Investigation of the effects of the anisotropy of gas-diffusion layers on heat and water transport in polymer electrolyte fuel cells

The aim of this work is to study the effects of gas-diffusion layer (GDL) anisotropy and the spatial variation of contact resistance between GDLs and catalyst layers (CLs) on water and heat transfer in polymer electrolyte fuel cells (PEFCs). A three-dimensional, two-phase, numerical PEFC model is employed to capture the transport phenomena inside the cell. The model is applied to a two-dimensional cross-sectional PEFC geometry with regard to the in-plane and through-plane directions. A parametric study is carried out to explore the effects of key parameters, such as through-plane and in-plane GDL thermal conductivities, operating current densities, and electronic and thermal contact resistances. The simulation results clearly demonstrate that GDL anisotropy and the spatial variation of GDL/CL contact resistance have a strong impact on thermal and two-phase transport characteristics in a PEFC by significantly altering the temperature, water and membrane current density distributions, as well as overall cell performance. This study contributes to the identification of optimum water and thermal management strategies of a PEFC based on realistic anisotropic GDL and contact-resistance variation inside a cell.     

Improved modeling and understanding of diffusion-media wettability on polymer-electrolyte-fuel-cell performance

A macroscopic-modeling methodology to account for the chemical and structural properties of fuel-cell diffusion media is developed. A previous model is updated to include for the first time the use of experimentally measured capillary pressure-saturation relationships through the introduction of a Gaussian contact-angle distribution into the property equations. The updated model is used to simulate various limiting-case scenarios of water and gas transport in fuel-cell diffusion media. Analysis of these results demonstrate that interfacial conditions are more important than bulk transport in these layers, where the associated mass-transfer resistance is the result of higher capillary pressures at the boundaries and the steepness of the capillary pressure-saturation relationship. The model is also used to examine the impact of a microporous layer, showing that it dominates the response of the overall diffusion medium. In addition, its primary mass-transfer-related effect is suggested to be limiting the water-injection sites into the more porous gas-diffusion layer.     

Analyzing oxygen transport resistance and Pt particle growth effect in the cathode catalyst layer of polymer electrolyte fuel cells

The oxygen transport resistance in the cathode catalyst layer (CL) of polymer electrolyte fuel cells (PEFCs) has been reported to be significantly higher than expected, especially when the platinum (Pt) loading is low and/or the degree of CL degradation is severe. In this paper, the oxygen transport resistance behavior in the cathode CL is numerically analyzed under various CL design and operating conditions. Particular emphasis is placed on the aged CL wherein Pt particle growth and active Pt surface area loss are observed. For this study, a previously developed micro-scale catalyst model is improved upon to account for Pt particle size. The new model includes calculations of catalyst activity and electrochemically active surface areas, as well as various transport resistances through the ionomer and liquid films. After coupling the micro-scale CL model with a three-dimensional PEFC model, multi-scale simulations are carried out under various PEFC catalyst designs (varying Pt loading, ionomer fraction, oxygen permeation rate through the ionomer film) and operating conditions (drying or flooding of the electrode, high or lower current density). The simulation results agree well with experimental oxygen transport resistance data and further indicate that CL design with low Pt loading is more susceptible to degradation. Providing extensive multi-dimensional contours of species concentration, temperature, and current density inside the PEFC, this study provides a comprehensive understanding of oxygen transport resistance in the cathode CL in different PEFC situations.     

Water balance simulations of a polymer-electrolyte membrane fuel cell using a two-fluid model

A previously published computational multi-phase model of a polymer-electrolyte membrane fuel cell cathode has been extended in order to account for the anode side and the electrolyte membrane. The model has been applied to study the water balance of a fuel cell during operation under various humidification conditions. It was found that the specific surface area of the electrolyte in the catalyst layers close to the membrane is of critical importance for the overall water balance. Applying a high specific electrolyte surface area close to the membrane (a water-uptake layer) can prevent drying out of the anode and flooding at the cathode while the average membrane water content is only weakly affected. The results also indicate that in contrast to common presumption membrane dehydration may occur at either anode or cathode side, entirely depending on the direction of the net water transport because the predominant transport mechanism is diffusion. Consequently, operating conditions with a high net water transport from anode to cathode should be avoided as it is important to keep the cathode catalyst layer well humidified in order to prevent high protonic losses. Addition of the micro-porous layer did not affect the overall water balance or membrane water content in our study.     

