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.     

Lattice Boltzmann method modeling and experimental study on liquid water characteristics in the gas diffusion layer of proton exchange membrane fuel cells

Water transport through the gas diffusion layer (GDL) is vital to proton exchange membrane fuel cells (PEMFCs), especially under flooding conditions. In this paper, a two-dimensional (2D) lattice Boltzmann method (LBM) is applied to reveal the water dynamic characteristics in GDL, and the computational domain is reconstructed based on the experiment. In-situ experiments, including I–V performance and electrochemical impedance spectroscopy (EIS) tests under flooding conditions, are carried out and analyzed. It is found that the porosity distribution inside the GDL is a crucial factor in water dynamic behavior research. The horizontal liquid water saturation (HS_w) under the channel of real GDL (with porosity distribution) at 0.4 relative thickness are 3.2 times, 2.1 times and 3.4 times higher than the ideal GDL (without porosity distribution) in the case of 0.8 mm, 1.2 mm and 2.0 mm, respectively. The numerical simulation and experimental study show that water dynamic characteristics under the rib influence cell performance directly. In our LBM model, the GDL water distribution inconsistency (Var_w) under 2.0 mm width rib is 43.1% and 28.0% higher than that under the 0.8 mm and 1.2 mm rib, respectively. With the rib wider from 0.8 mm to 2.0 mm, some parts of cell impedance such as R_mt, R_ct, and L_mt increase 64.22%, 98.89%, and 47.46%, respectively. However, GDL under the channel shows no influence on water transport process.     

Superhydrophobic PAN nanofibers for gas diffusion layers of proton exchange membrane fuel cells for cathodic water management

Proton exchange membrane (PEM) fuel cells are considered to be promising alternatives to natural resources for generating electricity and various other powers. Optimal water management in the gas diffusion layer (GDL) is critical to the high performance of fuel cells. The basic function of the GDL includes transporting the reactant gas from flow channels to the catalyst effectively, draining liquid water from the catalyst layer to the flow channels, and conducting electrons with low humidity. In this study, poly-acrylonitrile (PAN) was dissolved in a solvent and electrospun at various conditions to produce PAN nanofibers prior to their stabilization at atmospheric pressure at 280 °C for 1 h and carbonization at 850 °C for one more hour. The surface hydrophobicity of the carbonized PAN nanofibers were adjusted using superhydrophobic and hydrophilic agents. The thermal, mechanical, and electrical properties of the new GDLs showed better results than the conventional ones. Water condensation tests (superhydrophobic and hydrophilic) on the surfaces of the GDLs showed a crucial step towards improved water management in fuel cells. This study may open up new possibilities for developing high-performing GDL materials for future PEM fuel cell applications.     

Study on ice-melting performance of gradient gas diffusion layer in proton exchange membrane fuel cell

In this study, a three-dimensional model was established using the lattice Boltzmann method (LBM) to study the internal ice melting process of the gas diffusion layer (GDL) of the proton exchange membrane fuel cell (PEMFC). The single-point second-order curved boundary condition was adopted. The effects of GDL carbon fiber number, growth slope of the number of carbon fibers and carbon fiber diameter on ice melting were studied. The results were revealed that the temperature in the middle and lower part of the gradient distribution GDL is significantly higher than that of the no-gradient GDL. With the increase of the growth slope of the number of carbon fiber, the temperature and melting rate gradually increase, and the position of the solid-liquid interface gradually decreases. The decrease in the number of carbon fibers has a similar effect as the increase in the growth slope of the number of carbon fibers. In addition, as the diameter of the carbon fiber increases, the position of the solid-liquid interface gradually decreases first and then increases.     

Effect of electrochemical aging on the interaction between gas diffusion layers and the flow field in a proton exchange membrane fuel cell

Gas diffusion layer (GDL) is a porous medium placed between the flow field and the catalyst layer in a proton exchange membrane fuel cell (PEMFC), and experiences electrochemical aging and mechanical stresses during usage. In the present work carbon cloth and carbon paper, two commonly used GDLs in PEMFC, are electrochemically aged in a simulated PEMFC environment. The results indicate that carbon paper is less prone to oxidation when compared to carbon cloth, which can be attributed to higher degree of graphitization of carbon fibers in the paper. However, carbon paper suffers greater loss of structural stability due to the adverse effects of aging on the fiber matrix interface. Increased weakening of paper when compared to cloth, after electrochemical aging, results in higher residual strain when subjected to cyclic compression and an increased intrusion of paper into the flow field channel when compared to cloth GDL.     

