Numerical modeling of a non-flooding hybrid polymer electrolyte fuel cell

Experimental results were recently reported regarding a novel “non-flooding” hybrid fuel cell consisting of proton exchange membrane (PEM) and anion exchange membrane (AEM) half-cells on opposite sides of a water-filled, porous intermediate layer. Product water formed in the porous layer, where it could permeate to the exterior of the cell, rather than at the electrodes. Although electrode flooding was mitigated, the reported power output was low. To investigate the potential for increased power output, a physicochemical charge transport model of the porous electrolyte layer is reported here. Traditional electrochemical modeling was generalized in a novel way to consider both ion transport and reaction in the aqueous phase and electronic conduction in the graphitic scaffold using a unified Poisson–Nernst–Planck framework. Though the model used no arbitrary or fitting parameters, the ionic resistance calculated for the porous layer agreed well with the highly non-Ohmic experimental values previously reported for the entire fuel cell. Interestingly, electronic charge carriers in the scaffold were found to obviate the need for counterion presence in this unique electrolyte structure. Still, the thickness- and temperature-dependent model results offer limited prospects for improving the power output.     

A grouping-based global harmony search algorithm for modeling of proton exchange membrane fuel cell

In recent years, accurate identification of voltage versus current (V-I) characteristics of proton exchange membrane fuel cell (PEMFC) has attracted significant attention in the literature. However, the main drawback in accurate modeling is the lack of information about the precise values of the model parameters. In this paper, in order to overcome this drawback a grouping-based global harmony search algorithm, named GGHS, is proposed for parameter identification issue. The proposed algorithm attempts to provide an efficient way in which a new harmony can be properly improvised. In order to study the capability of the proposed algorithm, the results obtained by GGHS are compared with those obtained by two versions of harmony search (HS) algorithms, three versions of particle swarm optimization (PSO) algorithms, as well as seeker optimization algorithm (SOA). Simulation results accentuate the superiority of the GGHS over the other methods.     

Optimizing polymer electrolyte membrane thickness to maximize fuel cell vehicle range

Automotive hydrogen polymer electrolyte membrane (PEM) fuel cell systems require periodic purges to remove nitrogen and water from the anode. Purging increases system performance by limiting anode hydrogen dilution, but reduces hydrogen utilization. State of the art fuel cell membrane electrode assemblies utilize thin ionomer membranes in an effort to increase performance and reduce cost. Thinner membranes also increase the required anode purge rates due to the increased transport of inert gases. A model was developed to examine the relationship between membrane thickness and vehicle range which takes into account anode purge rate. The model includes changes in efficiency and hydrogen utilization as a function of PEM thickness for a variety of operating conditions. The model predicts that an optimal membrane thickness which maximizes vehicle range exists, but this thickness is highly dependent on other system conditions. The results of this study can be extended to help optimize stack development and balance of plant design.     

Validity of two-phase polymer electrolyte membrane fuel cell models with respect to the gas diffusion layer

A dynamic two-phase model of a proton exchange membrane fuel cell with respect to the gas diffusion layer (GDL) is presented and compared with chronoamperometric experiments. Very good agreement between experiment and simulation is achieved for potential step voltammetry (PSV) and sine wave testing (SWT). Homogenized two-phase models can be categorized in unsaturated flow theory (UFT) and multiphase mixture (M²) models. Both model approaches use the continuum hypothesis as fundamental assumption. Cyclic voltammetry experiments show that there is a deterministic and a stochastic liquid transport mode depending on the fraction of hydrophilic pores of the GDL. ESEM imaging is used to investigate the morphology of the liquid water accumulation in the pores of two different media (unteflonated Toray-TGP-H-090 and hydrophobic Freudenberg H2315 I3). The morphology of the liquid water accumulation are related with the cell behavior. The results show that UFT and M² two-phase models are a valid approach for diffusion media with large fraction of hydrophilic pores such as unteflonated Toray-TGP-H paper. However, the use of the homgenized UFT and M² models appears to be invalid for GDLs with large fraction of hydrophobic pores that corresponds to a high average contact angle of the GDL.     