Three‐dimensional modelling of catalyst layers in PEM fuel cells: Effects of non‐uniform catalyst loading

Improving the performance of polymer‐electrolyte membrane (PEM) fuel cells depends on the optimization of catalyst layer composition and structure for large active surfaces. Modelling studies provide a valuable tool for investigating the effects of catalyst layer composition and structure on the electrochemical and physical phenomena occurring in PEM fuel cells. Previous modelling studies have shown that the distribution of electrochemical reactions in catalyst layers is highly dependent on the complex interaction of activation and ohmic effects as well as contributions from transport limitations and variations in local and overall current densities. In this paper, three‐dimensional, multicomponent and multiphase transport computations are performed using a computational fluid dynamics (CFD) code (FLUENT^TM) with a new PEM fuel cell module, which has been further improved by taking into account the detailed composition and structure of the catalyst layers using the multiple thin‐film agglomerate model. The detailed modelling of reactions in the catalyst layers is used to determine methods of improving the effectiveness of catalyst layers for a given platinum loading. First, available data on catalyst layer composition and structure are used in CFD computations to predict reaction rate distributions. Based on these results, spatial variations in catalyst loading are then implemented in CFD computations for the same overall catalyst loading to investigate possible performance gains. It is found that grading catalyst loading towards the membrane in the anode and the gas channel inlet in the cathode provides the most beneficial effects on the fuel cell performance. Thus the results suggest that significant savings in cost can be attained by reducing the platinum loading in underutilized regions of the catalyst layers, while at the same time improving the performance. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of gas-diffusion electrode material heterogeneity on the structural integrity of polymer electrolyte fuel cell

In polymer electrolyte fuel cell (PEFC), gas-diffusion electrode (GDE) plays very significant role in force transmission from bipolar plate to the membrane. This paper investigates the effects of material heterogeneities of gas-diffusion electrode layer (gas-diffusion layer (GDL) and catalyst layer (CL)) on the assembly stress levels of single PEFC stack. In addition, we adopt a force transfer mechanism in a single fuel cell stack based on material heterogeneities of GDL and CL to understand the limitations and advantages associated with it through numerical analyses. Nanoscale heterogeneities in GDE are effectively implemented in the simulation cases along with the membrane swelling. Influence of presence or absence of CL interlayer in the numerical environment is found to have significant impact on the adjacent layers as well as interfaces.     

Oxygen gain analysis for proton exchange membrane fuel cells

Oxygen gain is the difference in hydrogen fuel cell performance operating on oxygen-depleted and oxygen-rich cathode fuel streams. Oxygen gain experiments provide insight into the degree of oxygen mass-transport resistance within a fuel cell. By taking these measurements under different operating conditions, or over time, one can determine how oxygen mass transport varies with operating modes and/or aging. This paper provides techniques to differentiate between mass-transport resistance within the catalyst layer and within the gas-diffusion medium for a polymer-electrolyte membrane fuel cell. Two extreme cases are treated in which all mass transfer limitations are located only (i) within the catalyst layer or (ii) outside the catalyst layer in the gas-diffusion medium. These two limiting cases are treated using a relatively simple model of the cathode potential and common oxygen gain experimental techniques. This analysis demonstrates decisively different oxygen gain behavior for the two limiting cases. For catalyst layer mass transfer resistance alone, oxygen gain values are limited to a finite range of values. However, for gas-diffusion layer mass transfer resistance alone, the oxygen gain is not confined to a finite range of values. Therefore, this work provides a straightforward diagnostic method for locating the prominent source of mass transfer degradation in a PEMFC cathode.     

Numerical investigation of the effect of cathode catalyst layer structure and composition on polymer electrolyte membrane fuel cell performance

The effect of the cathode catalyst layer's structure and composition on the overall performance of a polymer electrolyte membrane fuel cell (PEMFC) is investigated numerically. The starting point of the sub-grid scale catalyst layer model is the well-known flooded agglomerate concept. The proposed model addresses the effects of ionomer (Nafion) loading, catalyst (platinum) loading, platinum/carbon ratio, agglomerate size and cathode layer thickness. The sub-grid scale model is first validated against experimental data and previously published results, and then embedded within a two-dimensional validated computational fluid dynamics code that can predict the overall performance of the fuel cell. The integrated model is then used to explore a wide range of the compositional and structural parameter space, mentioned earlier. In each case, the model is able to correctly predict the trends observed by past experimental studies. It is found that the performance trends are often different at intermediate versus high current densities—the former being governed by agglomerate-scale (or local) losses, while the latter is governed by catalyst layer thickness-scale (or global) losses. The presence of an optimal performance with varying Nafion content in the cathode is more due to the local agglomerate-scale mass transport and conductivity losses in the polymer coating around the agglomerates than due to the amount of Nafion within the agglomerate. It is also found that platinum mass loading needs to be at a moderate level in order to optimize fuel cell performance, even if cost is to be disregarded.     