Influence of anisotropic gas diffusion layers on transport phenomena in a proton exchange membrane fuel cell

The gas diffusion layer is an anisotropic porous medium, which provides pathways for the reactant gases and produced water, conducts the electrical current, removes the generated heat, and provides mechanical support. However, the gas diffusion layer is mostly considered as isotropic in numerical simulations. In the present study, a three‐dimensional, two‐phase flow, and non‐isothermal agglomerate model with consideration of anisotropic permeability, mass diffusivity, thermal conductivity, and electrical conductivity was developed and employed to investigate effects of anisotropic properties on the transport phenomena in a proton exchange membrane fuel cell. The temperature of the anisotropic case is less than that of the isotropic case, and the temperature difference increases with increasing current density. Furthermore, the distributions of the oxygen mass fraction, liquid water saturation, water content, and local current density for both cases are also compared and discussed in detail. The cell performance is over‐predicted by the isotropic model, and the current density of the isotropic case is greater than that of the anisotropic case by approximately 10% at an operating cell voltage of 0.3 V. Both the local transport characteristics and overall cell performance are different for the isotropic and anisotropic cases. Accordingly, it is concluded that the anisotropic properties of the gas diffusion layer must be taken into account in the mathematical model. Copyright © 2017 John Wiley & Sons, Ltd.     

Effect of micro-cracks on the in-plane electronic conductivity of proton exchange membrane fuel cell catalyst layers based on lattice Boltzmann method

Micro-cracks commonly occur on the catalyst layers (CLs) during the manufacturing of catalyst coated membranes (CCMs). However, the crack shape parameters effect on CLs in-plane (IP) electronic conductivity λ_s is not clear. In this work, the relationship between crack parameters and the λ_s is obtained based on the two-dimensional (2D) multiple-relaxation time (MRT) lattice Boltzmann method (LBM). The LBM numerical model is validated by the normalized λ_s experiment applied on three different home-made cracked CLs, and the parameter study focus on crack width, length, quantity and phase angle are carried out. The results show that the decrease of λ_s has different sensitivity |k| to the parameters above. The crack width has little effect on λ_s decrease, and the |k_w| is 0.038. However, crack arm length and quantity show more significant impact, which |k_l| and |k_N| are 0.753 and 0.725, respectively. The CLs with different crack propagation directions show significant anisotropy on λ_s, and a 53.53% decrease in λ_s is observed between 0° and 90° crack phase angle change. To manufacture a high electronic conductivity CL, crack initiation and migration mitigation are highly encouraged.     

Microstructure reconstruction using fiber tracking technique and pore-scale simulations of heterogeneous gas diffusion layer

Two challenging tasks in pore-scale modeling of a gas diffusion layer (GDL) are realistic microstructure reconstruction and stress-strain simulation to differentiate the heterogeneous materials. This study proposes a novel method for reconstructing a GDL using fiber tracking technique and pore-scale modeling to investigate its stress-strain and anisotropic transport properties. X-ray computed tomography, fiber tracking, and morphological processing techniques were employed to reconstruct a realistic GDL. Pore-scale modeling was performed to compute the stress-strain, gas diffusivity, and electrical-thermal conductivity at different compression ratios. The sensitivity of compression speed and Young's modulus were investigated to balance the accuracy and computing cost of stress-strain simulation. The results showed that Young's modulus of 1 GPa and compression speed of 3 m/s meet the requirements for both accuracy and computational cost. The reconstructed GDL showed good agreements with the experimental data when considering fibers' orientation, length, and curvature. It was found that the stress among fibers was approximately five times higher than binders. The anisotropic ratios of diffusivity and conductivity decreased from 1.35 to 1.25, and 15 to 5, respectively, as the compression ratio increased to 25%. This study can provide accurate predictions and guidelines for GDL design with low stress and high performance.     

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.     

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.     

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.     

