Gas Diffusion Layer Samples Research Articles

Effect of porosity heterogeneity on the permeability and tortuosity of gas diffusion layers in polymer electrolyte membrane fuel cells

In this paper, we study the effect of porosity heterogeneity on the bulk hydrodynamic properties (permeability and tortuosity) of simulated gas diffusion layers (GDLs). The porosity distributions of the heterogeneous reconstructed samples are similar to those previously reported in the literature for Toray TGP-H 120™ GDLs. We use the lattice Boltzmann method to perform pore-level flow simulations in the reconstructed GDL samples. Using the results of pore-level simulations, the effect of porosity distribution is characterized on the predicted in- and cross-plane permeability and tortuosity. It was found that porosity heterogeneity causes a higher in-plane permeability and lower in-plane tortuosity, while the effect is opposite in the cross-plane direction, that is a lower cross-plane permeability and a higher cross-plane tortuosity.We further investigate the effect of adding poly-tetra-fluoro-ethylene (PTFE) & binder material to the reconstructed GDL samples. Three fiber volume percentages of 50, 75, and 100% are considered. Overall, increasing the fiber volume percentage reduces the predicted in- and cross-plane permeability and tortuosity values. A previously reported relationship for permeability of fibrous materials is fitted to the predicted permeability values, and the magnitude of the fitting parameter is reported as a function of fiber volume percentage.

Experimental and numerical comparison of water transport in untreated and treated diffusion layers of proton exchange membrane (PEM) fuel cells

In this paper, a fluorescein solution is injected into the gas diffusion layer (GDL) of a PEM fuel cell to simulate water flow through the porous medium under flooding conditions. The effect of the GDL hydrophobic treatment is studied by analyzing the images obtained from fluorescence microscopy. The intensity of images is correlated to the liquid water content in the medium. As a result, three distinguishable patterns are recognized between the treated and untreated GDL samples. These patterns include: (1) initial invasion, (2) progression and (3) pore filling. Based on the flow characteristics, a pore-network model is developed and applied to unique network geometry with different hydrophobic fractions to study the effect of hydrophobicity on the flow configuration. It is shown that the model predicts the flow configurations which are qualitatively in agreement with the experimental observation. The model is then used to obtain saturation for samples with different hydrophobic fractions. The trend is in agreement with the results reported in the past.

PEMFC Gas Diffusion Media Degradation Determined by Acid-Base Titrations

Numerous interlinked processes are responsible for limited durability of polymer electrolyte membrane fuel cells. One of the major phenomena that contribute to accelerated degradation of PEMFCs is loss of hydrophobicity of diffusion media caused by oxidation of carbon in the gas diffusion layer.1 The process is accompanied by formation of oxygen containing surface functional groups. While the vast majority of these groups produce characteristic signals in XPS, DRIFTS, FTIR ATR, etc., frequently an unfavorable signal to noise ratio in such measurements prevents accurate determination of the surface concentration of those functionalities. In this paper, we demonstrate successful application of Boehm type acid base titrations to determine concentrations of acidic functionalities in gas diffusion layer samples that underwent in situ and ex situ oxidation under different conditions and demonstrate correlations between those conditions and carbon oxidation.

Determination of the in-plane components of the electrical conductivity tensor in PEM fuel cell gas diffusion layers

The in-plane components of the electrical conductivity tensor for gas diffusion layers (GDLs) used in polymer electrolyte membrane fuel cells were measured using an alternative method that has not previously been applied to GDLs. This method uses a square electrode configuration, which offers many practical and theoretical advantages over conventionally used linear four point probe methods. Results obtained using this method were in excellent agreement with reported values where applicable. Pronounced anisotropy was found in the in-plane electrical conductivity for all samples, in agreement with other findings. Conductivity measurements were also performed on samples rotated relative to a fixed axis to determine the full extent of anisotropy, assumed to be due to fiber alignment, allowing the intrinsic components of the conductivity tensor to be found. The maximum and minimum conductivities were found at a rotation angle different from the main directions of the GDL sheet from which the tested samples were cut. The average in-plane conductivity of GDL samples was independent of rotation angle. Because the direction of maximum conductivity was found to differ from the main sheet axis, the measured conductivity tensor was rotated to yield the corrected 2-dimensional tensor relative to the main GDL axis. The method for performing this correction is discussed and an experimental method for measuring the necessary data from only a single sample is proposed.