Effect of cathode micro-porous layer on performance of anion-exchange membrane direct ethanol fuel cells

The effect of a cathode micro-porous layer that is composed of carbon powder or carbon nanotubes on cell performance is investigated. Polarization curves, together with the respective anode and cathode potentials, are measured. The results show that the cathode potential can be significantly improved with adding a hydrophobic micro-porous layer between the cathode catalyst layer and the gas-diffusion layer. The increased performance with the cathode micro-porous layer is mainly attributed to the fact that the cathode water flooding can be alleviated as a result of the reduced water crossover, which consequently facilitates the transport of oxygen to the catalyst layer. It is also found that a crack-free micro-porous layer made of carbon nanotubes gives a much higher cathode potential compared with a micro-porous layer composed of carbon powder.     

Effects of the electrical resistances of the GDL in a PEM fuel cell

In most PEM fuel cell models, the electrical resistance of the gas diffusion layers (GDL) is neglected under the assumptions that the GDL electrical conductivity is orders of magnitude higher than the ionic conductivity of the membrane. Recently some modeling efforts have taken the effects of electrical resistance of the GDL into consideration [H. Meng, C.Y. Wang, Electron transport in PEFCs, J. Electrochem. Soc. 151 (2004) A358–A367; B.R. Sivertsen, N. Djilali, CFD-based modeling of proton exchange membrane fuel cells, J. Power Sources 141 (2005) 65–78] and some of the results showed that under certain conditions, this effect was significant enough to alter the characteristics of current density distributions under the gas channels and the land areas. If these results are applicable to real-life fuel cells, the present design criteria and optimization procedures must be significantly changed to incorporate the effect of GDL electrical resistance. To examine this issue closely, a three-dimensional fuel cell model incorporating electron transport in the GDL is developed and employed to investigate the effect of electrical resistance through the GDL. In this model, the anisotropic nature of the GDL is taken into consideration by using different electrical conductivities in the through-plane and in-plane directions. The modeling results show that when realistic electrical conductivities for the GDL are used, the effect of the electrical resistance of GDL is slight and can be neglected for all industrial applications. It is believed that the over-estimations of the GDL resistance were mainly caused by neglecting the anisotropic nature of the GDL and/or lumping the contact resistance indiscriminately into the GDL, thus overestimating the electrical resistance of the GDL in the in-plane direction. Besides taking into consideration of the electrical resistance of GDL, the present model also take into consideration of the electron transport in the catalyst layers. When realistic values of electrical conductivities are used for both the GDL and catalyst layers, there is no significant change in the characteristics of current density distribution across the land and channel.     

Modelling of coupled electron and mass transport in anisotropic proton-exchange membrane fuel cell electrodes

As one of the key components of proton-exchange membrane fuel cells, the gas-diffusion layer (GDL) that is made of carbon fibres usually exhibits strong structural anisotropy. Nevertheless, the GDL has traditionally been simplified as a homogeneous porous structure in modelling the transport of species through the GDL. In this work, a coupled electron and two-phase mass transport model for anisotropic GDLs is developed. The effects of anisotropic GDL transport properties due to the inherent anisotropic carbon fibres and caused by GDL deformations are studied. Results indicate that the inherent structural anisotropy of the GDL significantly influences the local distribution of both cathode potential and current density. Simulation results further indicate that a GDL with deformation results in an increase in the concentration polarization due to the increased mass-transfer resistance in the deformed GDL. On the other hand, the ohmic polarization is found to be smaller in the deformed GDL as the result of the decreased interfacial contact resistance and electronic resistance in the GDL. This result implies that an optimum deformation needs to be achieved so that both concentration and ohmic losses can be minimized.     

