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.     

Characterization of transport properties in gas diffusion layers for proton exchange membrane fuel cells: 1. Wettability (internal contact angle to water and surface energy of GDL fibers)

This is the first in a series of papers in which we present state-of-the-art methods demonstrated at Case for the estimation of transport properties in gas diffusion layers (GDLs) for proton exchange membrane fuel cells (PEMFCs). Most of the methods used today for measuring wettability properties of GDLs are related to the external contact angle to water. The external contact angle however does not describe adequately capillary forces acting on the water inside the GDL pores. We show as well that the direct method of estimation of the internal contact angle using goniometry on micrographs is impractical. We propose and describe in this paper a method for estimating the internal contact angle to water and the surface energy of hydrophobic and hydrophilic gas diffusion media. The method was applied to GDLs having different contents of hydrophobic agent and carbon types. The method can be applied separately to different components of the GDL including macro-porous substrates and micro-porous layers. The uncertainty estimates using this method are usually within 3% of the measured value.     

Influence of properties of gas diffusion layers on the performance of polymer electrolyte-based unitized reversible fuel cells

Polymer electrolyte-based unitized reversible fuel cells (URFCs) combine the functionality of a fuel cell and an electrolyzer in a single device. In a URFC, titanium (Ti)-felt is used as a gas diffusion layer (GDL) of the oxygen electrode, whereas typical carbon paper is used as a GDL of the hydrogen electrode. Different samples of Ti-felt with different structural properties (porosity and fiber diameter) and PTFE content were prepared for use as GDLs of the oxygen electrode, and the relation between the properties of the GDL and the fuel cell performance was examined for both fuel cell and electrolysis operation modes. Experimental results showed that the cell with a Ti-felt GDL of 80 μm fiber diameter had the highest round-trip efficiency due to excellent fuel cell operation under relatively high-humidity conditions despite degradation in performance in the electrolysis mode.     

Modeling the original and cyclic compression behavior of non-woven gas diffusion layers for fuel cells

It is established that the compression behavior of gas diffusion layers (GDL) is dependent on the level of the mechanical stress it experienced during its lifetime. As a matter of fact, every cycle of compression induces damages in the GDL, including fibers breakage and/or their spatial reorganization. As observed in the experimental work, the first cycle of compression of GDLs as received from the suppliers is already altered by a previous compression that is applied during the manufacturing process. This paper then presents a model able to predict the cyclic behavior of GDL, considering the existence of this compressive stress applied during the manufacturing process. The experimental mechanical properties of the three main types of non-woven GDL (rolls, sheets and felts) were first measured and then predicted using the proposed model, thereby allowing to separate the influences of the manufacturing process, the type of fibers, the presence of a micro-porous layer and a hydrophobic treatment on the GDL.     

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.     

Ultra thin gas diffusion layer development for PEMFC

This research studies an ultra-thin carbon fiber paper fabrication process for proton exchange membrane fuel cells (PEMFCs). Polyacrylonitrile (PAN) based carbon fibers 6 mm long were dispersed and formed at aerial weights of 15 and 20 g/m² using a slurry molding machine. Polyscrylamide (PAM) and polyvinyl alcohol (PVA) dispersal agent solutions for fiber binding were added to evenly distribute the carbon fibers and increase the paper mechanical strength. The carbon fiber papers were dried after resin impregnation using a convective oven at 120 °C temperature for 10 min. The hot press machine was heated to 160 °C temperature and the workpieces were pressed for 5 min. Graphitization completed the gas diffusion substrate (GDS) process. GDL involves immersing the paper in a 5% polytetrafluoroethylene (PTFE) solution, coating the paper with a micro porous layer (MPL). This study shows the proposed ultra-thin GDL fabrication method is suitable for PEMFC applications and exhibits feasible functionality for fuel cells.     

