Effect of polytetrafluoroethylene-treatment and microporous layer-coating on the in-plane permeability of gas diffusion layers used in proton exchange membrane fuel cells

The in-plane permeability has been experimentally estimated for a number of carbon substrates and microporous layer (MPL)-coated gas diffusion layers (GDLs) as used in proton exchange membrane (PEM) fuel cells. The results show that the in-plane permeability of the tested carbon substrates decreases with increasing polytetrafluoroethylene (PTFE) loading and, in contrast, the greater is the PTFE loading in the MPL, the greater is the permeability. It has been shown that the in-plane permeability of the carbon substrates is reduced by an order of magnitude if they are coated with MPLs. Further, the permeability is different from one in-plane principal direction to another by a factor of about two. Finally, ignoring the inertial terms (for the reported flow rates) and the compressibility of the flowing air results in significant errors in the obtained values of the permeability.     

In-plane gas permeability of proton exchange membrane fuel cell gas diffusion layers

A new analytical approach is proposed for evaluating the in-plane permeability of gas diffusion layers (GDLs) of proton exchange membrane fuel cells. In this approach, the microstructure of carbon papers is modeled as a combination of equally-sized, equally-spaced fibers parallel and perpendicular to the flow direction. The permeability of the carbon paper is then estimated by a blend of the permeability of the two groups. Several blending techniques are investigated to find an optimum blend through comparisons with experimental data for GDLs. The proposed model captures the trends of experimental data over the entire range of GDL porosity. In addition, a compact relationship is reported that predicts the in-plane permeability of GDL as a function of porosity and the fiber diameter. A blending technique is also successfully adopted to report a closed-form relationship for in-plane permeability of three-directional fibrous materials.     

Estimation of through-plane and in-plane gas permeability across gas diffusion layers (GDLs): Comparison with equivalent permeability in bipolar plates and relation to fuel cell performance

The present work focusses on measuring the permeability across gas diffusion layers (GDLs) first in a dedicated cell and later in PEM fuel cell configuration with varying bi-polar plate designs. Eight carbon paper-based GDLs with and without the microporous layer (MPL), have been tested. An in-house designed dedicated cell allowed measuring pressure drop depending on flow rate, for i) through-plane and ii) in-plane direction. Further, transport measurements were conducted in 25 cm² bi-polar plates (BPs) in fuel cell configuration having single or multiple serpentine channels, by stacking the GDL inside. The results show that gas permeability in the dedicated cell for through-plane and in-plane can be estimated by using Darcy's law. However, for BPs, the flow is affected additionally by inertial contribution (Darcy-Forchheimer). Finally, the efficiency allowed by selected GDLs installed in a fuel cell under operation shows a relationship between the equivalent permeability and the fuel cell performance.     

Characterization of transport properties in gas diffusion layers for proton exchange membrane fuel cells: 2. Absolute permeability

This is the second in a series of papers in which we present methods demonstrated in our group for the estimation of transport properties in gas diffusion layers (GDLs) for proton exchange membrane fuel cells (PEMFCs). Here we describe a method for determining separately the in-plane (x, y-directions) and through-plane (z-direction), viscous and inertial permeability coefficients of macro-porous substrates and micro-porous layers by controlling the direction of the gas flow through the porous sample. The method is applied initially to the macro-porous substrate of the GDL alone and subsequently to the macro-porous substrate with different micro-porous layers applied on it. The permeability coefficients of the micro-porous layer are calculated from the two measurements. The permeability coefficients are calculated from the Darcy–Forchheimer equation by application of the method of least squares. The method was applied to GDLs having different contents of polytetrafluoroethylene (PTFE) and carbon types. The samples with a higher PTFE content have in-plane and through-plane viscous permeability coefficients higher than those of the samples with lower PTFE content. The in-plane and through-plane viscous permeability coefficients also depend on the carbon type.     