Enhanced mechanical and electrochemical durability of multistage PTFE treated gas diffusion layers for proton exchange membrane fuel cells

Gas Diffusion Layers (GDLs) of Proton Exchange Membrane Fuel Cells (PEMFCs) are usually subject to polytetrafluoroethylene (PTFE) treatment in a single stage. The impact of multistage PTFE treatment on the mechanical and electrochemical durability of GDLs used in PEMFCs, is reported here. With the same total amount of PTFE in the GDL, substrates treated with PTFE in multiple stages are seen to possess distinctly improved mechanical and electrochemical durability compared to GDLs treated with PTFE in a single stage. The difference in structure and hydrophobicity of the GDLs, when they are subjected to the two different PTFE treatment routes, are examined to understand the reasons for the improvements. The results indicate that there is a change in surface morphology, pore size distribution, and hydrophobicity of the GDL samples depending on the treatment route adopted. It is observed that it is possible to establish a gradient in PTFE profile in the GDL by adopting multistage treatment. Such gradients counteract loss in hydrophobicity resulting from compression cycles during cell assembly and carbon corrosion due to electrochemical aging. The results reveal that GDLs subject to multistage PTFE treatment, can have increased lifetime as opposed to conventional single stage PTFE treated GDL.

Dynamic characterization of partially saturated engineered porous media and gas diffusion layers using hydraulic admittance

Simple laboratory methods for determining liquid water distribution in polymer electrolyte membrane fuel cell gas diffusion layers (GDLs) are needed to engineer better GDL materials. Capillary pressure vs. liquid saturation measurements are attractive, but lack the ability to probe the hydraulic interconnectivity and distribution within the pore structure. Hydraulic admittance measurements of simple capillary bundles have recently been shown to nicely measure characteristics of the free-interfaces and hydraulic path. Here we examine the use of hydraulic admittance with a succession of increasingly complex porous media, starting with a laser-drilled sample with 154 asymmetric pores and progress to the behavior of Toray TGP-H090 carbon papers. The asymmetric laser-drilled sample clearly shows hydraulic admittance measurements are sensitive to sample orientation, especially when examined as a function of saturation state. Finite element modeling of the hydraulic admittance is consistent with experimental measurements. The hydraulic admittance spectra from GDL samples are complex, so we examine trends in the spectra as a function of wet proofing (0% and 40% Teflon loadings) as well as saturation state of the GDL. The presence of clear peaks in the admittance spectra for both GDL samples suggests a few pore types are largely responsible for transporting liquid water.

Visualization and back pressure analysis of water transport through gas diffusion layers of proton exchange membrane fuel cell

Transport of water through the gas diffusion layer (GDL) is explored to simulate the water flow in the cathode of a proton exchange membrane fuel cell (PEMFC). In this study, several commercial GDL media, including carbon paper and carbon cloth with or without a microporous layer (MPL), are employed. Liquid water is injected through the GDL media, and the differential pressure drop is measured to analyze the dynamic features of the water flow through the different structures of the GDL samples. Moreover, by combining the top-view images of the water droplet that emerges out of the GDL with the results of the dynamic measurement of the differential pressure drop, the water saturation inside the GDL after the water breakthrough through the GDL is analyzed. The “self-eruption transport” mechanism, which may control the water contained inside the GDL regardless of the water generation rate, is observed in the GDL whose one side is treated with MPL only. This suggests that a GDL with single-side MPL treatment may help effectively water management.

