Modelling of polymer electrolyte membrane fuel cell stacks based on a hydraulic network approach

Polymer electrolyte membrane (PEM) fuel cells convert the chemical energy of hydrogen and oxygen directly into electrical energy. Waste heat and water are the reaction by‐products, making PEM fuel cells a promising zero‐emission power source for transportation and stationary co‐generation applications. In this study, a mathematical model of a PEM fuel cell stack is formulated. The distributions of the pressure and mass flow rate for the fuel and oxidant streams in the stack are determined with a hydraulic network analysis. Using these distributions as operating conditions, the performance of each cell in the stack is determined with a mathematical, single cell model that has been developed previously. The stack model has been applied to PEM fuel cell stacks with two common stack configurations: the U and Z stack design. The former is designed such that the reactant streams enter and exit the stack on the same end, while the latter has reactant streams entering and exiting on opposite ends. The stack analysed consists of 50 individual active cells with fully humidified H₂ or reformate as fuel and humidified O₂ or air as the oxidant. It is found that the average voltage of the cells in the stack is lower than the voltage of the cell operating individually, and this difference in the cell performance is significantly larger for reformate/air reactants when compared to the H₂/O₂ reactants. It is observed that the performance degradation for cells operating within a stack results from the unequal distribution of reactant mass flow among the cells in the stack. It is shown that strategies for performance improvement rely on obtaining a uniform reactant distribution within the stack, and include increasing stack manifold size, decreasing the number of gas flow channels per bipolar plate, and judicially varying the resistance to mass flow in the gas flow channels from cell to cell. Copyright © 2004 John Wiley & Sons, Ltd.     

Fabrication and operation of a 1 kW class anode-supported flat tubular SOFC stack

A 1 kW class anode-supported flat tubular SOFC stack for intermediate temperature (700–800 °C) operation was fabricated and operated in this study. For this purpose, we fabricated anode-supported flat tubular cells by optimization of the current collecting method and the induction brazing process. After that, we designed a compact fuel and air manifold by adopting a simulation technique to uniformly supply fuel and air gas into the stack and a unique seal and insulation method to make a more compact stack. To assemble the stack, the prepared anode-supported flat tubular cells with an effective electrode area of 90 cm² were connected in series to 30 bundles, in which one unit bundle consists of two flat tubular cells connected in parallel. The performance of the stack in 3% humidified H₂ and air at 750 °C showed a maximum electrical power of 921 W (fuel utilization ratio = 25.2%).     

A silicon‐based micro direct methanol fuel cell stack with a serial flow path design

A 6‐cell silicon‐based micro direct methanol fuel cell (μDMFC) stack utilized the serial flow path design was developed. The effect of the structure of flow path on the performance of the stack was investigated using polarization characterization and electrochemical impedance analysis. Further, the voltage distribution for individual cells under different current density was discussed. The results indicated that the μDMFC stack with the serial flow path design exhibited better performance than that utilized the parallel flow path due to uniform mass transfer of methanol as a result of the use of the serial flow path. Such a μDMFC stack generates a peak output power of ca. 187 mW, corresponding to an average power density of ca. 21.7 mWcm^‐2, and exhibits a steady‐state power output for more than 100 h. Copyright © 2011 John Wiley & Sons, Ltd.     

Steady state and dynamic performance of proton exchange membrane fuel cells (PEMFCs) under various operating conditions and load changes

The steady-state performance and transient response for H₂/air polymer electrolyte membrane (PEM) fuel cells are investigated in both single fuel cell and stack configurations under a variety of loading cycles and operating conditions. Detailed experimental parameters are controlled and measured under widely varying operating conditions. In addition to polarization curves, feed gas flow rates, temperatures, pressure drop, and relative humidity are measured. Performance of fuel cells was studied using steady-state polarization curves, transient I–V response and electrochemical impedance spectroscopy (EIS) techniques. Different feed gas humidity, operating temperature, feed gas stoichiometry, air pressure, fuel cell size and gas flow patterns were found to affect both the steady state and dynamic response of the fuel cells. It was found that the humidity of cathode inlet gas had a significant effect on fuel cell performance. The experimental results showed that a decrease in the cathode humidity has a detrimental effect on fuel cell steady state and dynamic performance. Temperature was also found to have a significant effect on the fuel cell performance through its effect on membrane conductivity and water transport in the gas diffusion layer (GDL) and catalyst layer. The polarization curves of the fuel cell at different operating temperatures showed that fuel cell performance was improved with increasing temperature from 65 to 75 °C. The air stoichiometric flow rate also influenced the performance of the fuel cell directly by supplying oxygen and indirectly by influencing the humidity of the membrane and water flooding in cathode side. The fuel cell steady state and dynamic performance also improved as the operating pressure was increased from 1 to 4 atm. Based on the experimental results, both the steady state and dynamic response of the fuel cells (stack) were analyzed. These experimental data will provide a baseline for validation of fuel cell models.     

