A computational model for assessing impact of interfacial morphology on polymer electrolyte fuel cell performance

A two-dimensional, non-isothermal, anisotropic numerical model is developed to investigate the impact of the interfacial morphology between the micro-porous layer (MPL) and the catalyst layer (CL) on the polymer electrolyte fuel cell (PEFC) performance. The novel feature of the model is the inclusion of directly measured surface morphological information of the MPL and the CL. The interfacial morphology of the MPL and the CL was experimentally characterized and integrated into the computational framework, as a discrete interfacial layer. To estimate the impact of MPL|CL interfacial surface morphology on local ohmic, thermal and mass transport losses, two different model schemes, one with the interface layer and one with the traditionally used perfect contact are compared. The results show a ∼54 mV decrease in the performance of the cell due to the addition of interface layer at 1 A cm⁻². Local voids present at the MPL|CL interface are found to increase ohmic losses by ∼37 mV. In-plane conductivity adjacent to the interface layer is determined to be the key controlling parameter which governs this additional interfacial ohmic loss. When the interfacial voids are simulated to be filled with liquid water, the overpotential on the cathode side is observed to increase by ∼25 mV. Local temperature variation of up to 1 °C is also observed at the region of contact between the MPL and the CL, but has little impact on predicted voltage.     

Parametric study of the cathode and the role of liquid saturation on the performance of a polymer electrolyte membrane fuel cell—A numerical approach

A two-dimensional two-phase steady state model of the cathode of a polymer electrolyte membrane fuel cell (PEMFC) is developed using unsaturated flow theory (UFT). A gas flow field, a gas diffusion layer (GDL), a microporous layers (MPL), a finite catalyst layer (CL), and a polymer membrane constitute the model domain. The flow of liquid water in the cathode flow channel is assumed to take place in the form of a mist. The CL is modeled using flooded spherical agglomerate characterization. Liquid water is considered in all the porous layers. For liquid water transport in the membrane, electro-osmotic drag and back diffusion are considered to be the dominating mechanisms. The void fraction in the CL is expressed in terms of practically achievable design parameters such as platinum loading, Nafion loading, CL thickness, and fraction of platinum on carbon. A number of sensitivity studies are conducted with the developed model. The optimum operating temperature of the cell is found to be 80-85 °C. The optimum porosity of the GDL for this cell is in the range of 0.7-0.8. A study by varying the design parameters of the CL shows that the cell performs better with 0.3-0.35 mg cm⁻² of platinum and 25-30 wt% of ionomer loading at high current densities. The sensitivity study shows that a multi-variable optimization study can significantly improve the cell performance. Numerical simulations are performed to study the dependence of capillary pressure on liquid saturation using various correlations. The impact of the interface saturation on the cell performance is studied. Under certain operating conditions and for certain combination of materials in the GDL and CL, it is found that the presence of a MPL can deteriorate the performance especially at high current density.     

Experimental investigation of the role of a microporous layer on the water transport and performance of a PEM fuel cell

A highly reliable experimental system that consistently closed the overall water balance to within 5% was developed to study the role of a microporous layer (MPL), attached to carbon paper porous transport layer (PTL), on the water transport and performance of a standard 100 cm² active area PEM fuel cell. Various combinations of cells were built and tested with PTLs at the electrodes using either carbon fibre paper with a MPL (SGL 10BB) or carbon fibre paper without a MPL (SGL 10BA). The net water drag coefficient at three current densities (0.3, 0.5 and 0.7 A cm⁻²) for two combinations of anode/cathode relative humidity (60/100% and 100/60%) and stoichiometric ratios of H₂/air (1.4/3 and 1.4/2) was determined from water balance measurements. The addition of a MPL to the carbon fibre paper PTL at the cathode did not cause a statistically significant change to the overall drag coefficient although there was a significant improvement to the fuel cell performance and durability when a MPL was used at the cathode. The presence of a MPL on either electrode or on both electrodes also exhibited similar performance compared to when the MPL was placed at the cathode. These results indicate that the presence of MPL indeed improves the cell performance although it does not affect the net water drag coefficient. The correlation between cell performance and global water transport cannot be ascertained and warrants further experimental investigation.     