Effect of gas diffusion layer modulus and land-groove geometry on membrane stresses in proton exchange membrane fuel cells

The electrical functionality of PEM fuel cells is facilitated by minimizing the contact resistances between different materials in the fuel cell, which is achieved via compressive clamping. The effect of the gas diffusion layer (GDL) modulus on the in-plane stress in the membrane after clamping is studied via numerical simulations, including both isotropic and anisotropic GDL properties. Furthermore, the effect of cell width and land-groove width ratio on the in-plane stress in the membrane subjected to a single hygro-thermal cycle is investigated for aligned and alternating gas channel geometries. The results from varying the GDL properties suggest that the in-plane stress in the membrane after clamping is due to a non-linear and coupled interaction of GDL and membrane deformation. The results of the geometric studies indicate that when the gas channels are aligned, the cell width and land-groove width ratio affect the in-plane stress distribution, but do not significantly affect the stress magnitudes. However, when the gas channels are alternating, the cell width and land-groove width ratio have significant effect on the membrane in-plane stresses. The effect of land-groove geometry is qualitatively verified by a series of experimental compression tests.     

Water permeation through gas diffusion layers of proton exchange membrane fuel cells

Water transport through gas diffusion layer of proton exchange membrane fuels cells is investigated experimentally. A filtration cell is designed and the permeation threshold and the apparent water permeability of several carbon papers are investigated. Similar carbon paper with different thicknesses and different Teflon loadings are tested to study the effects of geometrical and surface properties on the water transport. Permeation threshold increases with both GDL thickness and Teflon loading. In addition, a hysteresis effect exists in GDLs and the permeation threshold reduces as the samples are retested. Moreover, several compressed GDLs are tested and the results show that compression does not affect the breakthrough pressure significantly. The measured values of apparent permeability indicate that the majority of pores in GDLs are not filled with water and the reactant access to the catalyst layer is not hindered.     

Evaluating breakthrough pressure in gas diffusion layers of proton exchange membrane fuel cells

This paper studied the breakthrough pressure for liquid water to penetrate the gas diffusion layer （GDL） of a pro- ton exchange membrane fuel cell （PEMFC）. An ex-situ testing was conducted on a transparent test cell to visu- alize the water droplet formation and detachment on the surface of different types of GDLs through a CCD cam- era. The breakthrough pressure, at which the liquid water penetrates the GDL and starts to form a droplet, was measured. The breakthrough pressure was found to be different for the GDLs with different porosities and thick- nesses. The equilibrium pressure, which is defined as the minimum pressure required maintaining a constant flow through the GDL, was also recorded. The equilibrium pressure was found to be much lower than the breakthrough pressure for the same type of GDL. A pore network model was modified to further study the relationship between the breakthrough pressure and the GDL properties and thicknesses. The breakthrough pressure increases for the thick GDL with smaller micro-pore size.     

Carbon film coating on gas diffusion layer for proton exchange membrane fuel cells

This study discusses a novel process to increase the performance of proton exchange membrane fuel cells (PEMFC). In order to improve the electrical conductivity and reduce the surface indentation of the carbon fibers, we modified the carbon fibers with pitch-based carbon materials (mesophase pitch and coal tar pitch). Compared with the gas diffusion backing (GDB), GDB-A240 and GDB-MP have 32% and 33% higher current densities at 0.5 V, respectively. Self-made carbon paper with the addition of a micro-porous layer (MPL) (GDL-A240 and GDL-MP) show improved performance compared with GDB-A240 and GDB-MP. The current densities of GDL-A240 and GDL-MP at 0.5 V increased by 37% and 31% compared with GDL, respectively. This study combines these two effects (carbon film and MPL coating) to promote high current density in a PEMFC.     