Annealing induced interfacial layers in niobium-clad stainless steel developed as a bipolar plate material for polymer electrolyte membrane fuel cell stacks

Roll-bonded niobium (Nb)-clad 304 L stainless steel (SS) is currently being developed as a metallic bipolar plate material for polymer electrolyte membrane fuel cell stacks. Prior work has shown that post-roll annealing significantly softens the constituent core and cladding materials, enhancing the ductility and formability of each. However under the vacuum annealing condition employed in the previous study (900 s, 982 °C (1800 F)), an interfacial layer was observed to form between the two bonded materials. Subsequent bending and flattening tests indicated brittle failure of this interfacial region under high strain conditions. The present study employs transmission electron microscopy to examine the composition, structure, and thickness of phases generated at the Nb/SS interface as functions of annealing temperature and time. Corresponding selected electron diffraction patterns indicate that above a threshold annealing temperature of ∼950 °C, the formation of (Fe_1−xCr_x)₂Nb appears to control the failure behavior of the Nb/304 L SS material. Annealing treatments conducted below this temperature generally avoid the formation of this intermetallic layer.     

Optimal catalyst layer structure of polymer electrolyte membrane fuel cell

In a membrane electrode assembly (MEA) of polymer electrolyte membrane fuel cells, the structure and morphology of catalyst layers are important to reduce electrochemical resistance and thus obtain high single cell performance. In this study, the catalyst layers fabricated by two catalyst coating methods, spraying method and screen printing method, were characterized by the microscopic images of catalyst layer surface, pore distributions, and electrochemical performances to study the effective MEA fabrication process. For this purpose, a micro-porous layer (MPL) was applied to two different coating methods intending to increase single cell performances by enhancing mass transport. Here, the morphology and structure of catalyst layers were controlled by different catalyst coating methods without varying the ionomer ratio. In particular, MEA fabricated by a screen printing method in a catalyst coated substrate showed uniformly dispersed pores for maximum mass transport. This catalyst layer on micro porous layer resulted in lower ohmic resistance of 0.087 Ω cm² and low mass transport resistance because of enhanced adhesion between catalyst layers and a membrane and improved mass transport of fuel and vapors. Consequently, higher electrochemical performance of current density of 1000 mA cm^-2 at 0.6 V and 1600 mAcm⁻² under 0.5 V came from these low electrochemical resistances comparing the catalyst layer fabricated by a spraying method on membranes because adhesion between catalyst layers and a membrane was much enhanced by screen printing method.     

A discrete particle packing model for the formation of a catalyst layer in polymer electrolyte fuel cells

We developed a reconstruction simulation model for a catalyst layer of a polymer electrolyte fuel cell to elucidate the effect of the size and shape of the catalyst agglomerates on the cell performance. The geometry of the catalyst layer was obtained by simulating the packing of carbon black agglomerates in ink modeled as multisphere objects by the discrete element method. Electrochemical reaction and mass transfer were modeled based on the resulting three-dimensional geometry of the catalyst. Both the size and shape of the agglomerate significantly influence the catalyst structure and performance. Branched agglomerates lead to higher porosity, larger pore sizes, and better cell performance. For each agglomerate shape, there is an optimum size at which the performance is the maximum, because of the optimum trade-off relationship between the oxygen diffusion and proton conduction. Understanding the mechanism of the catalyst formation can aid the design of catalysts to improve their performance.     