Effects of cathode gas diffusion layer design on polymer electrolyte membrane fuel cell water management and performance

The effects of a microporous layer (MPL) on performance and water management of polymer electrolyte fuel cells are investigated. The presence of an MPL on the cathode side is found to slightly improve performance, although the voltage gain is less significant than that obtained by wetter reactants. The effect of the MPL on water management depends on the cathode inlet-gas humidity. Differences in water crossover rate are insignificant for wet cathode feed (RH = 75%), while they are significant for dry feed (RH = 25%). A model based on transport resistance of the MPL is proposed to explain the experimental trends observed. Modeling results suggest that the presence of the MPL on the cathode side causes a reduction of the water flux from the cathode catalyst layer to the flow channels, effectively promoting water back diffusion through the membrane. Higher cathode humidity reduces the driving force for water transport from the electrode to the gas channels, also reducing the importance of the water transport resistance due to the presence of the MPL.     

A two-phase model for studying the role of microporous layer and catalyst layer interface on polymer electrolyte fuel cell performance

In this work, a two-phase, two-dimensional model is developed to investigate the role of interfacial voids at the microporous layer (MPL) and catalyst layer (CL) interface on the polymer electrolyte fuel cell (PEFC) performance. The model incorporates the MPL|CL interfacial region as a separate domain and simulates two-phase transport within the interfacial voids. Different case studies, including the experimentally-measured MPL|CL interface and a perfect contact interface, are conducted. Model simulations indicate that the MPL|CL interfacial morphology has a significant effect on performance, particularly in the high current density region (>1.0 A/cm²). The interfacial voids at the MPL|CL interface are found to retain liquid water during operation and induce mass transport resistance, resulting in nearly a 20% reduction in the limiting current density when compared to perfect interfacial contact. The liquid water saturation retained at the interface and the magnitude of the mass and charge transport resistance induced by the interface are found to be highly dependent upon the geometry and size of the interfacial voids. Finally, simulations indicate that the morphology of the MPL|CL interface affects the location where reactions tend to occur in the CL, and also has a direct impact on the temperature distribution within the cathode.     

Characterization of interfacial morphology in polymer electrolyte fuel cells: Micro-porous layer and catalyst layer surfaces

The interface between the micro-porous layer (MPL) and the catalyst layer (CL) can have an impact on thermal, electrical and two-phase mass transport in a polymer electrolyte fuel cell (PEFC). However, there is scant information available regarding the true morphology of the MPL and CL surfaces. In this work, optical profilometry is used to characterize the MPL and CL surfaces at the sub-micron level scale to gain a better understanding of the surface morphology. Selected MPL and CL surfaces were sputtered with a thin layer of gold to enhance the surface reflectivity for improved data acquisition. The results show that, for the materials tested, the MPL surface has a relatively higher roughness than the CL surface, indicating the potential dominance of the MPL surface morphology on the local transport and interfacial contact across the MPL|CL interface. The level of roughness can be on the order of 10 μm peak height, which is significant in comparison to other length scales involved in transport, and can result in significant interfacial water storage capacity (approximately 6-18% of the total water content in a PEFC [37]) along this interface. Another surface characteristic that can have a profound influence on multi-phase transport is the existence of deep cracks along the MPL and CL surfaces. The cracks on MPL and CL surfaces are observed to differ significantly in terms of their orientation, size, shape, depth and density. The areal crack density of the CL tested is calculated to be 3.4 ± 0.2%, while the areal crack density of the MPL is found to vary from 2.8% to 8.9%. The results of this study can be useful to understand the true nature of the interfacial transport in PEFCs.     

Effects of gas diffusion layer (GDL) and micro porous layer (MPL) on cathode performance in microbial fuel cells (MFCs)

This study focused on novel cathode structures to increase power generation and organic substrate removal in microbial fuel cells (MFCs). Three types of cathode structures, including two-layer (gas diffusion layer (GDL) and catalyst layer (CL)), three-layer (GDL, micro porous layer (MPL) and CL), and multi-layer (GDL, CL, carbon based layer (CBL) and hydrophobic layers) structures were examined and compared in single-chamber MFCs (SCMFCs). The results showed that the three-layer (3L) cathode structures had lower water loss than other cathodes and had a high power density (501 mW/m²). The MPL in the 3L cathode structure prevented biofilm penetration into the cathode structure, which facilitated the oxygen reduction reaction (ORR) at the cathode. The SCMFCs with the 3L cathodes had a low ohmic resistance (R_ohmic: 26-34 Ω) and a high cathode open circuit potential (OCP: 191 mV). The organic substrate removal efficiency (71-78%) in the SCMFCs with 3L cathodes was higher than the SCMFCs with two-layer and multi-layer cathodes (49-68%). This study demonstrated that inserting the MPL between CL and GDL substantially enhanced the overall electrical conduction, power generation and organic substrate removal in MFCs by reducing water loss and preventing biofilm infiltration into the cathode structure.     