Saturation Dependent Effective Transport Properties of PEFC Gas Diffusion Layers

Operating Polymer Electrolyte Fuel Cells (PEFC) under high current density conditions, causes significant losses related to liquid water saturation in the gas diffusion layer (GDL). The blockage of pores inside the material has a strong influence on its effective gas transport properties. Here we report on the combination of in-situ X-ray tomographic microscopy (XTM) of PEFC and the numerical determination of gas transport properties using Lattice Boltzmann and finite difference methods. The GDL domains (Toray TGP-H-060) of two identical cells, each with 11 mm2 active area, were analyzed in sections of about 0.3 to 0.8 mm2 size. Saturation levels between 0.1 and 0.4 were found, with higher saturation under the ribs. The saturated and the non-saturated states of the GDL samples were compared in order to quantify the dependence of gas phase permeability and effective relative diffusivity on liquid water saturation. Both these relative measures were found to follow power relationships of (1 − s)λ, where the exponent λ was approximately 3 for all cases except for the in-plane diffusivity where it was closer to 2.

Single phase through-plane permeability of carbon paper gas diffusion layers

Effects of mechanical compression and PTFE content on the through-plane gas permeability of gas diffusion layers (GDLs) of PEM fuel cells are investigated both experimentally and theoretically. A new test bed is designed and built which allows pressure drop and air flow rate measurement for various GDL samples. The measured values are used to calculate the through-plane permeability. Various GDLs are obtained and tested over a wide range of PTFE content and compression ratio. The experimental data show a reverse relationship between the through-plane permeability and both PTFE content and mechanical compression. An existing model for through-plane permeability of planar fibrous structures is revisited to develop a model that accommodates effects of PTFE content and mechanical compression. The proposed model captures the trends of the experimental data for the through-plane permeability, measured in the present study or reported by others.

Quantification and characterization of water coverage in PEMFC gas channels using simultaneous anode and cathode visualization and image processing

A new technique is presented to characterize and quantify the two-phase flow in the anode and cathode flow field channels using simultaneous anode and cathode visualization combined with image processing. In situ visualization experiments were performed at 35 °C with stoichiometric ratios (an/ca) of 1.5/2.5, 1.5/5, 3/8 to elucidate two-phase flow dynamics at lower temperature/low power conditions, when excess liquid water in the cell can be especially prevalent. Video processing algorithms were developed to automatically detect and quantify dynamic and static liquid water present in the flow field channels, as well as discern the distribution of water among different two-phase flow structures. The water coverage ratio was introduced as a parameter to capture the time-averaged flow field water content information through recorded high speed video sequences. The automated processing allows for efficient and robust spatial and temporal averaging of steady state channel water over very large visualization data sets acquired through high speed imaging. The developed algorithm calculates the water coverage ratio using the liquid water in the channels which is contacting the GDL surface, and selectively removes the superficial condensation on the visualization window from the coverage area. The water coverage ratio and distribution metrics techniques were demonstrated by comparing the performance of Freudenberg and Toray gas diffusion layers (GDLs) from a water management perspective, including direct anode to cathode comparisons of simultaneous water coverage data for each GDL sample. The anode water coverage ratio was found to exceed the cathode for both GDL samples at most operating conditions tested in this work. The Freudenberg GDL consistently demonstrated a higher water coverage ratio in the flow field gas channels than the Toray GDL, while the Toray GDL indicated a propensity for greater water retention within the membrane electrode assembly (MEA) based on performance, high frequency resistance (HFR), and water coverage metrics.

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.

Determination of effective water vapor diffusion coefficient in pemfc gas diffusion layers

The primary removal of product water in proton exchange membrane (PEM) fuel cells is through the cathode gas diffusion layer (GDL) which necessitates the understanding of vapor and liquid transport of water through porous media. In this investigation, the effect of microporous layer (MPL) coatings, GDL thickness, and polytetrafluorethylene (PTFE) loading on the effective water vapor diffusion coefficient is studied. MRC Grafil, SGL Sigracet, and Toray TGP-H GDL samples are tested experimentally with and without MPL coatings and varying PTFE loadings. A dynamic diffusion test cell is developed to produce a water vapor concentration gradient across the GDL and induce diffusion mass transfer. Tests are conducted at ambient temperature and flow rates of 500, 625, and 750 sccm. MPL coatings and increasing levels of PTFE content introduce significant resistance to diffusion while thickness has negligible effects.