Gas diffusion layer for proton exchange membrane fuel cells—A review

Gas diffusion layer (GDL) is one of the critical components acting both as the functional as well as the support structure for membrane-electrode assembly in the proton exchange membrane fuel cell (PEMFC). The role of the GDL is very significant in the H₂/air PEM fuel cell to make it commercially viable. A bibliometric analysis of the publications on the GDLs since 1992 shows a total of 400+ publications (>140 papers in the Journal of Power Sources alone) and reveals an exponential growth due to reasons that PEMFC promises a lot of potential as the future energy source for varied applications and hence its vital component GDL requires due innovative analysis and research. This paper is an attempt to pool together the published work on the GDLs and also to review the essential properties of the GDLs, the method of achieving each one of them, their characterization and the current status and future directions. The optimization of the functional properties of the GDLs is possible only by understanding the role of its key parameters such as structure, porosity, hydrophobicity, hydrophilicity, gas permeability, transport properties, water management and the surface morphology. This paper discusses them in detail to provide an insight into the structural parts that make the GDLs and also the processes that occur in the GDLs under service conditions and the characteristic properties. The required balance in the properties of the GDLs to facilitate the counter current flow of the gas and water is highlighted through its characteristics.     

Pore-network modeling of liquid water flow in gas diffusion layers of proton exchange membrane fuel cells

Fluid flow through the gas diffusion layer (GDL) of fuel cells is numerically studied using a pore network modeling approach. The model is developed based on an experimental visualization technique (fluorescence microscopy). The images obtained from this technique are analyzed to find patterns of flow inside the GDL samples with different hydrophobicity. Three different flow patterns are observed: initial invasion, progression, and pore-filling. The observation shows that liquid water flows into the majority of available pores on the boundary of the untreated GDL and several branches are segregated from the initial pathways. For the treated GDL, however, a handful of boundary pores are invaded and the original pathways extend toward the other side of the medium with minimum branching. The numerical model, developed based on an invasion percolation algorithm, is used to study the effects of GDL hydrophobicity and thickness on the flow configuration and breakthrough time as well as to determine the flow rate and saturation in different GDL samples. During the injection of water into the samples, it is numerically shown that the flow rates are monotonically decreasing for both treated and untreated samples. For the treated sample, however, the injection flow rate is constantly lower than that of the untreated sample, resulting in a lower overall water saturation at breakthrough. The numerical results also suggest that hydrophobic treatment of thick samples has minor effects on water management and overall performance. The developed model can be used to optimize the GDL properties for designing porous medium with effective transport characteristics.     

An analytical model for the transverse permeability of gas diffusion layer with electrical double layer effects in proton exchange membrane fuel cells

An analytical model is presented for the transverse permeability of gas diffusion layer (GDL) based on an ordered array of parallel charged circular cylinders at the steady state. The formula of calculating the permeability of the transverse direction is given by solving the fluid momentum equation in a unit cell. In the present approach, the proposed model is explicitly related to the porosity and fiber radius of fibrous porous media, the zeta potential, and the physical properties of the electrolyte solution. Besides, the effects of these parameters (the porosity, unit cell aspect ratio, fiber radius, and molar concentration) on the transverse permeability are discussed detailedly. The model predictions are compared with the previous studies in the available literature, and good agreement is found.     

Wire rod coating process of gas diffusion layers fabrication for proton exchange membrane fuel cells

Gas diffusion layers (GDLs) were fabricated using non-woven carbon paper as a macro-porous layer substrate developed by Hollingsworth & Vose Company. A commercially viable coating process was developed using wire rod for coating micro-porous layer by a single pass. The thickness as well as carbon loading in the micro-porous layer was controlled by selecting appropriate wire thickness of the wire rod. Slurry compositions with solid loading as high as 10 wt.% using nano-chain and nano-fiber type carbons were developed using dispersion agents to provide cohesive and homogenous micro-porous layer without any mud-cracking. The surface morphology, wetting characteristics and pore size distribution of the wire rod coated GDLs were examined using FESEM, Goniometer and Hg porosimetry, respectively. The GDLs were evaluated in single cell PEMFC under various operating conditions (temperature and RH) using hydrogen and air as reactants. It was observed that the wire rod coated micro-porous layer with 10 wt.% nano-fibrous carbon based GDLs showed the highest fuel cell performance at 85 °C using H₂ and air at 50% RH, compared to all other compositions.     

