Mechanism of improving oxygen transport resistance of polytetrafluoroethylene in catalyst layer for polymer electrolyte fuel cells

Oxygen transport resistance of catalyst layer (CL) has significant impact on the performance for polymer electrolyte fuel cells (PEFCs). Nano-Polytetrafluoroethylene (PTFE) particles are added into CL to improve the oxygen transport resistance. The CV curves indicate that PTFE do not reduce the utilization of Pt. The IV polarization curves suggest that the performance incorporated PTFE in CL gradually improve at high current densities and the output is 0.57 V at 1.8 A cm^?2, 70 mV higher than that without PTFE. The water contact angle for CL with 20 wt% PTFE shows that continuous hydrophobic network may not be formed at 150 °C heat treatment temperature. The total transport resistance of CL with PTFE decreases about 2.5% at 70 °C and 250 kPa, mainly caused by the reduction of pressure-independent resistance (R_other). In the R_other reduction, the Knudsen diffusion resistance reduction in CL account for 74%. The pore size distributions reveal that the porosity increases 29% and the proportion of pores at around 100 nm increases for primary pores in CL with PTFE. This finding indicates that not the hydrophobicity of PTFE but the porous structure conducive to Knudsen diffusion for CL plays the predominant role in improving the performance.     

On the gas permeability of the microporous layer used in polymer electrolyte fuel cells

In an attempt to obtain accurate values of the gas permeability of the microporous layer (MPL), substrates with negligible MPL penetration and of known gas permeability, i.e. membrane filters, have been employed. The values of the MPL permeability obtained using the membrane filters were compared with those obtained conventionally using the carbon substrates. Due to MPL penetration, the MPL permeability obtained using the carbon substrate were found to decrease with carbon loading. On the other, due to negligible penetration, the MPL permeability obtained using the membrane filters were found to be almost invariant with the carbon loadings. Furthermore, the MPL permeability was found to be sensitive to the substrate used: more cracks (and subsequently substantially higher permeability) were shown by the MPLs coating the carbon substrates. This implies that the MPLs coating the carbon substrates and the MPLs coating the membrane filters are structure-wise different. It subsequently means that the MPL permeability obtained using the membrane filters cannot be used to estimate the MPL penetration into the carbon substrates.     

Lattice Boltzmann simulations of water transport in gas diffusion layer of a polymer electrolyte membrane fuel cell

The effect of wettability on water transport dynamics in gas diffusion layer (GDL) is investigated by simulating water invasion in an initially gas-filled GDL using the multiphase free-energy lattice Boltzmann method (LBM). The results show that wettability plays a significant role on water saturation distribution in two-phase flow in the uniform wetting GDL. For highly hydrophobicity, the water transport falls in the regime of capillary fingering, while for neutral wettability, water transport exhibits the characteristic of stable displacement, although both processes are capillary force dominated flow with same capillary numbers. In addition, the introduction of hydrophilic paths in the GDL leads the water to flow through the hydrophilic pores preferentially. The resulting water saturation distributions show that the saturation in the GDL has little change after water breaks through the GDL, and further confirm that the selective introduction of hydrophilic passages in the GDL would facilitate the removal of liquid water more effectively, thus alleviating the flooding in catalyst layer (CL) and GDL. The LBM approach presented in this study provides an effective tool to investigate water transport phenomenon in the GDL at pore-scale level with wettability distribution taken into consideration.     

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.     

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.     