In situ measurement of temperature distribution within a single polymer electrolyte membrane fuel cell

A novel test scheme for in situ measurement of temperature within a single polymer electrolyte membrane fuel cell (PEMFC) is proposed, which possesses the following attractive features: measuring interference with the internal environment of the fuel cell is likely reduced to minimum; simultaneous measurements for local temperatures of both sides of the fuel cell are conducted with enough numbers of measurement locations; and the cell temperatures are controlled in relatively careful and stringent strategies. Thermal and electrical behaviors of the cell tested are investigated, including the local and averaged temperatures at the back sides of cathode and anode flow field plates (FFPs), the outlet currents, and their variations with the test time. It is found that both temperatures and outlet currents exhibit complex dynamic behaviors; and the rise of temperature and the non-uniformity of temperature distribution of the back sides of the two FFPs are not negligible.     

Parameter identification for proton exchange membrane fuel cell model using particle swarm optimization

The accurate mathematical model is an extremely useful tool for simulation and design analysis of fuel cell power systems. Particle swarm optimization (PSO) is a recently invented high-performance algorithm. In this work, a PSO-based parameter identification technique of proton exchange membrane (PEM) fuel cell models was proposed in terms of the voltage–current characteristics. Using the simulated and experimental voltage–current data, the validity of the proposed method has been confirmed. The results indicate that the PSO is an effective technique for identifying the parameters of PEM fuel cell models even in the presence of measuring noise. Moreover, the proposed method does not particularly necessitate initial guesses as close as possible to the solutions, required only is a broad range specified for each of the parameters. Therefore, the PSO method outperforms the GA and traditional optimization methods.     

Copolymer synergistic coupling for chemical stability and improved gas barrier properties of a polymer electrolyte membrane for fuel cell applications

A novel radiation grafted ETFE based proton conducting membrane was prepared by double irradiation grafting of two different monomers. The intrinsic oxidative stability of the ETFE-g-poly(styrene sulfonic acid-co-divinylbenzene) membrane was improved by reducing the gas crossover through incorporation of polymethacrylonitrile (PMAN) containing the strong polar nitrile group. A fuel cell test was carried out at 80 °C under constant current density of 500 mA cm⁻² for a time exceeding 1′900 h. The incorporation of PMAN considerably improves the interfacial properties of the membrane-electrode assembly. No significant change in the membrane hydrogen crossover and performance over the testing time was observed, except for a measured decrease in the membrane ohmic resistance after 1′000 h. The combination of the double irradiation induced grafting with the use of the PMAN as gas barrier in addition to its chelating abilities (e. g. Ce³⁺) offers a promising strategy to develop more durable membranes for fuel cells.     

Performance equations for a polymer electrolyte membrane fuel cell with unsaturated cathode feed

A mathematical formulation for the cathode of a membrane electrode assembly of a polymer electrolyte membrane fuel cell is proposed, in which the effect of unsaturated vapor feed in the cathode is considered. This mechanistic model formulates the water saturation front within the gas diffusion layer with an explicit analytical expression as a function of operating conditions. The multi-phase flows of gaseous species and liquid water are correlated with the established capillary pressure equilibrium in the medium. In addition, less than fully hydrated water contents in the polymer electrolyte and catalyst layers are considered, and are integrated with the relevant liquid and vapor transfers in the gas diffusion layer. The developed performance equations take into account the influences of all pertinent material properties on cell performance using first principles. The mathematical approach is logical and concise in terms of revealing the underlying physical significance in comparison with many other empirical data fitting models.     

Two dimensional dynamic modeling of a shell-and-tube water-to-gas membrane humidifier for proton exchange membrane fuel cell

Water management is a crucial factor in determining the performance of proton exchange membrane fuel cell (PEMFC) for automotive application. The shell-and-tube water-to-gas membrane humidifier is useful for humidifying the PEMFC due to its good performance. Shell-and-tube water-to-gas membrane humidifiers have liquid water on one side of the tube wall and a dry gas on the other. In order to investigate humidifier performance, a two-dimensional dynamic model of a shell-and-tube water-to-gas membrane humidifier is developed. The model is discretized into three control volumes – shell, tube and membrane – in the cross-sectional direction to resolve the temperature and species concentration of the humidifier. For validation, the dew point temperature of the simulation result is compared with that of experimental data and shows good agreement with only a slight difference. The distribution of humidification characteristics can be captured using the discretization along the air-flow direction. The humidification performance of two different flow configurations, counter and parallel, are compared under various operating conditions and geometric parameters. Finally, the dynamic response of the humidifier at the step-change of various air flow rates is investigated. These results suggest that the model can be used to optimize the inlet flow humidity of a PEMFC.     