Effect of cathode gas diffusion layer on water transport and cell performance in direct methanol fuel cells

The optimal design of the cathode gas diffusion layer (GDL) for direct methanol fuel cells (DMFCs) is not only to attain better cell performance, but also to achieve better water management for the DMFC system. In this work, the effects of both the PTFE loading in the cathode backing layer (BL) as well as in the micro-porous layer (MPL) and the carbon loading in the MPL on both water transport and cell performance were investigated experimentally. The experimental data showed that with the presence of a hydrophobic MPL in the GDL, the water-crossover flux through the membrane decreased slightly with increasing the PTFE loading in the BL. However, a higher PTFE loading in the BL not only lowered cell performance, but also resulted in an unstable discharging process. It was also found that the PTFE loading in the MPL had little effect on the water-crossover flux, but its effect on cell performance was substantial: the 40-wt% PTFE loading in the MPL was found to be the optimal value to achieve the best performance. The experimental results further showed that increasing the carbon loading in the MPL significantly lowered the water-crossover flux, but a too high carbon loading would decrease the cell performance as the result of the increased oxygen transport resistance; the 2.0-mg C cm⁻² carbon loading was found to exhibit the best performance.     

Double microporous layer cathode for membrane electrode assembly of passive direct methanol fuel cells

A novel membrane electrode assembly (MEA) is described that utilizes a double microporous layer (MPL) structure in the cathode of a passive direct methanol fuel cell (DMFC). The double MPL cathode uses Ketjen Black carbon as an inner-MPL and Vulcan XC-72R carbon as an outer-MPL. Experimental results indicate that this double MPL structure at the cathode provides not only a higher oxygen transfer rate, but enables more effective back diffusion of water; thus, leading to an improved power density and stability of the passive DMFC. The maximum power density of an MEA with a double MPL cathode was observed to be ca. 33.0 mW cm⁻², which is found to be a substantial improvement over that for a passive DMFC with a conventional MEA. A. C. impedance analysis suggests that the increased performance of a DMFC with the double MPL cathode might be attributable to a decreased charge transfer resistance for the cathode oxygen reduction reaction.     

Liquid water flooding process in proton exchange membrane fuel cell cathode with straight parallel channels and porous layer

Liquid water management plays a significant role in proton exchange membrane fuel cell (PEMFC) performance, especially when the PEMFC is operating with high current density. Therefore, understanding of liquid water behavior and flooding process is a critical challenge that must be addressed. To overcome PEMFC durability problems, a liquid water flooding process is studied in the cathode side of a PEMFC with straight parallel channels and a porous layer using FLUENT^® v6.3.26 software with a volume-of-fluid (VOF) algorithm and user-defined-function (UDF). The general process of liquid water flooding within this type of PEMFC cathode is investigated by analyzing the behavior of liquid water in porous layer and gas flow channels. Two important phenomena, the “first channel phenomenon” and the “last channel phenomenon”, and their effects on the flow distribution along different parallel channels are discussed.     

Cold-start icing characteristics of proton-exchange membrane fuel cells

Understanding the icing characteristics of proton-exchange membrane fuel cells (PEMFCs) is essential for optimizing their cold-start performance. This study examined the effects of start-up temperature, current density, and microporous layer (MPL) hydrophobicity on the cold-start performance and icing characteristics of PEMFCs. Further, the cold-start icing characteristics of PEMFCs were studied by testing the PEMFC output voltage, impedance, and temperature changes at different positions of the cathode gas diffusion layer. Observation of the MPL surface after cold-start failure allowed determination of the distribution of ice formation at the catalytic layer/MPL interface. At fuel cell temperatures below 0 °C, supercooled water in the cell was more likely to undergo concentrated instantaneous freezing at higher temperatures (−4 and −5 °C), whereas the cathode tended to freeze in sequence at lower temperatures (−8 °C). In addition, a more hydrophobic MPL resulted in two successive instantaneous icing phenomena in the fuel cell and improved the cold-start performance.     

Effect of surface dynamic wettability in proton exchange membrane fuel cells

It is known that the static contact angle reflecting the “contact area” between liquid and solid is insufficient to represent the dynamic wettability of a solid surface, and another parameter called the sliding angle is needed to describe the relative easiness of liquid moving on a solid surface. However, sliding angle has been largely neglected in the previous studies for proton exchange membrane fuel cell (PEMFC). In this study, three-dimensional multiphase simulations are carried out for a PEMFC with single straight flow channels considering both the static contact angles and sliding angles of gas diffusion layer (GDL) and catalyst layer (CL). The results show that the liquid water volume fraction in cathode CL (CCL) and GDL (CGDL) can be increased by several times when the sliding angle is increased while the static contact angle is kept constant. This could have significant implication on the water management strategy due to the considerable changes in the water transport and removal processes. Since GDL is much thicker than CL, changing the surface dynamic wettability of GDL has more significant effect on liquid water transport than changing the surface dynamic wettability of CL.     