Water transport in the gas diffusion layer of proton exchange membrane fuel cell under vibration conditions

Fuel cell vehicles face complicated road conditions, which may impact on the output performance of fuel cell stacks. In the present study, the water transport in the gas diffusion layer (GDL) of proton exchange membrane fuel cell (PEMFC) under vibration conditions are investigated. A stochastic method is employed to reconstruct the 3-D GDL with experimentally validated varying porosities. The volume of fluid (VOF) method is adopted to investigate the two-phase problems. Sinusoidal vibration source terms are superposed, which can vary with required amplitudes and directions. Over time, the water transport process takes three steps: water intrusion, water accumulation, and water removal. The water intrusion tends to start from the sides of the GDL, then spreads into the central area. Compared with the no-vibration case, the water saturations are higher in both the vertical and horizontal vibration cases. The vibration will enhance the water transport through GDL layers. As such, the higher the vibration amplitude and frequency, the larger the water saturation. Accordingly, the water saturation of the GDL vary sinusoidally over time. The water breakthrough paths are identified and compared during the water removal processes. Vibration in the horizontal direction is much easier to promote the water transport inside a layer compared with vibration in the vertical direction. More substantial water saturation in the GDL layers will restrict the gas transfer paths. Consequently, less oxygen will participate in the reaction, which will further impact on the fuel cell performance.     

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.     

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.     

Investigation of gas diffusion layer compression by electrochemical impedance spectroscopy on running polymer electrolyte membrane fuel cells

Two gas diffusion layers based on the same carbon cloth substrate, produced by an Italian Company (SAATI), and coated with microporous layers of different hydrophobicities, were assembled in a polymer electrolyte membrane fuel cell and its performances assessed. For comparison the cell mounting the carbon cloth without microporous layer was also tested. The membrane electrode assembly was made of Nafion^® 212 with Pt load 0.3/0.6 mg cm⁻² (anode/cathode). The cell testing was run at 60 °C and 80 °C with fully humidified air (100%RH) and 80%RH hydrogen feedings. The assembly of gas diffusion layers and membrane with electrodes was compressed to 30% and 50% of its initial thickness. For each configuration polarization and power curves were recorded; in order to evaluate the role of different GDLs, AC impedance spectroscopy of the running cell was also performed.The higher compression ratio caused the worsening of cell performances, partially mitigated when the operating temperature was raised to 80 °C. The presence of the microporous layer onto the carbon cloth resulted extremely beneficial for the operations especially at high current density; moreover, it sensibly reduces the high frequency resistance of the overall assembly.     

Numerical analyses on oxygen transport resistances in polymer electrolyte membrane fuel cells using a novel agglomerate model

Characterizing oxygen transport resistances in different components of a polymer electrolyte membrane fuel cell (PEMFC) is essential to achieve better cell performance at high current under low Pt loading. In this work, a macroscopic three-dimensional model, together with a novel agglomerate model was proposed to analyze impacts of operating conditions on these resistances via limiting current strategy. By introducing a focusing factor obtained with lattice Boltzmann method at mesoscopic level, the structure-dependent local transport resistance in ionomer thin-film of the electrode was comprehensively captured and validated by existing experimental studies. Contributions of the cell components to the total transport resistance were dissected. Results show that the present agglomerate model could well reproduce the local transport behaviors of oxygen in catalyst layer by fully considering the detailed nanoscale diffusion and adsorption processes. A small mass fraction of oxygen was favored to minimize the relative deviation of the local transport resistance from its intrinsic one due to the water production and heat generation, which can reach 7% for the mass fraction of oxygen of 1%. Contribution of the in-plane diffusion of oxygen in the inactive electrode is around 1%. The total transport resistance increased with the absolute pressure, mainly due to the dominated molecular diffusion mechanism in gas channel and gas diffusion layer. Gas convection accounted for 26% of the oxygen transport resistance originated from gas channel. The transport resistance of catalyst layer increased significantly with the reduction of Pt loading, and decreased with relative humidity and operating temperature, particularly at high Pt loading.     

