Experimental study on carbon corrosion of the gas diffusion layer in polymer electrolyte membrane fuel cells

Generally, the GDL of a PEM fuel cell experiences three external attacks: dissolution of water, erosion of gas flow, and corrosion of electric potential. Of these degradation factors, this study focuses on the carbon corrosion of electric potential and investigates its impact through the accelerated carbon corrosion test. This study confirms that carbon corrosion occurs at the GDL, which decreases the operating fuel cell’s performance. To discover the effects of carbon corrosion, the GDL property changes are measured through various devices, including a scanning electron microscopy, a thermo gravimetric analyzer, and a tensile stress test. Carbon corrosion causes not only loss of weight and thickness but also degradation of mechanical strength in the GDL. In addition, the GDL shows serious damage in its center.     

The impact of rib structure on the water transport behavior in gas diffusion layer of polymer electrolyte membrane fuel cells

Using the multiphase lattice Boltzmann method (LBM), the liquid water transport dynamics is simulated in a gas diffusion layer (GDL) of polymer electrolyte membrane fuel cells (PEMFCs). The effect of rib structure on the water invasion process in the micro-porous GDL is explored by comparing the two cases, i.e., with rib and without rib structures. The liquid water distribution and water saturation profile are presented to determine the wetting mechanism in the GDL. The results show that the liquid water transport in the GDL is strongly governed by capillary force and the rib structure plays a significant role on water distribution and water transport behavior in the GDL. Comparison of two cases confirms that the rib structure influences on the location of water breakthrough. The liquid water distribution and water saturation profile indicate that the high resistance force underneath the rib suppresses the growth of water cluster, resulting in the change of flow path. After water breakthrough, the liquid water distribution under the channel has little variation, whereas that under the rib continues to change. The predicted value of effective permeability is in good agreement with Carman-Kozeny correlation and experimental results in the literature. The results suggest that the LBM approach is an effective tool to investigate the water transport behavior in the GDL.     

Effects of gas diffusion layer structure on the open circuit voltage and hydrogen crossover of polymer electrolyte membrane fuel cells

The clamping pressure of polymer electrolyte membrane fuel cells for vehicle applications should be typically high enough to minimize contact resistance. However, an excessive compression pressure may cause a durability problem. In this study, the effects of gas diffusion layer (GDL) structure on the open circuit voltage (OCV) and hydrogen crossover have been closely examined. Results show that the performances of fuel cells with GDL-1 (a carbon fiber felt substrate with MPL having rough surface) and GDL-3 (a carbon fiber paper substrate with MPL having smooth surface) are higher than that with GDL-2 (a carbon fiber felt substrate with MPL having smooth surface) under low clamping torque conditions, whereas when clamping torque is high, the GDL-1 sample shows the largest decrease in cell performance. Hydrogen crossover for all GDL samples increases with the increase of clamping torque, especially the degree of increase of GDL-1 is much greater than that of the other two GDL samples. The OCV reduction of GDL-1 is much greater than that of GDL-2 and GDL-3. It is concluded that the GDL-3 is better than the other two GDLs in terms of fuel cell durability, because the GDL-3 shows the minimum OCV reduction.     

Microporous layer coated gas diffusion layers for enhanced performance of polymer electrolyte fuel cells

The influence of microporous layer (MPL) design parameters for gas diffusion layers (GDLs) on the performance of polymer electrolyte fuel cells (PEFCs) was clarified. Appropriate MPL design parameters vary depending on the humidification of the supplied gas. Under low humidification, decreasing both the MPL pore diameter and the content of polytetrafluoroethylene (PTFE) in the MPL is effective to prevent drying-up of the membrane electrode assembly (MEA) and enhance PEFC performance. Increasing the MPL thickness is also effective for maintaining the humidity of the MEA. However, when the MPL thickness becomes too large, oxygen transport to the electrode through the MPL is reduced, which lowers PEFC performance. Under high humidification, decreasing the MPL mean flow pore diameter to 3 μm is effective for the prevention of flooding and enhancement of PEFC performance. However, when the pore diameter becomes too small, the PEFC performance tends to decrease. Both reduction of the MPL thickness penetrated into the substrate and increase in the PTFE content to 20 mass% enhance the ability of the MPL to prevent flooding.     