Pore-scale numerical study of multiphase reactive transport processes in cathode catalyst layers of proton exchange membrane fuel cells

understanding interactions between multiphase flow and reactive transport processes in catalyst layers (CL) of proton exchange membrane fuel cells is crucial for obtaining better performance and lower cost. In this study, a pore-scale model is developed to simulate coupled processes occurring in CLs, including oxygen diffusion, electrochemical reaction, and air-liquid two phase flow. Simulation conducted in an idealized local CL structures shows that the pore-scale model successfully captures dynamic behaviors of liquid water including generation, growth and subsequent migration, as well as the interaction between multiphase flow and reactive transport. Pore-scale simulation is then conducted in hydrophobic CLs with complicated structures where carbon, platinum, ionomer and pores are resolved. It is found that filling modes of the liquid water in the CLs are different. Before forming the continuous flow paths in CLs, liquid water presents as tiny droplets in pores surrounding relative large pores. After the continuous flow paths are formed, liquid water dynamic behaviors follow the capillary fingering mechanism. The multiphase flow and reactive transport processes are closely coupled with each other, and as liquid water saturation increases the reaction rate decreases. Increasing the hydrophobicity can alleviate the water flooding, accelerate the water breakthrough, and facilitate the water evaporation.     

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.     

Surface modification of gas diffusion layers by inorganic nanomaterials for performance enhancement of proton exchange membrane fuel cells at low RH conditions

Prompted by our earlier study that fumed silica on gas diffusion layer (GDL) favored a performance improvement of the single fuel cell at lower RH conditions, the present study has been carried out with inorganic oxides in the nanoscale such as TiO₂, Al₂O₃, commercially available mixed oxides, hydrophilic silica and aerosil silica. The structure of each of the oxide coating on the GDL surface has resulted in refinement with graded pore dimension as seen from the Hg porosimetry data. The fuel cell evaluation at various RH conditions (50–100%) revealed that the performance of all the inorganic oxides loaded GDL is very high compared to that of pristine GDL. The results confirm our earlier observation that inorganic oxides on GDL bring about structural refinement favorable for the transport of gases, and their water retaining capacity enable a high performance of the fuel cell even at low RH conditions.     

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.     

Effect of deformation on electrical properties of carbon fibers used in gas diffusion layer of proton exchange membrane fuel cells

In proton exchange membrane fuel cells, the stacks of anode, cathode, and membrane layers including gas diffusion layer (GDL) are held together by a compressive force applied through a bipolar plate. In this work, we studied the electrical properties of a carbon fiber of a GDL under deformation using four-point measurement methods inside a scanning electron microscope (SEM). We found out that through bending deformation the electrical resistivity of carbon fibers will be reduced. The drop in resistance during deformation may be the result of increasing conduction channels in the carbon fiber and parallel transport through them. Our finding offers a new insight on the effect of deformation on tuning the electrical properties of GDL materials.     

Carbon nano-chain and carbon nano-fibers based gas diffusion layers for proton exchange membrane fuel cells

Gas diffusion layers (GDL) for proton exchange membrane fuel cell have been developed using a partially ordered graphitized nano-carbon chain (Pureblack^® carbon) and carbon nano-fibers. The GDL samples’ characteristics such as, surface morphology, surface energy, bubble-point pressure and pore size distribution were characterized using electron microscope, inverse gas chromatograph, gas permeability and mercury porosimetry, respectively. Fuel cell performance of the GDLs was evaluated using single cell with hydrogen/air at ambient pressure, 70 °C and 100% RH. The GDLs with combination of vapor grown carbon nano-fibers with Pureblack carbon showed significant improvement in mechanical robustness as well as fuel cell performance. The micro-porous layer of the GDLs as seen under scanning electron microscope showed excellent surface morphology showing the reinforcement with nano-fibers and the surface homogeneity without any cracks.     

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.     

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.     

Highly efficient single-layer gas diffusion layers for the proton exchange membrane fuel cell

In the present study, a series of highly efficient single-layer gas diffusion layers (SL-GDLs) was successfully prepared by the addition of a vapor grown carbon nanofiber (VGCF) in the carbon black/poly(tetrafluoroethylene) composite-based SL-GDL through a simple and inexpensive process. The scanning electron micrographs of the as-prepared VGCF-containing SL-GDLs (SL-GDL-CFs) showed that the GDLs had a microporous layer (MPL)-like structure, while the wire-like VGCFs were well dispersed and crossed among the carbon black particles in the SL-GDL matrix. Utilization of the SL-GDL-CFs for MEA fabrication was also done by direct coating with the catalyst layer. Due to the presence of VGCFs, the properties of the SL-GDL-CFs, including electronic resistivity, mechanical characteristic, gas permeability, and water repellency, varied with the VGCF content, with the overall effect beneficial to the performance of the proton exchange membrane fuel cell (PEMFC). The best performances obtained from the PEMFC with VGCFs at 15 wt.% was approximately 63% higher than those without VGCFs, and about 85% as efficient as ELAT GDL, a commercial dual-layer GDL, for both the H₂/O₂ and H₂/air systems.