Numerical modeling and analysis of micro-porous layer effects in polymer electrolyte fuel cells

It is well known that a micro-porous layer (MPL) plays a crucial role in the water management of polymer electrolyte fuel cells (PEFCs), and thereby, significantly stabilizes and improves cell performance. To ascertain the exact roles of MPLs, a numerical MPL model is developed in this study and incorporated with comprehensive, multi-dimensional, multi-phase fuel-cell models that have been devised earlier. The effects of different porous properties and liquid-entry pressures between an MPL and a gas diffusion layer (GDL) are examined via fully three-dimensional numerical simulations. First, when the differences in pore properties and wettability between the MPL and GDL are taken into account but the difference in the entry pressures is ignored, the numerical MPL model captures a discontinuity in liquid saturation at the GDL|MPL interface. The simulation does not, however, capture the beneficial effects of an MPL on cell performance, predicting even lower performance than in the case of no MPL. On the other hand, when a high liquid-entry pressure in an MPL is additionally considered, the numerical MPL model predicts a liquid-free MPL and successfully demonstrates the phenomenon that the high liquid-entry pressure of the MPL prevents any liquid water from entering the MPL. Consequently, it is found from the simulation results that a liquid-free MPL significantly enhances the back-flow of water across the membrane into the anode, which, in turn, helps to avoid membrane dehydration and alleviate the level of GDL flooding. As a result, the model successfully reports the beneficial effects of MPLs on PEFC performance and predicts higher performance in the presence of MPLs (e.g., an increase of 67 mV at 1.5 A cm⁻²). This study provides a fundamental explanation of the function of MPLs and quantifies the influence of their porous properties and the liquid-entry pressure on water transport and cell performance.     

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.     

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.     

Development of simulated gas diffusion layer of polymer electrolyte fuel cells and evaluation of its structure

In polymer electrolyte fuel cell (PEFC), it is important to understand the behavior of liquid water in gas diffusion layer (GDL) which is one of the constructional elements so as to improve the output performance and the durability. As this behavior of liquid water is attributed to not only the hydrophilicity but also inhomogeneous structure, it is needed to examine in consideration of an actual GDL structure. In this study, as the basic examination of two-phase flow analysis in an actual GDL, a simulated GDL was made by numerical analysis considering the fiber placement. Furthermore, the prediction methods for pore size distribution, permeability and tortuosity of this simulated GDL were developed with the numerical analysis. These parameters of flow and mass transfer were compared with other studies, and the validity of this simulated GDL was confirmed. In addition, effective diffusion coefficient was calculated from tortuosity in simulated GDL, and PEFC output performance was evaluated by a simple model. Moreover, the optimal GDL was examined in consideration of the effect of porosity and fiber diameter at the fiber level.     

Two-phase transport in the cathode gas diffusion layer of PEM fuel cell with a gradient in porosity

Two-phase transport in the cathode gas diffusion layer (GDL) of a proton exchange membrane fuel cell (PEMFC) is studied with a porosity gradient in the GDL. The porosity gradient is formed by adding micro-porous layers (MPL) with different carbon loadings on the catalyst layer side and on the flow field side. The multiphase mixture model is employed and a direct numerical procedure is used to analyze the profiles of liquid water saturation and oxygen concentration across the GDL as well as the resulting activation and concentration losses. The results show that a gradient in porosity will benefit the removal rate of liquid water and also enhance the transport of oxygen through the cathode GDL. The present study provides a theoretical support for the suggestion that a GDL with porosity gradient will improve the cell performance.     

Utilization of 3D printed carbon gas diffusion layers in polymer electrolyte membrane fuel cells

3D printing and carbonisation is used to produce designed gas diffusion layer materials for polymer electrolyte membrane fuel cells (PEMFC). Using a desktop UV 3D printer, designed porous microstructures are printed with micro and macro-scale features. Successful improvement of the pyrolysis process maintains the structural accuracy during carbonisation, reducing the material to electrically conductive carbon. The size of the material allows for testing in a lab scale fuel cell with 1.5 × 1.5 cm electrode size, which shows lower but interesting electrochemical performance (power density of 205 mW cm^?2). Challenges associated with integration of a 3D printed structure into a membrane electrode assembly are highlighted, including the low open circuit voltage caused by large amounts of membrane deformation and subsequent hydrogen crossover. This study shows that it is possible to design and manufacture a gas diffusion layer for fuel cells. Numerical simulation on the new GDL structure shows that advective-diffusive transport of oxygen in the 3D printed design is superior to conventional carbon paper. This study serves as the first attempt to implement 3D printed microstructures as GDL into PEMFC.     