Studies on the cathode humidification by exhaust gas recirculation for PEM fuel cell

For high efficiency and long durability of proton exchange membrane fuel cells (PEMFCs), polymer electrolyte membranes should be kept wet. Reactant gases should be humidified on this account. For the humidification, the PEMFC system uses an external or internal humidifier as a part of balance of plants (BOPs). However, external humidifiers have many disadvantages such as parasitic power loss, system complexity, high cost and bulky volume. As such, efforts have been made to remove the external humidifier or replace it with an advanced humidifier. In this work, to remove a humidifier, humidification by exhaust gas recirculation is investigated by theoretical analysis and experiments with 5-cell stack of an active area 250 cm². In the theoretical analysis, species conservation equations and energy conservation equation are solved to obtain the O₂ concentration, stoichiometric ratio, humidity ratio, temperature, amount of condensed water and so on. With the theoretical results, experiments with 5-cell, 250 cm² fuel cell stack were carried out in order to analyze the stack performance at the theoretical conditions of the cathode process stream of exhaust gas recirculation.     

Development of a stack having an optimized flow field structure with low cross transport effects

PEM fuel cells when operated on hydrogen from renewable sources are viewed as one of the most environmentally friendly energy conversion systems due to their high electrical efficiency. However, this advantage is depending on the overall system design, which is largely determined by the allowable operating conditions of the fuel cell stack itself. Besides the active materials, design and shape of the gas distribution zone have a significant influence on stack operation. In order to optimize overall system performance, a fuel cell stack with improved flow field design and performance was developed. An investigation on channel geometries led to a serpentine flow field with a moderate degree of parallelization and ribs with variable width to reduce cross transport effects. The resulting flow field subsequently has been modified slightly to allow a high volume production process. Summarizing, power as well as the degrees of H₂ and air utilization could be enhanced leading to a power density enhancement. Furthermore, weight reduction of end plates nearly by half using an improved end plate design led to an overall improved stack design.     

Voltage instability in a simulated fuel cell stack correlated to cathode water accumulation

Single fuel cells running independently are often used for fundamental studies of water transport. It is also necessary to assess the dynamic behavior of fuel cell stacks comprised of multiple cells arranged in series, thus providing many paths for flow of reactant hydrogen on the anode and air (or pure oxygen) on the cathode. In the current work, the flow behavior of a fuel cell stack is simulated by using a single-cell test fixture coupled with a bypass flow loop for the cathode flow. This bypass simulates the presence of additional cells in a stack and provides an alternate path for airflow, thus avoiding forced convective purging of cathode flow channels. Liquid water accumulation in the cathode is shown to occur in two modes; initially nearly all the product water is retained in the gas diffusion layer until a critical saturation fraction is reached and then water accumulation in the flow channels begins. Flow redistribution and fuel cell performance loss result from channel slug formation. The application of in-situ neutron radiography affords a transient correlation of performance loss to liquid water accumulation. The current results identify a mechanism whereby depleted cathode flow on a single cell leads to performance loss, which can ultimately cause an operating proton exchange membrane fuel cell stack to fail.     

Experimental analysis of internal gas flow configurations for a polymer electrolyte membrane fuel cell stack

The internal gas distribution system utilised for supplying fresh reactants and removing reaction products from the individual cells of a fuel cell stack can be designed in a parallel, a serial or a mixture of parallel and serial gas flow configuration. In order to investigate the interdependence between the internal stack gas distribution configuration and single cell as well as overall stack performance, a small laboratory-scale fuel cell stack consisting of identical unit cells was subject to operation with different gas distribution configurations and different operating parameters. The current/voltage characteristics measured with the different gas distribution configurations are analysed and compared on unit cell- as well as on stack-level. The results show the significant impact of the internal stack gas distribution system on operation and performance of the individual unit cells and the overall stack.     