Influence of anisotropic bending stiffness of gas diffusion layers on the electrochemical performances of polymer electrolyte membrane fuel cells

The effects of gas diffusion layer’s (GDL’s) anisotropic bending stiffness on the electrochemical performances of polymer electrolyte membrane fuel cells have been investigated for carbon fiber-felt and -paper GDLs. The bending stiffness values of all GDLs in the machine direction are higher than those in the cross-machine direction. We have prepared GDL sheet samples such that the machine direction of GDL roll is aligned with the major flow field direction of a metallic bipolar plate at angles of 0° (parallel: ‘0° GDL’) and 90° (perpendicular: ‘90° GDL’). The I–V performances of all the 5-cell stacks with 90° GDLs are higher than those with 0° GDLs. All the 5-cell stacks with 90° GDLs show lower values of high-frequency resistance (HFR) than those with 0° GDLs. However, the gas pressure differences at both anode and cathode of 5-cell stacks with 90° GDLs appear to be similar to or slightly lower than those with 0° GDLs, making the lower HFR as a dominant factor for the improved I–V performances. This may result from the reduced intrusion of 90° GDLs into gas channels than 0° GDLs as observed by less thickness reduction under compression of 90° GDLs. A 45° GDL (skew alignment) also shows better performances than the 0° GDL.     

Controlling gas diffusion layer oxidation by homogeneous hydrophobic coating for polymer electrolyte fuel cells

Reduced production costs and enhanced durability are necessary for practical application of polymer electrolyte fuel cells. There has been a great deal of concern about degradation of the gas diffusion layer located outside the membrane electrode assembly. However, very few studies have been carried out on the degradation process, and no suitable methods for improving the durability of the cell have been found.In this work, the influence on the cell performance and factors involved in the degradation of the gas diffusion layer has been clarified through power generation tests.Long-term power generation tests on single cells for 6000 h were carried out under high humidity conditions with homogeneous and inhomogeneous hydrophobic coating gas diffusion layers. The results showed that the increase in the diffusion overvoltage from the gas diffusion layer could be controlled by the use of a homogeneous coating. Post-analyses indicated that this occurred by controlling oxidation of the carbon fiber.     

Influence of anisotropic bending stiffness of gas diffusion layers on the degradation behavior of polymer electrolyte membrane fuel cells under freezing conditions

The effects of gas diffusion layer’s (GDL’s) anisotropic bending stiffness on the degradation behavior of polymer electrolyte membrane fuel cells have been investigated under freezing conditions. We have prepared GDL sheet samples such that the higher stiffness direction of GDL roll is aligned with the major flow field direction of a metallic bipolar plate at angles of 0° (parallel: ‘0° GDL’) and 90° (perpendicular: ‘90° GDL’). The I-V performances before and after 1000 temperature cycles between −10 and 1 °C of 90° GDL stack are higher than those of 0° GDL stack, and the voltages of 90° GDL stack are decreased slower than those of 0° GDL stack, indicating a higher durability of 90° GDL stack. Furthermore, the values and increasing rates of high-frequency resistance of 90° GDL stack are lower than those of 0° GDL stack. However, the H₂ and air pressure differences before and after 1000 temperature cycles of 90° GDL stack are very similar to those of 0° GDL stack. The surface of anode catalyst layer (CL) of membrane-electrode assembly (MEA) with catalyst-coated membrane type in 0° GDL stack appears to be more severely damaged than that in 90° GDL stack, especially under the channels, whereas the surfaces of cathode CLs of MEAs in both 0° and 90° GDL stacks are slightly damaged after 1000 temperature cycles.     

Apparent contact angles of liquid water droplet breaking through a gas diffusion layer of polymer electrolyte membrane fuel cell

The lattice Boltzmann method is used to simulate the three-dimensional dynamic process of liquid water breaking through the gas diffusion layer (GDL) in the polymer electrolyte membrane fuel cell. An accurate method is introduced to analyze asymmetric droplet shape. Ten micro-structures of Toray GDL were built based on a stochastic geometry model. It was found that asymmetric droplets are produced on the GDL surfaces. Their local apparent contact angles vary with different view angles and geometries. They are different to the idealized contact angles by symmetric simplification. It was concluded that the apparent contact angles are influenced by GDL structures and view angles. This information can help to bridge the gap between mesoscale and cell-scale simulations in the field of fuel cell simulation.     