Physically stable proton exchange membrane with ordered electrolyte for elevated temperature PEM fuel cell

Dimensional change and humidity-induced stress of the proton exchange membrane were demonstrated to be main reasons for membrane physical failure during the long-term fuel cell operation. In this work, UV laser ablation was proposed to prepare physically stable polyimide supports to reduce the dimensional swelling and humidity-induced stress of the proton exchange membrane under variable humidities. Long-range ordered straight holes with definable open pattern and diameter of 50–200 μm were formed through the polyimide support. Composite proton exchange membrane prepared from the straight-hole polyimide support presented desirable performance and high durability in fuel cells. When Nafion fraction in the composite membrane increased to 48.67%, the proton conductivities of the composite membranes were equal to or greater than that of the conventional Nafion membrane with activation energies lower than that of the Nafion 211 membrane. The dimensions of the composite membranes are very stable in both low and elevated temperature conditions. The proportion of humidity-induced stress to the yield strength for the composite membrane is 0.20%–0.21%, much lower than that of the conventional Nafion membrane (24.77%). As a result, the composite proton exchange membrane prepared from the straight-hole polyimide presented high durability in the fuel cell operation. In the open circuit voltage accelerated test under in situ accelerating RH cyclic test, the irreversible OCV reduction rate of the composite membranes was 2.41–2.72 × 10⁻⁵ V/cycle, 37.1%–41.8% lower than that of the conventional Nafion 211 membrane.     

Convergence criteria establishment for 3D simulation of proton exchange membrane fuel cell

A validated 3 dimensional (3D) computational fluid dynamics model of a single cell proton exchange membrane fuel cell (PEMFC) was used for investigating convergence criteria. The simulation study was carried out using the commercial PEMFC simulation module built in to ANSYS FLUENT 12.1 software package and compared with published experimental data. Convergence data up to 19,000 iterations were collected in order to establish expectations for convergence errors and differences in convergence rates for different boundary conditions. Species mass fluxes and current density were used to perform a dual verification of experimentally verifiable simulation predictions. The results of the simulation showed that convergence trends were consistent for different boundary conditions and that the solution trends asymptotically to a final value with species mass flux errors approaching to constant values. The data were used to establish convergence criteria for future 3D PEMFC simulations where residual monitoring alone is insufficient to ensure convergence.     

Pore network modeling of cathode catalyst layer of proton exchange membrane fuel cell

In this paper, a pore network model is developed to investigate the coupled transport and reaction processes in the cathode catalyst layer (CCL) of proton exchange membrane fuel cell (PEMFC). The developed model is validated by comparing the predicted polarization curve with the experimental data, and the parametric studies are carried out to elucidate the effects of CCL design parameters. With the decrease of the CCL thickness and the Nafion content, the cell voltage reduces at the low current density but increases when the current density is higher. The cell performance is also improved by increasing the proton conductivity of the Nafion film in the CCL. As compared to the CCL of uniformly distributed Nafion, the CCL with the Nafion volume decreasing along the thickness direction exhibits better performance at the high current density.     

Development of a proton exchange membrane fuel cell cogeneration system

A proton exchange membrane fuel cell (PEMFC) cogeneration system that provides high-quality electricity and hot water has been developed. A specially designed thermal management system together with a microcontroller embedded with appropriate control algorithm is integrated into a PEM fuel cell system. The thermal management system does not only control the fuel cell operation temperature but also recover the heat dissipated by FC stack. The dynamic behaviors of thermal and electrical characteristics are presented to verify the stability of the fuel cell cogeneration system. In addition, the reliability of the fuel cell cogeneration system is proved by one-day demonstration that deals with the daily power demand in a typical family. Finally, the effects of external loads on the efficiencies of the fuel cell cogeneration system are examined. Results reveal that the maximum system efficiency was as high as 81% when combining heat and power.     