Control and experimental characterization of a methanol reformer for a 350 W high temperature polymer electrolyte membrane fuel cell system

This work presents a control strategy for controlling the methanol reformer temperature of a 350 W high temperature polymer electrolyte membrane fuel cell system, by using a cascade control structure for reliable system operation. The primary states affecting the methanol catalyst bed temperature is the water and methanol mixture fuel flow and the burner fuel/air ratio and combined flow. An experimental setup is presented capable of testing the methanol reformer used in the Serenergy H3 350 Mobile Battery Charger; a high temperature polymer electrolyte membrane (HTPEM) fuel cell system. The experimental system consists of a fuel evaporator utilizing the high temperature waste gas from the cathode air cooled 45 cell HTPEM fuel cell stack. The fuel cells used are BASF P1000 MEAs which use phosphoric acid doped polybenzimidazole membranes. The resulting reformate gas output of the reformer system is shown at different reformer temperatures and fuel flows, using the implemented reformer control strategy. The gas quality of the output reformate gas is of HTPEM grade quality, and sufficient for supporting efficient and reliable HTPEM fuel cell operation with CO concentrations of around 1% at the nominal reformer operating temperatures. As expected increasing temperatures also increase the dry gas CO content of the reformate gas and decreases the methanol slip. The hydrogen content of the gas was measured at around 73% with 25% CO₂.     

The oil bath thermal cycling absorption process design and separation process research

Thermal cycling absorption process (TCAP) has been developed for years to support the separation of hydrogen isotopes, which has the characteristics of high separation efficiency and high recovery rate. The design of separation column structure, heating and cooling (H&C) system and technological parameters are the basis of TCAP technical process study and are the key points of TCAP engineering research. In this work, an improved separation system has been designed and built based on an oil bath H&C system for the first time. The separation column in this facility is 45 m long and the packing weight in the column is up to 8 kg. The separation experiments were carried out based on this facility, and the process parameters were adjusted according to the size of the separation column, which proved the superior performance of this facility. The separation experiments show that for 50% D₂ - 50% H₂ feed gas, the deuterium abundance can reach to 99% and the steady state extraction can be realized in production mode with the processing capacity over 400 standard L per day. Another experiment has been carried out with 1% D₂ - 99% H₂ feed gas, and the deuterium abundance exceeded 10%, verifying the separation ability at low abundance deuterium feed gas. Furthermore, the extraction rate can reach to 25% column capacity when the deuterium abundance in production gas is 5%.     

Performance characteristic of a tubular carbon-based fuel cell short stack coupled with a dry carbon gasifier

A carbon gasified carbon-based fuel cell (CFC) short stack was fabricated and investigated for generating effective carbon fuel cell reactions. Anode-supported tubular CFC cells with a 45 cm² active electrode area were used to manufacture the CFC short stack, which was coupled with a dry gasifier induced by a reverse Boudouard reaction. Activated carbon (BET area 1800 m²/g) powder was mixed with K₂CO₃ powder (5 wt.%) and used to fill a dry gasifier as a solid carbon fuel, and pure CO₂ gas was supplied to the gasifier. The CO fuel generated by the reverse Boudouard reaction in the dry gasifier increased the performance of the CFC short stack. The tubular CFC short stack showed a maximum power of 29.4 W at 800 °C. It was operated under a range of operating conditions by changing the operating temperature, flow rate of the pure CO₂ and the thermal cycle operation. The results indicate that the fabricated tubular CFC is a promising power generation system candidate for many practical applications, such as residential power generation (RPG) and stationary power systems.     

Effect of water vapor on deuterium separation by a polymer electrolyte fuel cell

Hydrogen isotopes are a valuable source of hydrogen energy through fusion reactions. The materials used in polymer electrolyte fuel cells (PEFCs), such as the hydrophobic support and Pt catalyst, are essentially the same to those used in the conventional isotope-separation method by water–hydrogen chemical exchange. Here, deuterium (D) separation was performed with a PEFC. A gas mixture of H₂ and D₂ was supplied while changing the humidity. The hydrogen gas and water vapor from the PEFC were analyzed to investigate the D mass balance. Without power generation, D was separated into the water vapor. This can be explained by the vapor-phase catalytic exchange reaction occurring on the platinum catalyst. The fuel-cell reaction enhanced D separation. A large amount of D (approximately 45%) was transferred to the water vapor during power generation. The present results demonstrate the synergistic effect of vapor-phase catalytic exchange and the PEFC on D separation.     

