Effects of porosity gradient in gas diffusion layers on performance of proton exchange membrane fuel cells

A three-dimensional, two-phase, non-isothermal model has been developed to explore the interaction between heat and water transport in proton exchange membrane fuel cells (PEMFCs). Water condensate produced from the electrochemical reaction may accumulate in the open pores of the gas diffusion layer (GDL) and retard the oxygen transport to the catalyst sites. This study predicts the enhancement of the water transport for linear porosity gradient in the cathode GDL of a PEMFC. An optimal porosity distribution was found based on a parametric study. Results show that a optimal linear porosity gradient with ?₁ = 0.7 and ?₂ = 0.3 for the parallel and z-serpentine channel design leads to a maximum increase in the limiting current density from 10,696 Am⁻² to 13,136 Am⁻² and 14,053 Am⁻² to 16,616 Am⁻² at 0.49 V, respectively. On the other hand, the oxygen usage also increases from 36% to 46% for the parallel channel design and from 55% to 67% for the z-serpentine channel design. The formation of a porosity gradient in the GDL enhances the capillary diffusivity, increases the electrical conductivity, and hence, benefits the oxygen transport throughout the GDL. The present study provides a theoretical support for existing reports that a GDL with a gradient porosity improves cell performance.     

Recent progress of gas diffusion layer in proton exchange membrane fuel cell: Two-phase flow and material properties

Proton exchange membrane (PEM) fuel cells are a promising candidate as the next-generation power sources for portable, transportation, and stationary applications. Gas diffusion layers (GDL) coated with microporous layers (MPL) are a vital component of PEM fuel cells, providing multiple functions of mechanical support, reactant transport, liquid water removal, waste heat removal, and electron conductance. In this review, we explain several most important aspects in the research and development (R&D) of this fuel cell component, including material characterization, liquid water detection/quantitation, structure reconstruction, fundamental modeling, transport properties, and durability. Specially, the commonly used microstructure reconstruction methods for GDLs are presented and discussed. Visualization techniques for liquid water detection in the GDL and MPL microstructures are described. Major modeling approaches, such as the multiphase mixture (M²) formulation, pore networks model (PNM), lattice Boltzmann method (LBM) and volume of fluid (VOF) approach, are reviewed and explained. Important material properties and parameters that greatly influence two-phase flow and fuel cell performance, and GDL-related material degradation issues are discussed and summarized to further advance on the GDL material design and development.     

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.     

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.     

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.     

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.     

Development of gas diffusion electrodes for low relative humidity proton exchange membrane fuel cells

A series of polyaniline nanofibers (PANFs) were synthesized and incorporated into gas diffusion electrodes (GDE) of proton exchange membrane fuel cells (PEMFC) to improve their performances at low relative humidity (RH) conditions. Three different placements to incorporate the PANFs in the anodes include (1) placing a PANFs layer between catalyst layer (CL) and membrane, (2) coating the CL with PANFs and catalyst mixed slurry, and (3) placing a PANFs layer between the CL and gas diffusion layer (GDL). Fuel cell performance data indicates that the last method is superior to the others and is adopted as incorporation method thereafter. Extensive studies on single cell performances have been conducted to compare the membrane electrode assemblies with and without the incorporation of PANFs in both anode and cathode. Polarization curves show the incorporation of H₂SO₄-doped PANFs is highly effective in improving the hydrophilic characteristic of the electrodes and thus can promote the PEMFC performance at low RH conditions. For example, with a lowering of reactant RH from 100 to 70%, the electrode with H₂SO₄-doped PANFs layer exhibits an increase in power density from 0.57 to 0.7 W cm⁻². On the other hand, a traditional carbon-supported platinum electrode exhibits a decline of performance from 0.73 to 0.55 W cm⁻².     

Optimal microporous layer for proton exchange membrane fuel cell

This study elucidates how fabrication processes (screen-printing and spraying) and constituent materials (carbon paper as backing, Acetylene Black (AB) carbon (42 nm), XC-72R carbon (30 nm) or BP2000 (15 nm) as carbon powders, and 10-50% fluorinated ethylene propylene (FEP) as hydrophobic substances) for microporous layers (MPLs) affect the performance of proton exchange membrane fuel cells. The screen-printing process produces MPLs with smaller surface fractures than does the spraying process. The effect of optimal FEP content on cell performance is noted. The presence of an optimal FEP content is due to the counterbalance between enhanced performance produced with increased gas permeability and decreased performance yielded with small contact area and electrical conductivity with excess FEP. The MPL with large carbon powders is preferred when oxygen supply is limited; otherwise, small carbon powders should be utilized. Optimal MPL design should address negative effects possibly associated with contact resistance, gas permeation resistance, and excess water resistance.     

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.     