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.     

Dynamic modeling of a proton exchange membrane fuel cell system with a shell-and-tube gas-to-gas membrane humidifier

The proton exchange membrane fuel cell (PEMFC) system with a shell-and-tube gas-to-gas membrane humidifier is considered to be a promising PEMFC system because of its energy-efficient operation. However, because the relative humidity of the dry air flowing into the stack depends on the stack exhaust air, this system can be unstable during transients. To investigate the dynamic behavior of the PEMFC system, a system model composed of a lumped dynamic model of an air blower, a two-dimensional dynamic model of a shell-and-tube gas-to-gas membrane humidifier, and a one-dimensional dynamic model of a PEMFC system is developed. Because the water management during transient of the PEMFC system is one of the key challenges, the system model is simulated at the step change of current. The variations in the PEMFC system characteristics are captured. To confirm the superiority of the system model, it is compared with the PEMFC component model during transients.     

Silicon carbide fiber-reinforced composite membrane for high-temperature and low-humidity polymer exchange membrane fuel cells

Currently, efforts are being made to commercialize a fuel cell system through research on fuel cell material enhancements. In particular, improvements in the membrane-electrode assembly, a key component of polymer electrolyte membrane (PEM) fuel cells, are essential to increase the performance of a fuel cell, in addition to accelerating its commercialization. Therefore, in this study, we used silicon carbide (SiC) fibers (web type) by electrospinning, which possess superior material, thermal, and chemical properties, as a structural material for the composite electrolyte membrane in the membrane-electrode assembly by impregnating it with the polymer electrolyte ionomer of short-side chain (SSC). In addition, we enhanced the ion-exchange capability of functionalized SiC fibers by introducing the hydroxyl (OH) group and phosphoric acid. The resulting functionalized composite electrolyte membrane exhibited a 70% better ion-exchange capability than the conventional cast electrolyte membrane and SiC webs composite electrolyte membranes was observed to excellent mechanical strength. We characterized and illustrative modeled the functionalized silicon carbide fibers, on the basis of which we further developed composite membrane. We then fabricated a unit cell of PEMFC based on this composite electrolyte membrane, and evaluated its single-cell performance, electrochemical properties, and accelerated voltage life-time durability test of operating 35 h according to the electro- and physic-chemical characteristics of the MEA under high-temperature and low humidity (120 °C/RH 40%).     

Transient computation fluid dynamics modeling of a single proton exchange membrane fuel cell with serpentine channel

The proton exchange membrane fuel cell (PEMFC) has become a promising candidate for the power source of electrical vehicles because of its low pollution, low noise and especially fast startup and transient responses at low temperatures. A transient, three-dimensional, non-isothermal and single-phase mathematical model based on computation fluid dynamics has been developed to describe the transient process and the dynamic characteristics of a PEMFC with a serpentine fluid channel. The effects of water phase change and heat transfer, as well as electrochemical kinetics and multicomponent transport on the cell performance are taken into account simultaneously in this comprehensive model. The developed model was employed to simulate a single laboratory-scale PEMFC with an electrode area about 20 cm². The dynamic behavior of the characteristic parameters such as reactant concentration, pressure loss, temperature on the membrane surface of cathode side and current density during start-up process were computed and are discussed in detail. Furthermore, transient responses of the fuel cell characteristics during step changes and sinusoidal changes in the stoichiometric flow ratio of the cathode inlet stream, cathode inlet stream humidity and cell voltage are also studied and analyzed and interesting undershoot/overshoot behavior of some variables was found. It was also found that the startup and transient response time of a PEM fuel cell is of the order of a second, which is similar to the simulation results predicted by most models. The result is an important guide for the optimization of PEMFC designs and dynamic operation.