A novel self-humidifying membrane electrode assembly with water transfer region for proton exchange membrane fuel cells

A novel self-humidifying membrane electrode assembly (MEA) with the active electrode region surrounded by a unactive “water transfer region (WTR)” was proposed to achieve effective water management and high performance for proton exchange membrane fuel cells (PEMFCs). By this configuration, excess water in the cathode was transferred to anode through Nafion membrane to humidify hydrogen. Polarization curves and power curves of conventional and the self-humidifying MEAs were compared. The self-humidifying MEA showed power density of 85 mW cm⁻² at 0.5 V, which is two times higher than that of a conventional MEA with cathode open. The effects of anode hydrogen flow rates on the performance of the self-humidifying MEA were investigated and its best performance was obtained at a flow rate of 40 ml min⁻¹. Its performance was the best when the environmental temperature was 40 °C. The performance of the self-humidifying MEA was slightly affected by environmental humidity. The area of WTR was optimized, and feasible area ratio of the self-humidifying MEA was 28%.     

A study of water transport as a function of the micro-porous layer arrangement in PEMFCs

Electrochemical losses as a function of the micro-porous layer (MPL) arrangement in Proton Exchange Membrane Fuel Cells (PEMFCs) are investigated by electrochemical impedance spectroscopy (EIS). Net water flux across the polymer membrane in PEMFCs is investigated for various arrangements of the MPL, namely with MPL on the cathode side alone, with MPL on both the cathode and the anode sides and without MPL. EIS and water transport are recorded for various operating conditions, such as the relative humidity of the hydrogen inlet and current density, in a PEMFC fed by fully-saturated air. The cell with an MPL on the cathode side alone has better performance than two other types of cells. Furthermore, the cell with an MPL on only the cathode increases the water flux from cathode to anode as compared to the cells with MPLs on both electrodes and cells without MPL. Oxygen-mass-transport resistances of cells in the presence of an MPL on the cathode are lower than the values for the other two cells, which indicates that the molar concentration of oxygen at the reaction surface of the catalyst layer is higher. This suggests that the MPL forces the liquid water from the cathode side to the anode side and decreases the liquid saturation in GDL at high current densities. Consequently, the MPL helps in maintaining the water content in the polymer membrane and decreases the cathode charge transfer and oxygen-mass transport resistances in PEMFCs, even when the hydrogen inlet has a low relative humidity.     

Experimental investigation on the performance and durability of hydrogen AEMFC with electrochemical impedance spectroscopy

In situ experimental tests and scanning electron microscope (SEM) observations are done to explore the impact of geometry structure and operating conditions on the performance and durability of alkaline electrolyte membrane fuel cell (AEMFC) accompanied by electrochemical diagnosis. The results show that low anode and cathode polarization resistances can be achieved by selecting a proper ionomer mass fraction (IMF) of the catalyst layer (CL). Increasing the IMF can improve the tolerance to inlet gas humidity. The presence of the anode microporous layer (MPL) greatly improves the cell performance, but cathode MPL plays a reverse effect. After the durability test, the homogeneity of CL is seriously deformed, leading to a great increment of anode and cathode polarization resistances, verified by the electrochemical impedance spectroscopy (EIS) and SEM results. An enhancement of fuel cell durability is achieved by adding nanoscale polytetrafluoroethylene (PTFE) into CL. This work can provide some guidance for the structural and operating parameter optimization of the AEMFC researches in the future.     

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.     

Experimental study of commercial size proton exchange membrane fuel cell performance

Commercial sized (16 × 16 cm² active surface area) proton exchange membrane (PEM) fuel cells with serpentine flow chambers are fabricated. The GORE-TEX® PRIMEA 5621 was used with a 35-μm-thick PEM with an anode catalyst layer with 0.45 mg cm⁻² Pt and cathode catalyst layer with 0.6 mg cm⁻² Pt and Ru or GORE-TEX® PRIMEA 57 was used with an 18-μm-thick PEM with an anode catalyst layer at 0.2 mg cm⁻² Pt and cathode catalyst layer at 0.4 mg cm⁻² of Pt and Ru. At the specified cell and humidification temperatures, the thin PRIMEA 57 membrane yields better cell performance than the thick PRIMEA 5621 membrane, since hydration of the former is more easily maintained with the limited amount of produced water. Sufficient humidification at both the cathode and anode sides is essential to achieve high cell performance with a thick membrane, like the PRIMEA 5621. The optimal cell temperature to produce the best cell performance with PRIMEA 5621 is close to the humidification temperature. For PRIMEA 57, however, optimal cell temperature exceeds the humidification temperature.     