A Two‐dimensional Network Study on Oxygen Transport in Porous Gas Diffusion Layer

AbstractOxygen transport in the porous gas diffusion layer (GDL), which is generally characterised by the oxygen effective diffusivity, is of great importance for the performance of proton exchange membrane fuel cells (PEMFCs). The determination of the oxygen effective diffusivity is challenging due to the complex structure of the porous GDL samples. In the present study, a two‐dimensional network consisting of arms and nodes is adopted to illustrate how oxygen effective diffusivity is affected by the GDL structure under the condition with/without water invasion. Water permeation in the network is simulated using the invasion percolation algorithm and oxygen transport in the arms is described by Fick's law. The simulation results reveal that oxygen effective diffusivity under dry condition decreases with increase in the network heterogeneity. With water permeation, the oxygen effective diffusivity goes to zero even though water saturation is rather less than unity. The critical water saturation, above which the oxygen effective diffusivity becomes zero, is found to decrease with increasing heterogeneity. To enhance oxygen transport, four different modified networks are introduced in the present study. It is found that the network with large arms in oxygen transport direction has the best oxygen and water transport properties.

A Numerical Study of Structural Change and Anisotropic Permeability in Compressed Carbon Cloth Polymer Electrolyte Fuel Cell Gas Diffusion Layers

AbstractThe effect of compression on the actual structure and transport properties of the carbon cloth gas diffusion layer (GDL) of a polymer electrolyte fuel cell (PEFC) are studied here. Structural features of GDL samples compressed in the 0.0–100.0 MPa range are encapsulated using polydimethylsiloxane (PDMS) and by employing X‐ray micro‐tomography to reconstruct direct digital 3D models. Pore size distribution (PSD) and porosity data are acquired directly from these models while permeability, degree of anisotropy and tortuosity are determined through lattice Boltzmann (LB) numerical modelling. The structural models reveal that structural change proceeds through a three‐step process, while PSD data suggests a characteristic peak in the pore diameter of 10–14 μm and a decrease in the mean pore diameter from 33 to 12 μm over the range of tested pressures. A mathematical relationship between compression pressure and permeability is determined based on the Kozeny–Carman equation, revealing a one order of magnitude reduction in through‐plane permeability for a two order of magnitude increase in pressure. The results also reveal that the degree of anisotropy peaks in the range of 0.3–10.0 MPa, suggesting that in‐plane permeability can be maximised relative to through‐plane permeability within a material‐specific range of compression pressures.

Measurement of Average Contact Angles of Gas Diffusion Layers Using a Novel Fluorescence Microscopy Method

One of the major problems of current proton exchange membrane (PEM) fuel cells is water management. The gas diffusion layer (GDL) of the fuel cell plays an important role in water management since humidification and water removal are both achieved through the GDL. Various numerical models were developed to illustrate the multiphase flow and transport in the fuel cell. The accuracy of these models depends on the accurate measurement of the GDL properties such as wettability, surface energy, and porosity. Most of the studies conducted for measuring the wettability of the GDL are based on the external contact angle measurements. However, the external contact angle does not describe adequately the capillary forces acting on the water inside the GDL pores. In a recent study, the capillary penetration technique has been used to measure indirectly the wettability of the GDL based on the experimental height increase due to penetration of the liquid into the porous sample. In essence, the height penetration technique was used along with the general Washburn equation to determine the surface properties of GDLs [Friess and Hoorfar, 2010, “Measurement of Internal Wettability of Gas Diffusion Porous Media of PEM Fuel Cells,” J. Power Sources, 195, pp. 4736–4742]. The shortcoming of this method is that it is only effective for thin GDL samples with low poly(tetrafluoroethylene) (PTFE) loading since the digital images acquired to find the height of penetration has a limited contrast between the penetrated and unpenetrated areas. Since fuel cells need to use different combinations of PTFE loading and thickness depending on the desired use of the cell, it is important to find a way to measure the contact angle of the GDLs with different PTFE loadings and thicknesses. This paper presents a novel fluorescence microscopy method that drastically improves the contrast in the images and allows for the accurate measurement of the height of penetration of the test liquid at each time step. This penetrated height values are then used along with an optimization method (which finds the best fit between the general Washburn equation and the experimental data) to calculate the contact angle of the test liquid on the GDL sample.