Characteristics of intraphase transport processes in methanol reforming microchannel reactors: A computational fluid dynamics study

Ignoring possible effects due to intraphase diffusion within catalyst layers is a common feature of computational fluid dynamics models developed for reforming microchannel reactors. Resistance to diffusion within the catalyst layers applied to such a reactor is often ignored on the grounds that the catalyst layers are sufficiently thin to allow reactants unrestricted access to all available reaction sites. However, this assumption is not necessarily correct, and intraphase diffusion effects could be important. Three-dimensional numerical simulations were carried out using computational fluid dynamics to investigate the characteristics of intraphase transport processes within the catalyst layers arranged in a thermally integrated methanol reforming microchannel reactor. The heat and mass transfer effects involved in the reforming process were evaluated, and the optimum thickness of catalyst layers was determined for the reactor. Particular focus was placed on how to optimize the thickness of catalyst layers in order to operate the reactor more efficiently. The results indicated that the performance of the reactor can be greatly improved by means of proper design of catalyst layer thickness to enhance heat and mass transfer into the catalyst layers. The thickness of the catalyst layers can be optimized to minimize diffusional resistance while maximizing methanol conversion and hydrogen yield. Thick catalyst layers offer higher reactor performance, whereas thin catalyst layers improve catalyst utilization and thermal uniformity. The thickness scale at which intraphase diffusion effects become noticeable was finally determined on the basis of reactor performance. The critical thickness was found to be about 0.10 mm, and catalyst layers should be designed beyond this dimension to achieve the desired level of conversion. The critical thickness will vary depending upon layer properties and operating conditions.     

Catalyst layers for proton exchange membrane fuel cells prepared by electrospray deposition on Nafion membrane

The electrospray deposition method has been used for preparation of catalyst layers for proton exchange membrane fuel cells (PEMFC) on Nafion membrane. Deposition of Pt/C + ionomer suspensions on Nafion 212 gives rise to layers with a globular morphology, in contrast with the dendritic growth observed for the same layers when deposited on the gas diffusion layer, GDL (microporous carbon black layer on carbon cloth) or on metallic Al foils. Such a change is discussed in the light of the influence of the Nafion substrate on the electrospray deposition process. Nafion, which is a proton conductor and electronic insulator, gives rise to the discharge of particles through proton release and transport towards the counter electrode, compared with the direct electron transfer that takes place when depositing on an electronic conductor. There is also a change in the electric field distribution in the needle to counter-electrode gap due to the presence of Nafion, which may alter conditions for the electrospray effect. If discharging of particles is slow enough, for instances with a low membrane protonic conductivity, the Nafion substrate may be charged positively yielding a change in the electric field profile and, with it, in the properties of the film. Single cell characterization is carried out with Nafion 212 membranes catalyzed by electrospray on the cathode side. It is shown that the internal resistance of the cell decreases with on-membrane deposited cathodic catalyst layers, with respect to the same layers deposited on GDL, giving rise to a considerable improvement in cell performance. The lower internal resistance is due to higher proton conductivity at the catalyst layer-membrane interface resulting from on-membrane deposition. On the other hand, electroactive area and catalyst utilization appear little modified by on-membrane deposition, compared with on-GDL deposition.     

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.     

Catalyst loading for Pt-nanowire thin film electrodes in PEFCs

Among electrocatalysts with novel nanostructures in low temperature polymer electrolyte fuel cells (PEFCs), Pt nanowires (Pt-NWs), as one-dimensional (1-D) nanomaterials, are recognized as promising candidates. It has also been reported that the excellent catalytic performance of the nanostructure benefited from their unique 1-D features, but also bring unusual shapes and bulky specific volumes, which make Pt-NWs difficult to fabricate into fuel cell electrodes by any conventional procedures. To understand the effect of catalyst loading on the Pt-NW electrode structure, Pt-NW thin film electrodes of various catalyst loadings were examined towards the oxygen reduction reaction (ORR) ability at the cathode side in low temperature PEFCs. SEM, XRD and electrochemical impedance spectroscopy (EIS) measurements were performed to help understanding and elucidating the electrode role under ‘real’ conditions. The results showed a similar optimal catalyst loading as compared with conventional GDEs with spherical electrocatalysts, but exhibiting a different electrode structure with increasing Pt-NW loading, although a similar larger mass transfer resistance was observed at high Pt-NW loading. The mechanism is further discussed in this paper.     