Fractal model for prediction of effective hydrogen diffusivity of gas diffusion layer in proton exchange membrane fuel cell

This paper presents a novel prediction model of the effective hydrogen diffusivity for the gas diffusion layer (GDL) in proton exchange membrane fuel cell (PEMFC) by using fractal theory to characterize microstructure. With the consideration of pore-size distribution and Knudsen diffusion effect, a relationship between micro-structural parameters and effective hydrogen diffusivity of GDL is deduced. The prediction of effective hydrogen diffusivities of two samples shows that Knudsen diffusion effect makes the effective diffusivity value decrease, and after being treated with polytetrafluoroethylene (PTFE), carbon paper, a basal material of the GDL, exhibits a lower effective diffusivity value due to the decrease in the pore space and porosity. From the parametric effect study, it can be concluded that effective diffusivity has a positive correlation with pore area fractal dimension D_p or porosity ?, whereas it has a negative correlation with tortuosity fractal dimension D_t.     

Effect of water distribution in gas diffusion layer on proton exchange membrane fuel cell performance

Water management of proton exchange membrane fuel cells remains a prominent issue in research concerning fuel cells. In this study, the gas diffusion layer (GDL) of a fuel cell is partially treated with a hydrophobic agent, and the effect of GDL hydrophobicity on the water distribution in the fuel cell is examined. First, the effect of the position of the cathode GDL hydrophobic area relative to the channel on the fuel cell performance is investigated. Then, the water distribution in the fuel cell cathode GDL is observed using X-ray imaging. The experimental results indicate that when the hybrid GDL's hydrophobic area lies on the channel, water tends to accumulate under the rib, and the water content in the channel is low; this improves the fuel cell performance. When the hydrophobic area is under the rib, the water distribution is more uniform, but the performance deteriorates.     

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.     

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.     

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.     

Water transport characteristics in the gas diffusion media of proton exchange membrane fuel cell - Role of the microporous layer

Water transport through the gas diffusion media of a proton exchange membrane fuel cell (PEMFC) was investigated with a focus on the role of the microporous layer (MPL) coated on the cathode gas diffusion layer (GDL). The capillary pressure of the MPL and GDL, which plays a significant role in water transport, is derived as a function of liquid saturation using a pore size distribution (PSD) model. PSD functions are derived with parameters that are determined by fitting to the measured total PSD data. Computed relations between capillary pressure and liquid saturation for a GDL and a double-layered GDL (GDL + MPL) show good agreement with the experimental data and proposed empirical functions. To investigate the role of the MPL, the relationship between the water withdrawal pressure and liquid saturation are derived for a double-layered GDL. Water transport rates and cell voltages were obtained for various feed gas humidity using a two-dimensional cell model, and are compared with the experimental results. The calculated results for the net drag with application of the capillary pressure derived from the PSD model show good agreement with the experimental values. Furthermore, the results show that the effect of the MPL on the cell output voltage is significant in the range of high humidity operation.     

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.     

Effective permeability of gas diffusion layer in proton exchange membrane fuel cells

In gas diffusion layers (GDLs) of proton exchange membrane fuel cells (PEMFCs), effective permeability is a key parameter to be determined and engineered. In this study, through-plane (TP) and in-plane (IP) flow behaviors of GDLs are investigated analytically based on a scaling estimate method. The TP permeability and IP permeability of unidirectional fibers are determined first, based on that the minimum distance and the inscribed radius between fibers are adopted as the characteristic lengths for normal and parallel flows, respectively. The permeabilities of two-dimensional (2D) and three-dimensional (3D) GDLs are estimated by a proper mixture of the local TP and IP permeabilities of fiber alignments. The mechanistic model agrees closely with experimental and numerical results over a wide porosity range. With the new model, the influences of porosity and fiber orientation on flow behaviors are analyzed.     

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).     

Effects of the carbon black properties in gas diffusion layer on the performance of proton exchange membrane fuel cells

The microporous layer (MPL) as a part of diffusion medium has an important impact on mass transfer of proton exchange membrane fuel cell (PEMFC). In this study, MPLs of gas diffusion layers (GDLs) are prepared with different carbon blacks, and the properties of carbon blacks and their effects as MPLs on cell performance are systematically investigated. The results show that the GDL prepared by Acetylene Black (ACET) exhibits the best performance with a maximum power density up to 2.05 W cm⁻². Moreover, it still maintains extremely high performance with increasing current density even at humidity condition of 100% relative humidity, which means its excellent water/gas transportation capacity. This study contributes to deeply understanding the correlations between the properties of MPL material itself and their corresponding performance exhibited in cell. It also provides an important reference for enhancing cell performance and further advancing the practical applications of MPLs in PEMFC field.     

Optimization of cathode microporous layer materials for proton exchange membrane fuel cell

The microporous layer (MPL) of diffusion medium has an important impact on the water management ability of proton exchange membrane fuel cells. In this study, six kinds of carbon black were used to prepare the cathode MPL. The thickness, conductivity, pore structure, hydrophobicity, and surface microstructure of MPL were characterized. The single cell was prepared and electrochemical tests were performed. The results showed that the single cell prepared by Acetylene black (ACET) and Vulcan XC-72R has a considerable power generation performance. In addition, polyvinylidene fluoride hexafluoropropylene copolymer P(VDF-HFP) was used to replace Polytetrafluoroethylene (PTFE) as hydrophobic binder. MPL with different P(VDF-HFP) contents were prepared, and the single cell performance was investigated. The results showed that all the single cells prepared by P(VDF-HFP) were worse than that of PTFE. This study provides an important reference for further improving the performance of fuel cells from the perspective of material optimization with MPL.