Effect of Surface Modification for the Growth of Multi-Walled Carbon Nanotubes on Carbon Paper for Proton Exchange Membrane Fuel Cells

Gas Diffusion Layers (GDL) were fabricated with carbon paper substrate and multi-walled carbon nanotubes (MWCNTs) grown in situ as microporous layer by chemical vapor deposition (CVD) process. In order to nucleate, various nano-oxides viz., aerosil-380, hydrophilic silica, hydrophobic silica, Al2O3 and a mixed oxide (Al2O3 and SiO2) and TiO2 were evaluated for optimum growth of MWCNTs. The GDL samples with the MWCNTs were characterized by surface morphology, and wetting characteristics using a scanning electron microscope and goniometer, respectively. Pt nanocatalyst was deposited on the MWCNTs both for anode and cathode. The fuel cell performance of the Pt/MWCNTs/carbon paper cathodes was evaluated by using PEMFC with H2/O2 and H2/air, at 80 oC and at different RH conditions using Nafion-212 electrolyte. Al2O3 led to homogenous growth of MWCNTs and the GDL exhibited the maximum performance. The in-situ Pt/CNT/carbon paper electrodes showed 1 and 0.5 W.cm-2 with H2/O2 and H2/air, respectively.

Water management studies in PEM fuel cells, part III: Dynamic breakthrough and intermittent drainage characteristics from GDLs with and without MPLs

The transport of liquid water and gaseous reactants through a gas diffusion layer (GDL) is one of the most important water management issues in a proton exchange membrane fuel cell (PEMFC). In this work, the liquid water breakthrough dynamics, characterized by the capillary pressure and water saturation, across GDLs with and without a microporous layer (MPL) are studied in an ex-situ setup which closely simulates a real fuel cell configuration and operating conditions. The results reveal that recurrent breakthroughs are observed for all of the GDL samples tested, indicating the presence of an intermittent water drainage mechanism in the GDL. This is accounted for by the breakdown and redevelopment of the continuous water paths during water drainage as demonstrated by Haines jumps. For GDL samples without MPL, a dynamic change of breakthrough locations is observed, which originates from the rearrangement of the water configuration in the GDL following the drainage. For GDL samples with MPL, no dynamic change of breakthrough location can be found and the water saturation is significantly lower than the samples without MPL. These results suggest that the MPL not only limits the number of water entry locations into the GDL (such that the water saturation is drastically reduced), but also stabilizes the water paths (or morphology). The effect of MPL on the two-phase flow dynamics in gas channels is also studied with multi-channel flow experiments. The most important result is that GDL without MPL promotes film flow and shifts the slug-to-film flow transition to lower air flow rates, compared with the case of GDL with MPL. This is closely related to the larger number of water breakthrough locations through GDL without MPL, which promotes the formation of water film.