Performance analysis of a PEM fuel cell cathode with multiple catalyst layers

The cathode catalyst layer (CL) of a PEM fuel cell (PEMFC) plays an important role in the performance of the cell because of the rate limiting mechanisms that take place in it. For enhancing the performance of a PEMFC, the use of multiple, ultra thin CLs instead of a single CL is considered in the present work. Since the concentration of oxygen decreases in a CL from the diffusion medium-CL interface towards the polymer membrane, the CL adjacent to the diffusion medium should be of higher porosity than the other CLs. Similarly, the CL adjacent to the polymer membrane should contain more ionomer than the other CLs. Furthermore, liquid water should be removed without causing significant mass transport and/or ohmic losses. Therefore, the design parameters of a CL can be varied spatially to minimize losses in a PEMFC. However, such a continuously graded CL is difficult to manufacture due to lack of commercially available techniques and associated costs. As an alternative, a combination of layers can be synthesized where each layer is manufactured with different design parameters. This approach provides the opportunity to optimize the design parameters of each layer. With this objective in mind, a detailed steady state model of a PEMFC cathode with multiple layers is developed. The model considers liquid water in all the layers. The catalyst layer microstructure is modeled as a network of spherical agglomerates. For improved water management, a thin micro-porous layer is considered between the gas diffusion layer (GDL) and the first catalyst layer. The performance curves for various combinations of the design parameters are shown and the results are analyzed. The results show that there exists an optimum combination of design parameters for each catalyst layer that can significantly improve the performance of a PEMFC.     

Performance of high temperature fuel cells with different types of PBI membranes as analysed by impedance spectroscopy

In order to study how PBI membranes influence the operation of HT-PEFC cathode we analyse the performance of HT-PEFC based on three different PBI membrane types (meta-PBI, ABPBI and PBI-O-PhT) by means of stationary voltamperometry and impedance spectroscopy. For impedance spectra interpretation we use an equivalent circuit containing transmission line distributed element. This approach allows us to measure the distributed ohmic resistance of proton transport inside cathode catalyst layer. It is shown that this resistance depends on the membrane type used and has even more pronounced influence on the FC performance than ohmic resistance of the membrane itself.     

A study of the effect of compression on the performance of polymer electrolyte fuel cells using electrochemical impedance spectroscopy and dimensional change analysis

Compression plays an important role in the performance of polymer electrolyte fuel cells (PEFCs). In this study, dynamic compression is applied using a cell compression unit (CCU) to study the effect on performance of a membrane electrode assembly (MEA) with dimension change. The stress/strain characteristics of the MEA are observed to be dominated by the gas diffusion layer (GDL), with the GDL exhibiting a degree of plasticity. Electrochemical impedance spectroscopy (EIS) is used to delineate the effect of compression on contact resistance and mass transfer losses.     

Nafion nanofibers and their effect on polymer electrolyte membrane fuel cell performance

Current fuel cell research is focused on reducing manufacturing costs by reducing platinum catalyst loading without sacrificing performance. Although improvements have been demonstrated by using platinum supported on porous carbon nanoparticles, significant losses in “active” platinum surface area within the catalyst layer (CL) still occur. Optimizing the reactant gas/Nafion^®/platinum triple phase boundary (TPB) in the CL (i.e., CL morphology) will result in increased “active” catalyst area and overall fuel cell performance. In this study, the effect of temperature on the formation of Nafion^® nanofibers in the CL during fuel cell operation and its subsequent improvement on fuel cell performance was clearly characterized. Post mortem scanning electron micrographs clearly show that Nafion^® nanofibers improve the TPB, where Nafion^® nanofibers act as a more efficient proton transport route from the catalyst particles to the polymer electrolyte membrane reducing ohmic and mass transport resistance.     

Engineering the catalyst layers towards enhanced local oxygen transport of Low-Pt proton exchange membrane fuel cells: Materials,designs, and methods

Proton exchange membrane fuel cells (PEMFCs) help to achieve decarbonized energy demand due to their advantages of no pollution emission and high power efficiency. But the commercialization of fuel cells has encountered difficulties due to the high-cost issue. The key to addressing the cost issue of PEMFCs lies in reducing Pt amount. However, concentration polarization in the high current density region increases as the decrease of Pt loading, of which the local transport loss of oxygen in the cathode catalyst layer (CCL) occupies the most significant part. Therefore, reducing local oxygen transport resistance is necessary to achieve ultra-low Pt loading in practical PEMFC. This paper focuses on summarizing various electrode design methods for the CCL that optimize the local transport resistance of oxygen, including modifications to the ionomer layer, catalyst structure, and overall electrode structure. Each improvement method is explained with the mechanism of the local oxygen transport process, investigating the effect of different ionomer and Pt-based nanoparticle structures, distribution, and surface chemistries on the local transport pathways. The insights proposed in this paper provide recommendations for the fabrication and design of high-efficiency low-platinum fuel cells.