Freezing characteristics of supercooled water in gas diffusion layer of proton exchange membrane fuel cells

The freezing characteristics of supercooled water in a gas diffusion layer (GDL), which are the bases for the cold start-up of proton exchange membrane fuel cells (PEMFCs), were investigated. An experimental apparatus for noncontact temperature measurement and observation systems was developed. GDL and GDL with a microporous layer (MPL) were prepared, and freezing experiments using a water-containing GDL under various cooling rates were performed with variations in polytetrafluoroethylene (PTFE) content and water saturation. Furthermore, based on the experimental results, the freezing initiation probability was theoretically investigated to elucidate the freezing characteristics. Results showed that, with increasing supercooling of water in GDL, the freezing probability of water increased abruptly. The effect of saturation showed a different trend depending on PTFE addition. For the GDL without PTFE, the freezing initiations occurred at approximately 6 °C of supercooling degree, and the probability approached 1.0 at approximately 9.5–11.5 °C, with saturation dependency. In contrast, for both GDL and GDL + MPL containing PTFE, the initiation temperature characteristics were relatively similar, which were approximately 8–12 °C, regardless of the saturation and PTFE content. In these cases, the ice-nucleating activity of water in the GDL was possibly stronger than that in the MPL.     

Liquid transport in gas diffusion layer of proton exchange membrane fuel cells: Effects of micro-porous layer cracks

Micro porous layer (MPL) is a carbon layer (～15 μm) that coated on the gas diffusion layer (GDL) to enhance the electrical conduction and membrane hydration of proton exchange membrane fuel cell (PEMFC). However, the liquid transport behavior from MPL to GDL and its impact on water management remain unclear. Thus, a three-dimensional volume of fluid (VOF) model is developed to investigate the effects of MPL crack properties on liquid water saturation, liquid pathway formation, and the two-phase mass transport mechanism in GDL. Firstly, a stochastic orientation method is used to reconstruct the fibrous structure of the GDL. After that, the liquid water saturation calculated from the numerical results agrees well with the experimental data. With considering the full morphology of the overlap between MPL and GDL, it's found that this overlap determines the preferred liquid emerging port of both MPL and GDL. Three crack design shapes in MPL are proposed on the base of the similarity crack formation processes of soil mud. In addition, the effects of crack shape, distance between cracks, and crack number on liquid water transport from MPL to GDL are investigated. It is found that the liquid water saturation of GDL increases with crack number and the distance between cracks, while presents little correlation to the crack shape. Hopefully, these results can help the development of PEMFC models without reconstructing full MPL morphology.     

Numerical simulation of two-phase flow in gas diffusion layer and gas channel of proton exchange membrane fuel cells

Liquid water within the cathode Gas Diffusion Layer (GDL) and Gas Channel (GC) of Proton Exchange Membrane Fuel Cells (PEMFCs) is strongly coupled to gas transport properties, thereby affecting the electrochemical conversion rates. In this study, the GDL and GC regions are utilized as the simulation domain, which differs from previous studies that only focused on any one of them. A Volume of Fluid (VOF) method is adopted to numerically investigate the two-phase flow (gas and liquid) behavior, e.g., water transport pattern evolution, water coverage ratio as well as local and total water saturation. To obtain GDL geometries, an in-house geometry-based method is developed for GDL reconstruction. Furthermore, to study the effect of GDL carbon fiber diameter, the same procedure is used to reconstruct three GDL structures by varying the carbon fiber diameter but keeping the porosity and geometric dimensions constant. The wall wettability is introduced with static contact angles at carbon fiber surfaces and channel walls. The results show that the GDL fiber microstructure has a significant impact on the two-phase flow patterns in the cathode field. Different stages of two-phase flow pattern evolution in both cathode domains are observed. The liquid water in the GDL experiences water invasion, spreading, and rising, followed by the droplet breakthrough in the GDL/GC interface. In the GC, the water droplets randomly experience accumulation, combination, attachment, and detachment. Due to the difference in surface wettability, the water coverage of the GDL/GC interface is smaller than that of the channel side and top walls. It is also found that the water saturation inside the GDL stabilizes after the water breakthrough, while local water saturation at the interface keeps irregular oscillations. Last but not the least, a water saturation balance requirement between the GDL and GC is observed. In terms of varying fiber diameter, a larger fiber diameter would result in less water saturation in the GDL but more water in the GC, in addition to faster water movement throughout the total domain.     