Pore network modeling of fibrous gas diffusion layers for polymer electrolyte membrane fuel cells

A pore network model of the gas diffusion layer (GDL) in a polymer electrolyte membrane fuel cell is developed and validated. The model idealizes the GDL as a regular cubic network of pore bodies and pore throats following respective size distributions. Geometric parameters of the pore network model are calibrated with respect to porosimetry and gas permeability measurements for two common GDL materials and the model is subsequently used to compute the pore-scale distribution of water and gas under drainage conditions using an invasion percolation algorithm. From this information, the relative permeability of water and gas and the effective gas diffusivity are computed as functions of water saturation using resistor-network theory. Comparison of the model predictions with those obtained from constitutive relationships commonly used in current PEMFC models indicates that the latter may significantly overestimate the gas phase transport properties. Alternative relationships are suggested that better match the pore network model results. The pore network model is also used to calculate the limiting current in a PEMFC under operating conditions for which transport through the GDL dominates mass transfer resistance. The results suggest that a dry GDL does not limit the performance of a PEMFC, but it may become a significant source of concentration polarization as the GDL becomes increasingly saturated with water.     

Electrochemical durability of gas diffusion layer under simulated proton exchange membrane fuel cell conditions

An effective ex-situ method for characterizing electrochemical durability of a gas diffusion layer (GDL) under simulated polymer electrolyte membrane fuel cell (PEMFC) conditions is reported in this article. Electrochemical oxidation of the GDLs are studied following potentiostatic treatments up to 96 h holding at potentials from 1.0 to 1.4 V (vs.SCE) in 0.5 mol L⁻¹ H₂SO₄. From the analysis of morphology, resistance, gas permeability and contact angle, the characteristics of the fresh GDL and the oxidized GDLs are compared. It is found that the maximum power densities of the fuel cells with the oxidized GDLs hold at 1.2 and 1.4 V (vs.SCE) for 96 h decreased 178 and 486 mW cm⁻², respectively. The electrochemical impedance spectra measured at 1500 mA cm⁻² are also presented and they reveal that the ohmic resistance, charge-transfer and mass-transfer resistances of the fuel cell changed significantly due to corrosion at high potential.     

Analysis of surface and interior degradation of gas diffusion layer with accelerated stress tests for polymer electrolyte membrane fuel cell

The effects of surface and interior degradation of the gas diffusion layer (GDL) on the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) have been investigated using three freeze-thaw accelerated stress tests (ASTs). Three ASTs (ex-situ, in-situ, and new methods) are designed from freezing ?30 °C to thawing 80 °C by immersing, supplying, and bubbling, respectively. The ex-situ method is designed for surface degradation of the GDL. Change of surface morphology from hydrophobic to hydrophilic by surface degradation of GDL causes low capillary pressure which decreased PEMFC performance. The in-situ method is designed for the interior degradation of the GDL. A decrease in the ratio of the porosity to tortuosity by interior degradation of the GDL deteriorates PEMFC performance. Moreover, the new method showed combined effects for both surface and interior degradation of the GDL. It was identified that the main factor that deteriorated the fuel cell performance was the increase in mass transport resistance by interior degradation of GDL. In conclusion, this study aims to investigate the causes of degraded GDL on the PEMFC performance into the surface and interior degradation and provide the design guideline of high-durability GDL for the PEMFC.     

Effect of capillary pressure on liquid water removal in the cathode gas diffusion layer of a polymer electrolyte fuel cell

In order to investigate the effect of capillary pressure on the transport of liquid water in the cathode gas diffusion layer (GDL) of a polymer electrolyte fuel cell, a one-dimensional steady-state mathematical model was developed, including the effect of temperature on the capillary pressure. Numerical results indicate that the liquid water saturation significantly increases with increases in the operating temperature of the fuel cell. An elevated operating temperature has an undesirable influence on the removal of liquid water inside the GDL. A reported peculiar phenomenon in which the flooding of the fuel cell under a high operating temperature and an over-saturated environment is more serious in a GDL combined with a micro-porous layer (MPL) than in a GDL without an MPL [Lim and Wang, Electrochim. Acta 49 (2004), 4149–4156] is explained based on the present analysis.     