Experimental study of the effect of dissolution on the gas diffusion layer in polymer electrolyte membrane fuel cells

The gas diffusion layer (GDL) is important for maintaining the performance of polymer electrolyte membrane (PEM) fuel cells, as its main function is to provide the cells with a path for fuel and water. In this study, the mechanical degradation process of the GDL was investigated using a leaching test to observe the effect of water dissolution. The amount of GDL degradation was measured using various methods, such as static contact angle measurements and scanning electron microscopy. After 2000 h of testing, the GDL showed structural damage and a loss of hydrophobicity. The carbon-paper-type GDL showed weaker characteristics than the carbon-felt-type GDL after dissolution because of the structural differences, and the fuel cell performance of the leached GDL showed a greater voltage drop than that of the fresh GDL. Contrary to what is generally believed, the hydrophobicity loss of GDL was not caused by the decomposition of polytetrafluoroethylene (PTFE).     

Contact resistance between bipolar plate and gas diffusion layer in high temperature polymer electrolyte fuel cells

One of the major contributors to the ohmic loss in fuel cells originates at the interface between adjacent cell components. The compressive pressure used to achieve contact in cells should be carefully estimated to ensure that resistive losses arising from contact behavior remain minimal. In present work, a generic model is developed, capable of estimating contact resistance as a function contact pressure at the interface of graphite bipolar plate and carbon fiber based gas diffusion layer at different temperatures. A good agreement is observed between the results obtained from the model and experiments. Compressive pressure in the ranges of 3–4 MPa is found optimum for achieving low contact resistance. The contact resistance obtained for carbon paper and BPP while using recommended pressure lies between ∼9 and 4 mΩ cm² considering the operating regime of HT-PEMFC (120–180 °C). Operating under similar conditions, the contact resistance values for carbon cloth and BPP is ∼13 to 7 mΩ cm².     

A study on the transport process in gas diffusion layer of proton exchange membrane fuel cells

Gas diffusion layer(GDL) plays a great important role in proton exchange membrane fuel cell(PEMFC).Water transport mechanism in GDL is still not clear.In the present study,an ex-situ transparent setup is built to visualize the transport phenomena and to measure the threshold pressure of water in GDL at different temperatures.It is found that the relationship between the breakthrough pressure and the temperature is nearly linear(i.e.the pressure decreases linearly with the increase of temperature).To avoid the problems faced by the continuum models,the pore network model is developed to simulate the liquid water transport through the carbon paper.A uniform pressure boundary condition is used in simulation and the results are similar to the ones obtained in the experiment.The reason is that the contact angle and surface tension coefficient of water in GDLs change accordingly with the change of temperature.     

Development of carbon-filled gas diffusion layer for polymer electrolyte fuel cells

The fabrication and electrochemical performance of polymer electrolyte fuel cells based on a carbon-filled gas diffusion layer (CFGDL) were studied in detail. The CFGDL consists of a PE-704 carbon electrode backing filled with a mixture of carbon powder and PTFE. The results obtained from the performance evaluation and cyclic voltammetry (CV) analyses indicate that the loading of the carbon powder in the CFGDL plays a critical role in the performance of the fuel cell and utilization of Pt, but the presence of PTFE in the CFGDL has less influence. The carbon content in the CFGDL not only affects the area specific resistance of the CFGDL but also affects the Pt utilization of the catalyst layer, the total cell resistance and thus the cell performance. The optimal performance of the PEFC was obtained when the CFGDL was filled with carbon to 6 mg cm⁻² and PTFE of 40%. The relationship between the surface morphology and microstructure of the CFGDL and the electrocatalytic activity of the cell is also discussed.