Fabrication of a carbon nanofiber sheet as a micro-porous layer for proton exchange membrane fuel cells

A carbon nanofiber sheet (CNFS) has been prepared by electrospinning, stabilisation and subsequent carbonisation processes. Imaging with scanning electron microscope (SEM) indicates that the CNFS is formed by nonwoven nanofibers with diameters between 400 and 700 nm. The CNFS, with its three-dimensional pores, shows excellent electrical conductivity and hydrophobicity. In addition, it is found that the CNFS can be successfully applied as a micro-porous layer (MPL) in the cathode gas diffusion layer (GDL) of a proton exchange membrane fuel cell (PEMFC). The GDL with the CNFS as a MPL has higher gas permeability than a conventional GDL. Moreover, the resultant cathode GDL exhibits excellent fuel cell performance with a higher peak power density than that of a cathode GDL fabricated with a conventional MPL under the same test condition.     

Transient analysis for the cathode gas diffusion layer of PEM fuel cells

A one-dimensional, non-isothermal, two-phase transient model has been developed to study the transient behaviour of water transport in the cathode gas diffusion layer of PEM fuel cells. The effects of four parameters, namely the liquid water saturation at the interface of the gas diffusion layer and flow channels, the proportion of liquid water to all of the water at the interface of the cathode catalyst layer and the gas diffusion layer, the current density, and the contact or wetting angle, on the transient distribution of liquid water saturation in the cathode gas diffusion layer are investigated. Especially, the time needed for liquid water saturation to reach steady state and the liquid water saturation at the interface of the cathode catalyst layer and gas diffusion layer are plotted as functions of the above four parameters. The ranges of water vapour condensation and liquid water evaporation are identified across the thickness of the gas diffusion layer. In addition, the effects of the above four parameters on the steady state distributions of gas phase pressure, water vapour concentration, oxygen concentration and temperature are also presented. It is found that increasing any one of the first three parameters will increase the water saturation at the interface of the catalyst layer and gas diffusion layer, but decrease the time needed for the liquid water saturation to reach steady state. When the liquid water saturation at the interface of the gas diffusion layer and flow channels is high enough (≥0.1), the liquid water saturation at steady state is almost uniformly distributed across the thickness of the gas diffusion layer. It is also found that, under the given initial and boundary conditions in this paper, evaporation takes place within the gas diffusion layer close to the channel side and is the major process for water phase change at low current density (<2000 A m⁻²); condensation occurs close to the catalyst layer side within the gas diffusion layer and dominates the phase change at high current density (>5000 A m⁻²). For hydrophilic gas diffusion layers, both the time needed for liquid water saturation to reach steady state and the water saturation at the interface of the catalyst layer and gas diffusion layer will increase when the contact angle increases; but for hydrophobic gas diffusion layers, both of them decrease when the contact angle increases.     

Influence of the dispersion state of ionomer on the dispersion of catalyst ink and the construction of catalyst layer

The ionomer state in the catalyst ink of a proton exchange membrane fuel cell (PEMFC) plays a critical role in the formation of the catalyst/ionomer interface on the catalyst layer (CL). In this study, the effect of ionomer dispersion state on catalyst ink dispersion and the construction of a reasonable CL was investigated. The study of catalyst inks revealed that the dispersion of n-propanol (NPA) -ionomer dispersion or sonication could effectively reduce the catalyst particle size in inks. For shear-dispersion and homogenizer-dispersion inks, the catalyst particle size was reduced from 6.17 nm to 5.12 nm and from 5.12 nm to 4.67 nm, respectively. The ionomer dispersion was capable of significantly reducing the size of agglomerates in the ink, which resulted in a reduction in the particle size of agglomerates on the surface of the cathode CL and an improvement in its flatness. The pore size distributions of the MEA cathode catalyst layers showed that water bath ultrasonic treatment of the ionomer could result in a more reasonable pore structure for the catalyst layer. The single-cell test revealed that changing the ionomer's dispersion state could significantly increase the fuel cell's output voltage to 0.707 V at 1000 mA cm⁻², and the cell's power density to 1028 mW cm⁻² at 2000 mA cm⁻².