Effect of air flow on liquid water transport through a hydrophobic gas diffusion layer of a polymer electrolyte membrane fuel cell

The transport of liquid water through an idealized 2-D reconstructed gas diffusion layer (GDL) of a polymer electrolyte membrane (PEM) fuel cell is computed subject to hydrophobic boundary condition at the fibre–fluid interface. The effect of air flow, as would occur in parallel/serpentine/interdigitated type of flow fields, on the liquid water transport through the GDL, ejection into the channel in the form of water droplets and subsequent removal of the droplets has been simulated. Results show that typically water flow through the fibrous GDL occurs through a fingering and channelling type of mechanism. The presence of cross-flow of air has an effect both on the path created within the GDL and on the ejection of water into the channel in the form of droplets. A faster rate of liquid water evacuation through the GDL (i.e., more frequent ejection of water droplets) as well as less flooding of the void space results from the presence of cross-flow. These results agree qualitatively with experimental observations reported in the literature.     

Porosity-graded micro-porous layers for polymer electrolyte membrane fuel cells

In this paper, the effect of porosity-graded micro-porous layer (GMPL) on the performance of polymer electrolyte membrane fuel cells (PEMFCs) was studied in detail. The GMPL was prepared by printing micro-porous layers (MPL) with different content of NH₄Cl pore-former and the porosity of the GMPL decreased from the inner layer of the MPLs at the membrane/MPL interface to the outer layer of the MPLs at the gas diffusion electrode/MPL interface. The morphology and porosity of the GMPLs were characterized and the performance of the cell with GMPLs was compared with those having conventional homogeneous MPLs. The result demonstrates that the fuel cells consisting of GMPL have better performance than those consisting of conventional homogeneous MPLs, especially at high current densities. Micro-porous layer with graded porosity is beneficial for the electrode process of fuel cell reaction probably by facilitating the liquid water transportation through large pores and gas diffusion via small pores in the GMPLs.     

Characterisation of mechanical behaviour and coupled electrical properties of polymer electrolyte membrane fuel cell gas diffusion layers

Local compression distribution in the gas diffusion layer (GDL) of a polymer electrolyte membrane fuel cell (PEMFC) and the associated effect on electrical material resistance are examined. For this purpose a macroscopic structural material model is developed based on the assumption of orthotropic mechanical material behaviour for the fibrous paper and non-woven GDLs. The required structural material parameters are measured using depicted measurement methods. The influence of GDL compression on electrical properties and contact effects is also determined using specially developed testing tools. All material properties are used for a coupled 2D finite element simulation approach, capturing structural as well as electrical simulation in combination. The ohmic voltage losses are evaluated assuming constant current density at the catalyst layer and results are compared to cell polarisation measurements for different materials.     

Experimental study on dual recirculation of polymer electrolyte membrane fuel cell

Durability and start-up ability in sub-zero environment are two technical bottlenecks of vehicular polymer electrolyte membrane (PEM) fuel cell systems. With exhaust gas recirculation on the anode and cathode side, the cell voltage at low current density can be reduced, and the membrane can be humidified without external humidifier. They may be helpful to prolong the working lifetime and to promote the start-up ability. This paper presents an experimental study on a PEM fuel cell system with anodic and cathodic recirculation. The system is built up based on a 10 kW fuel cell stack, which consists of 50 cells and has an active area of 261 cm². A cathodic recirculation pump and a hydrogen recirculation pump are utilized on the cathode and anode side, respectively. Key parameters, e.g., stack current, stack voltage, cell voltage, air flow, relative humidity on the cathode side, oxygen concentration at the inlet and outlet of the cathode side, are measured. Results show that: 1) with a cathodic recirculation the system gets good self-humidification effect, which is similar to that with an external humidifier; 2) with a cathodic recirculation and a reduction of fresh air flux, the cell voltage can be obviously reduced; 3) with an anodic recirculation the cell voltage can also be reduced due to a reduction in the hydrogen partial pressure, the relative humidity on the cathode side is a little smaller than the case with only cathode recirculation. It indicates that, for our stack the cathodic recirculation is effective to clamp cell voltage at low current density, and a self-humidification system is possible with cathodic recirculation. Further study will focus on the dynamic model and control of the dual recirculation fuel cell system.     

