supply system of a 5 kW PEMFC test platform. The experiment results are analyzed and demonstrate the efficacy of the proposed control approach under load changes, external disturbances and parameter uncertainties of PEFMC system.     

Investigation of the effect of microporous layers on water management in a proton exchange membrane fuel cell using novel diagnostic methods

Water management remains a significant challenge for the Proton Exchange Membrane Fuel Cell (PEMFC) with respect to performance, lifetime and operational flexibility. In recent years, microporous layers (MPL) have been widely used on the cathode side of the PEMFC in order to improve fuel cell performance and water management capabilities. Many modeling and experimental studies have with limited success attempted to analyze the underlying mechanisms that are responsible for the performance improvement due to the MPL. In this study, porous inserts along with various in-situ experimental techniques are used to investigate the MPLs. It was observed that the anode pressure drop increased when a cathode MPL was present, indicating water cross-over from the cathode towards the anode side. Further testing identified that the MPL improved cell performance due to the reduction of water saturation in the cathode catalyst layer, which resulted in enhanced oxygen diffusion. The influence of the MPL on the anode side was also studied with the aid of porous inserts and other techniques, and it was observed that the anode MPL improves cell voltage stability and reduces water accumulation in the anode catalyst layer. The present investigation provides further important information on the critical role of the MPL in the PEMFC.     

Study on voltage clamping and self-humidification effects of pem fuel cell system with dual recirculation based on orthogonal test method

Durability and reliability are still major challenges of vehicular polymer electrolyte membrane fuel cell (PEMFC) systems. With exhaust gas recirculation on both the anode and cathode sides, two important functions can be achieved: the voltage clamping in low current density, and the self-humidification without any external humidifiers. The former restrains catalyst decay in small load working conditions, and the latter is beneficial for improving the cold-start ability. In this study, dynamic performances and stable characteristics of a fuel cell system with dual exhaust gas recirculation are firstly experimentally studied using an orthogonal test method. System parameters, including humidification temperature of cathode external humidifier, fresh air stoichiometric ratio (SR), current density, cathode and anode recirculation pump speeds, are regarded as key factors in the experiments based on the testing conditions of the test-bench. Two four-factor and three-level orthogonal tables are designed, and the effects of key factors on system performance indices (average cell voltage, relative humidity (RH) at cathode inlet, high frequency resistance (HFR), oxygen concentrations at cathode inlet and outlet, and the concentration difference between these two positions) are investigated. Results show that: (1) with the cathode recirculation, the cell voltage can be reduced in low current densities by coordinately adjusting the recycled gas flow and reducing fresh air SR; (2) with the dual recirculation, the fuel cell membrane can be well hydrated, and system performance only shows 3% reduction compared with a system with an external humidifier; (3) the difference between the oxygen molar concentration at the inlet and outlet of cathode gas channels becomes small using dual recirculation.     

质子交换膜燃料电池建模及水热传输特性分析

针对质子交换膜燃料电池(PEMFC)水管理开展了研究,建立了一维非等温两相流解析模型,研究了不同电流密度、微孔层接触角和不同加湿方案对电池内部水分布和温度分布的影响,提出了更好的进气加湿方案。结果表明:电流密度增大会导致阳极拖干、阴极水淹加剧,导致电池各部分温度上升。因各层材料亲水性不同,在交界面处能观察到液态水阶跃现象。增大微孔层接触角促进阴极液态水反扩散到阳极,一定程度上缓解阳极变干,但过大的接触角可能导致阴极水淹加剧。通过采取"阳极充分加湿、阴极低加湿"的进气加湿方案可以有效提高电池性能,并且能在一定程度改善电池内部受热,提高电池使用寿命。     

Transient response of a unit proton-exchange membrane fuel cell under various operating conditions

The transient response of proton-exchange membrane fuel cells (PEMFCs) is an important criterion in their application to automotive systems. Nevertheless, few papers have attempted to study experimentally this dynamic behaviour and its causes. Using a large-effective-area (330 cm²) unit PEMFC and a transparent unit PEMFC (25 cm²), systematic transient response and cathode flooding during load changes are investigated. The cell voltage is acquired according to the current density change under a variety of stoichiometry, temperature and humidity conditions, as well as different flooding intensities. In the case of the transparent fuel cell, the cathode gas channel images are obtained simultaneously with a CCD imaging system. The different levels of undershoot occur at the moment of load change under different cathode stoichiometry, both cathode and anode side humidity and flooding intensity conditions. It is shown that undershoot behaviour consists of two stages with different time delays: one is of the order of 1 s and the other is of the order of 10 s. It takes about 1 s for the product water to come up on to the flow channel surface so that oxygen supply is temporarily blocked, which causes voltage loss in that “undershoot”. The correlation of dynamic behaviour with stoichiometry and cathode flooding is analyzed from the results of these experiments.