Experimental investigation of the effect of hydrogen recirculation on the performance of a proton exchange membrane fuel cell

The hydrogen recirculation in proton exchange membrane fuel cell (PEMFC) is recommended for the hydrogen supply of PEMFC, and hydrogen ejectors are gradually being used in fuel cell vehicles due to low noise and low energy consumption. However, there is a lack of discussion about the influence of recirculation rate on the stack. Due to passive regulating mechanism of the ejectors, a miniature speed-adjustable peristaltic pump is used to simulate the hydrogen ejector in this study to investigate the effect of hydrogen recirculation on the performance of PEMFC stack. Experiments are conducted under different pump flow rates. The stack with hydrogen recirculation is proven to have better performance, but over high pump flow rate can lead to hydrogen shortage. It is interesting to find that the flow rate fluctuation of hydrogen inlet affects the stability of stack performance, and pressure drop and recovery time during purge process are proposed as effective indicators for performance analysis. Finally, pump flow rates between 60 ml/min and 105 ml/min are defined as “effective area”. Based on the analysis of effective indicators, keeping at “effective area” is further proved to improve the performance of the stack, which is also useful to design hydrogen recirculation.     

Deuterium isotope separation by polymer electrolyte fuel cells connected in series

The separation of hydrogen isotopes has important applications for fundamental science and nuclear engineering. This study investigates isotope separation by stacked polymer electrolyte fuel cells that form part of a combined electrolysis and fuel cell (CEFC) system. Fuel gas containing deuterium (D) was generated by water electrolysis and passed through three fuel cells (FCs) connected in series. Increasing the number of operating FCs in the series greatly improved D separation, but had only a modest impact on power consumption. When all three FCs were individually controlled, the separation efficiency depended on the power condition in each FC. At high current the separation factor of the CEFC system reached over 100 owing to the relationship between fuel gas utilization and separation efficiency.     

Numerical modeling of an automotive derivative polymer electrolyte membrane fuel cell cogeneration system with selective membranes

Cogeneration power plants based on fuel cells are a promising technology to produce electric and thermal energy with reduced costs and environmental impact. The most mature fuel cell technology for this kind of applications are polymer electrolyte membrane fuel cells, which require high-purity hydrogen.The most common and least expensive way to produce hydrogen within today's energy infrastructure is steam reforming of natural gas. Such a process produces a syngas rich in hydrogen that has to be purified to be properly used in low temperature fuel cells. However, the hydrogen production and purification processes strongly affect the performance, the cost, and the complexity of the energy system.Purification is usually performed through pressure swing adsorption, which is a semi-batch process that increases the plant complexity and incorporates a substantial efficiency penalty. A promising alternative option for hydrogen purification is the use of selective metal membranes that can be integrated in the reactors of the fuel processing plant. Such a membrane separation may improve the thermo-chemical performance of the energy system, while reducing the power plant complexity, and potentially its cost. Herein, we perform a technical analysis, through thermo-chemical models, to evaluate the integration of Pd-based H₂-selective membranes in different sections of the fuel processing plant: (i) steam reforming reactor, (ii) water gas shift reactor, (iii) at the outlet of the fuel processor as a separator device. The results show that a drastic fuel processing plant simplification is achievable by integrating the Pd-membranes in the water gas shift and reforming reactors. Moreover, the natural gas reforming membrane reactor yields significant efficiency improvements.     

Analysis of thermal balance in high-temperature proton exchange membrane fuel cells with short stacks via in situ monitoring with a flexible micro sensor

The heat produced from the electrochemical reaction in a fuel cell is worth studying, the heat recycled make the fuel cell more efficiency, especially in a high-temperature proton exchange membrane fuel cell (HTPEMFC). In low temperature PEMFC system, the heat is removed by cooling system avoid the membrane degradation exceed 100 °C. But in HTPEMFC system, the membrane can afford higher temperature (T_g 420 °C), means the cooling system could be removing and through changing the inside flow field to uniform the unit cell temperature in stack. In this study, a 50–100 W HTPEMFC stack is demonstrated and a micro sensor was integrated with the HTPEMFC stack for in situ measurements during the experiments. The results show that when the stack is operated at low and high current loads, the heat generation from the fuel cell causes noticeable changes in the cell temperature, especially in the middle of the stack. In the middle cell of the stack, the temperature exceeds the operating temperature (160 °C) by 10–30 °C when the current increases. Moreover, changing the flow field to counter-flow or co-flow with U- or Z-type flow fields causes changes to the thermal balance in the stack. The performance, however, remains almost the same for each type of flow field when there is no water affecting the HTPEMFC, even though the change in thermal balance in the stack still occurs. The results of the micro sensor in situ monitoring for each type of flow field displayed higher temperatures on the middle cells. If the waste heat is appropriately used, the high-temperature fuel cell will then be more efficient than the low-temperature fuel cell. The results also show that, in the HTPEMFC stack, the heat generated from the fuel cell can be reused in other ways.     