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

The purpose of this study is to investigate the effect of ploytetrafluoroethylene (PTFE)-treatment and microporous layer (MPL)-coating on the electrical conductivity of gas diffusion layers (GDLs), as used in proton exchange membrane fuel cells (PEMFCs). The results show that, for PTFE-treated GDLs, the electrical conductivity in orthogonal in-plane directions is almost invariant with the PTFE loading. On the other hand, the in-plane conductivity of the MPL-coated GDL SGL 10BE (50% PTFE) was found to be higher than that of the counterpart SGL 10BC (25% PTFE) and this was explained by the presence of more conductive carbon particles in the MPL of SGL 10BE. Further, the conductivity of each GDL sample was measured in two perpendicular in-plane directions in order to investigate the in-plane anisotropy. The results show that the electrical conductivity of the GDL sample in one direction is different to that in the other direction by a factor of about two. The contact resistance, the main factor affecting the through-plane conductivity, of PTFE-treated GDLs shows a different trend to the corresponding in-plane conductivity, namely it increases as the PTFE loading increases. On the other hand, the contact resistance of the MPL-coated GDL SGL 10BE (50% PTFE) was found to be lower than that of the counterpart SGL 10BC (25% PTFE) and again this was explained by the presence of more conductive carbon particles in the MPL of SGL 10BE. Also, it was noted that the MPL coating appears to have a positive effect in reducing the contact resistance between the GDL and the bipolar plate. This is most likely due to the compressibility of the MPL layers that allows them to fill in the ‘gaps’ that exist in the surface of the bipolar plates and therefore establishes a good contact between the latter plates and the GDLs. Finally, good curve fitting of the contact resistance as a function of the clamping pressure has been achieved.

In situ accelerated degradation of gas diffusion layer in proton exchange membrane fuel cell: Part I: Effect of elevated temperature and flow rate

Past studies have shown that both the substrate and microporous layer of the gas diffusion layer (GDL) significantly affect water balance and performance of a proton exchange membrane (PEM) fuel cell. However, little effort has been made to investigate the importance of GDL properties on the durability of PEM fuel cells. In this study, the in situ degradation behaviour of a commercial GDL carbon fiber paper with MPL was investigated under a combination of elevated temperature and elevated flow rate conditions. To avoid the possible impact of the catalyst layer during degradation test, different barriers without catalyst were utilized individually to isolate the anode and cathode GDLs. Three different barriers were evaluated on their ability to isolate GDL degradation and their similarity to a fuel cell environment, and finally a novel Nafion/MPL/polyimide barrier was chosen. Characterization of the degraded GDL samples was conducted through the use of various diagnostic methods, including through-plane electrical resistivity measurements, mercury porosimetry, relative humidity sensitivity, and single-cell performance curves. Noticeable decreases in electrical resistivity and the hydrophobic properties were detected for the degraded GDL samples. The experimental results suggested that material loss plays an important role in GDL degradation mechanisms, while excessive mechanical stress prior to degradation weakens the GDL structure and changes its physical property, which consequently accelerates the material loss of the GDL during aging.

The effects of wetproofing on the capillary properties of proton exchange membrane fuel cell gas diffusion layers

In the analysis of proton exchange membrane (PEM) fuel cell components, the capillary pressure vs. saturation ( P C ( S L )) curve is an increasingly popular tool for understanding the interaction of liquid water with the porous gas diffusion layer (GDL) material. In this study, hysteretic water/air P C ( S L ) measurements were combined with mercury intrusion porosimetry (MIP) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging to quantify the effects of fluoropolymer loading on GDL samples. Commercially wetproofed carbon fiber papers with 0–40 wt.% Teflon loading were investigated. MIP showed a slight reduction in characteristic pore radii and a significant loss of pore volume at the highest Teflon loading. Water/air P C ( S L ) measurements showed a significant reduction in water wetting between samples with 0 and 5 wt.% Teflon loading, but negligible additional wetproofing at loadings from 10 to 40 wt.%. ToF-SIMS imaging, a technique that is sensitive to monolayer surfaces coverages, found that GDL materials with 5 wt.% Teflon loading displayed nearly complete fluoropolymer coverage on the carbon substrate, confirming P C ( S L ) measurements showing that all of the wetproofing occurs in a narrow range of Teflon loadings. Results for P C ( S L ) measurements were fitted using a bundle-of-capillaries model. The apparent water intrusion contact angles fell between 130° and 133° in the rough Teflonated pore space (regardless of loading), whereas the apparent gas intrusion contact angles fell between 66° and 70° for the same materials.