Enhancement of proton exchange membrane fuel cell performance by titanium-coated anode gas diffusion layer

Titanium was coated onto an anode gas diffusion layer (GDL) by direct current sputtering to improve the performance and durability of a proton exchange membrane fuel cell (PEMFC). Scanning electron microscopy (SEM) images showed that the GDLs were thoroughly coated with titanium, which showed angular protrusion. Single-cell performance of the PEMFCs with titanium-coated GDLs as anodes was investigated at operating temperatures of 25 °C, 45 °C, and 65 °C. Cell performances of all membrane electrode assemblies (MEAs) with titanium-coated GDLs were superior to that of the MEA without titanium coating. The MEA with titanium-coated GDL, with 10 min sputtering time, demonstrated the best performance at 25 °C, 45 °C, and 65 °C with corresponding power densities 58.26%, 32.10%, and 37.45% higher than that of MEA without titanium coating.     

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.     

Liquid water breakthrough pressure through gas diffusion layer of proton exchange membrane fuel cell

The dynamic behavior of liquid water transport through the gas diffusion layer (GDL) of the proton exchange membrane fuel cell is studied with an ex-situ approach. The liquid water breakthrough pressure is measured in the region between the capillary fingering and the stable displacement on the drainage phase diagram. The variables studied are GDL thickness, PTFE/Nafion content within the GDL, GDL compression, the inclusion of a micro-porous layer (MPL), and different water flow rates through the GDL. The liquid water breakthrough pressure is observed to increase with GDL thickness, GDL compression, and inclusion of the MPL. Furthermore, it has been observed that applying some amount of PTFE to an untreated GDL increases the breakthrough pressure but increasing the amount of PTFE content within the GDL shows minimal impact on the breakthrough pressure. For instance, the mean breakthrough pressures that have been measured for TGP-060 and for untreated (0 wt.% PTFE), 10 wt.% PTFE, and 27 wt.% PTFE were 3589 Pa, 5108 Pa, and 5284 Pa, respectively.     

Investigation of fabrication of gas diffusion substrate for proton exchange membrane fuel cells

The gas diffusion substrate (GDS) is essential in the proton exchange membrane fuel cells. Its fabrication techniques affect the performance significantly and are worthy of investigation. In this study, a manufacturing process of the GDS is proposed to understand the formation process of GDS and promote its structure and performance more pertinently. Different states during the preparation process, raw carbon paper, pre-curing, curing, carbonation, and graphitization, are characterized and measured. Experimental and numerical methods are employed to determine the relationships between microstructure, transport, and mechanical performance variation with the fabricating processes. The results show that its porosity, average pore size, and effective diffusivity decrease first and increase after curing. These parameters after graphitization are lower than that of the carbon paper (CP). The electrical resistivity increases dramatically while pre-curing and decreases gradually after curing, carbonation, and graphitization, and it is much reduced after graphitization. Moreover, mechanical measurement results show that both the picks of tensile strength and flexural modulus occur after curing. Its tensile strength shows little change after graphitization compared to the initial paper's. In contrast, the flexural modulus is improved significantly.     

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.