Computational model to predict thermal dynamics of planar solid oxide fuel cell stack during start-up process

Solid oxide fuel cell (SOFC) systems have been recognized as the most advanced power generation system with the highest thermal efficiency with a compatibility with wide variety of hydrocarbon fuels, synthetic gas from coal, hydrogen, etc. However, SOFC requires high temperature operation to achieve high ion conductivity of ceramic electrolyte, and thus SOFC should be heated up first before fuel is supplied into the stack. This paper presents computational model for thermal dynamics of planar SOFC stack during start-up process. SOFC stack should be heated up as quickly as possible from ambient temperature to above 700 °C, while minimizing net energy consumption and thermal gradient during the heat up process. Both cathode and anode channels divided by current-collecting ribs were modeled as one-dimensional flow channels with multiple control volumes and all the solid structures were discretized into finite volumes. Two methods for stack-heating were investigated; one is with hot air through cathode channels and the other with electric heating inside a furnace. For the simulation of stack-heating with hot air, transient continuity, flow momentum, and energy equation were applied for discretized control volumes along the flow channels, and energy equations were applied to all the solid structures with appropriate heat transfer model with surrounding solid structures and/or gas channels. All transient governing equations were solved using a time-marching technique to simulate temporal evolution of temperatures of membrane-electrode-assembly (MEA), ribs, interconnects, flow channels, and solid housing structure located inside the insulating chamber. For electrical heating, uniform heat flux was applied to the stack surface with appropriate numerical control algorithm to maintain the surface temperature to certain prescribed value. The developed computational model provides very effective simulation tool to optimize stack-heating process minimizing net heating energy and thermal gradient within the stack.     

A non-sealed solid oxide fuel cell micro-stack with two gas channels

Non-sealed solid oxide fuel cell (NS-SOFC) micro-stacks with two gas channels were fabricated and operated successfully under various CH₄/O₂ gas mixtures in a box-like stainless-steel chamber. The cells with an anode-facing-cathode configuration were connected in serial by zigzag sliver sheets. Each cell consisted of the Ni/yttria-stabilized zirconia (YSZ) anode, the YSZ electrolyte, and the Sm_0.2Ce_0.8O_1.9-impregnated (La_0.75Sr_0.25)_0.95MnO₃ cathode. In this configuration, to ensure the identical gas distribution over the electrode surfaces, two gas channels with small vents flanking the stacks were used as gas channels of methane and oxygen for anodes and cathodes, respectively. The selectivity requirement of both the anode and cathode for the oxidation and reduction of CH₄ and O₂ was lowered and the sheets could extend the residence time of gas flow over the electrode surface. By the direct flame heat with a liquefied petroleum gas burner, the stacks presented a rapid start-up and full utilization of the exhaust gas. Eventually, an open-circuit voltage (OCV) of 1.8 V and maximum power output of 276 mW was produced by a two-cell stack. For a four-cell stack, a maximum power output of 373 mW was obtained.     

Ethanol catalytic membrane reformer for direct PEM FC feeding

In this paper an ethanol reformer based on catalytic steam reforming with a catalytic honeycomb loaded with RhPd/CeO₂ and palladium separation membranes with an area of 30.4 cm² has been used to generate a pure hydrogen stream of up to 100 ml/min to feed a PEM fuel cell with an active area of 5 cm². The fuel reformer behavior has been extensively studied under different temperature, ethanol–water flow rate and gas pressure at a fixed S/C ratio of 1.6 (molar). The hydrogen yield has been controlled by acting upon the ethanol–water fuel flow and gas pressure.     

Water removal characteristics of proton exchange membrane fuel cells using a dry gas purging method

Water removal from proton exchange membrane fuel cells (PEMFC) is of great importance to improve start-up ability and mitigate cell degradation when the fuel cell operates at subfreezing temperatures. In this study, we report water removal characteristics under various shut down conditions including a dry gas-purging step. In order to estimate the dehydration level of the electrolyte membrane, the high frequency resistance of the fuel cell stack was observed. Also, a novel method for measuring the amount of residual water in the fuel cell was developed to determine the amount of water removal. The method used the phase change of liquid water and was successfully applied to examine the water removal characteristics. Based on these works, the effects of several parameters such as purging time, flow rate of purging gas, operation current, and stack temperature on the amount of residual water were investigated.