Prevention of the water flooding by micronizing the pore structure of gas diffusion layer for polymer electrolyte fuel cell

In polymer electrolyte fuel cells, high humidity must be established to maintain high proton conductivity in the polymer electrolyte. However, the water that is produced electrochemically at the cathode catalyst layer can condense in the cell and cause an obstruction to the diffusion of reaction gas in the gas diffusion layer and the gas channel. This leads to a sudden decrease of the cell voltage. To combat this, strict water management techniques are required, which usually focus on the gas diffusion layer. In this study, the use of specially treated carbon paper as a flood-proof gas diffusion layer under extremely high humidity conditions was investigated experimentally. The results indicated that flooding originates at the interface between the gas diffusion layer and the catalyst layer, and that such flooding could be eliminated by control of the pore size in the gas diffusion layer at this interface.     

Study on water transport in hydrophilic gas diffusion layers for improving the flooding performance of polymer electrolyte fuel cells

For hydrogen-based polymer electrolyte fuel cells (PEFCs), water transport control in gas diffusion layers (GDLs) by wettability distribution is useful to suppress the flooding problem. In this study, the water transport of a novel GDL with hydrophilic-hydrophobic patterns was investigated. First, we clarified that the water motion in the hydrophilic GDL with microstructures could be reproduced by the enlarged scale model. The scale model experiment also showed that the same water behavior in hydrophilic GDL can be obtained from Capillary numbers (Ca) in a range of Ca ~ 10^?5 to 10^?3. As the computational load is inversely proportional to Ca, the computational load could be reduced by 1/100th by using Ca ~ 10^?3, which is 100 times higher than PEFC operation (Ca ~ 10^?5). Finally, the simulation with Ca ~ 10^?3 was performed, and we showed that the GDL with straight region of contact angle 50° minimized the water accumulation.     

Electrical/flow heterogeneity of gas diffusion layer and inlet humidity induced performance variation in polymer electrolyte fuel cells

A three-dimensional single-flow channel computational model is used to investigate the performance characteristics of polymer electrolyte fuel cells (PEFC). The combined influence of non-uniform interfacial contact resistance (ICR) and inlet relative humidity (RH), along with the heterogeneous flow properties of the gas diffusion layer (GDL) on the PEFC performance is evaluated. The study considers combinations of full and partial humidification of anode and cathode reactants. Results reveal heterogeneous GDL with non-uniform ICR distribution results in a slight ∼4.4% reduction in current density at 0.3V compared to the homogeneous case. However, under same electrical/flow heterogeneities, the current density is observed to increase by ∼19% to ∼1.3A/cm² under fully humidified anode and partially humidified cathode (i.e., RH_a|RH_c = 100%|60%) as compared to ∼1.1A/cm² under symmetric RH_a|RH_c = 100%|100%. Interesting observations are made on the temperature distribution and cathodic water fractions. The variation in anodic inlet humidity is observed to have no impact on temperature distribution in the membrane, whereas variation in cathodic inlet humidity is effective in reducing the temperature in the channel regime with a 4K (kelvin) difference among all the cases. It is noted here that the overpotential map is not an indicator for performance loss, at least at full inlet humidity. This parameter is observed to depend on water concentration in the cathode. The study provides a detailed analysis of the distribution of reactant mass fraction, water concentration, current density, temperature, cathodic overpotential, and cell performance for all the simulated cases.     

Investigating effect of different gas diffusion layers on water droplet characteristics for proton exchange membrane (PEM) fuel cells

In this work, advanced x-ray radiographic techniques available at the Canadian Light Source (CLS) were utilized to study water droplet dynamics in a serpentine flow channel mimicking a proton exchange membrane fuel cell (PEMFC). High spatial and temporal resolution coupled with high energy photons of an x-ray beam provided high-resolution images of water droplets. This technique solved the problem caused by the opaqueness of fuel cell materials including the gas diffusion layer by providing a unique way to study water droplet dynamics at different operating conditions. From the captured images, droplet emergence and formation on porous gas diffusion layers (GDLs) were analyzed. Three commercially available GDLs (Sigracet AA, Sigracet BA, and Sigracet BC) were used and droplet detachment height was found to decrease in the following order AA < BA < BC under the same flow condition. Increasing the superficial gas velocity was found to decrease the droplet detachment height for all GDLs tested. Average droplet cycle for various operating conditions was obtained. It was found that humidified air did not show a difference in droplet dimensions at detachment compared to dry air used at the inlet gas. However, it did show an impact on droplet cycle time, which might be due to condensation.