Gas diffusion through differently structured gas diffusion layers of PEM fuel cells

Proton exchange membrane fuel cell (PEMFC) gas diffusion layers (GDLs) play important parts in diffusing gas, discharging liquid water, and conducting electricity, etc. When liquid water is discharged through GDL to gas channel, there will be some pores of GDLs occupied by liquid water. In this study, based on a one-dimensional model, the distribution of liquid water phase saturation is analyzed for different GDL structures including GDL with uniform porosity, GDL with sudden change porosity (GDL with microporous layer (MPL)) and GDL with gradient porosity distribution. The effect on gas diffusion of the changes of porosity and liquid saturation due to water remaining in GDL pores is calculated. The conclusions are that for uniform porosity GDL, the gas diffusion increases with the increase of porosity and contact angle and increases with the decrease of the thickness of GDL; for GDL with MPL, the larger the MPL porosity and the thinner the MPL thickness are, the stronger the gas diffusion is; for gradient change porosity GDL with the same average equivalent porosity, the larger the porosity gradient is, the more easily the gas diffuses. The optimization for GDL gradient structure shows that the GDL with a linear porosity distribution of 0.4x+0.4$0.4x+0.4$ is the best of the computed cases.     

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.     

Liquid water transport in gas flow channels of PEMFCs: A review on numerical simulations and visualization experiments

Proper water management in gas flow channels of a proton exchange membrane fuel cell (PEMFC) necessitates a comprehensive understanding of liquid water generation and motion, which are strongly related to droplet dynamics and flow patterns. Based on existing literature on numerical simulations using Volume of Fluid (VOF) method and Lattice Boltzmann method (LBM), this review identifies and analyzes the main factors in detail that affect the droplet dynamics including surface wettability, initial states of liquid water, geometrical structures of channels, and operating conditions. In addition, visualization experiments can effectively compensate for numerical simulations restricted by the limitations of length and time scale. This review focuses on optical photography, which is currently considered as the most convenient and low-cost method and discusses experimental apparatuses, qualitative flow pattern maps, and quantitative information. Finally, strategies for liquid water removal from gas flow channels are extracted to further enhance the performance of low-temperature PEMFCs.     

Facilitating mass transport in gas diffusion layer of PEMFC by fabricating micro-porous layer with dry layer preparation

For a proton exchange membrane fuel cell (PEMFC), dry layer preparation was optimized and applied to fabricate a micro-porous layer (MPL) for a gas diffusion layer (GDL). The MPLs fabricated by dry layer preparation and the conventional wet layer preparation were compared by physical and electrochemical methods. The PEMFC using dry layer MPLs showed better performance than that using wet layer MPLs, especially when the cells were operated under conditions of high oxygen utilization rate and high humidification temperature of air. The mass transport properties of the GDLs with the dry layer MPLs were also better than with the wet layer MPLs, and were found to be related to the pore size distribution in GDLs. The differences in surface morphology and pore size distribution for the GDLs with the dry layer and wet layer MPLs were investigated and analyzed. The dry layer preparation for MPLs was found to be more beneficial for forming meso-pores (pore size in the range of 0.5–15 μm), which are important and advantageous for facilitating gas transport in the GDLs. Moreover, the GDLs with the dry layer MPLs exhibited better electronic conductivity and more stable hydrophobicity than those with the wet layer MPLs. The reproducibility of the dry layer preparation for MPLs was also satisfying.     

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.     

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.     

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.     

Water permeation analysis on gas diffusion layers of proton exchange membrane fuel cells for Teflon-coating annotation

This study presents an analysis of water permeation of a polytetrafluoroethylene (PTFE)-coated gas diffusion layer (GDL) to determine the influence of hydrophobic treatment on the GDL for diagnosis of water flooding. It is found that the behaviour of water drainage is controlled by the pore configuration instead of the hydrophobicity in GDL. Better water drainage is achieved by the action of the Teflon coating in modulating the GDL pore configuration to give both a larger average pore size and a wider distribution of pore size. The results show that water penetration through the GDL must overcome a threshold surface tension defined by the largest pore range. A 30 wt.% PTFE coating of a GDL is shown to generate a satisfactory pore configuration, explaining the improved cell polarization performance with a lower driven pressure (∼1.91 kPa) and a higher rate of water drainage.     

Single-walled carbon nanotube interlayer modified gas diffusion layers to boost the cell performance of self-humidifying proton exchange membrane fuel cells

A tradeoff between the low humidity and the high performance remains a key challenge for the proton exchange membrane fuel cell (PEMFC). In this work, a novel self-humidifying gas diffusion layer (GDL) with a single-walled carbon nanotube (SWCNT) nonwoven layer between the gas diffusion substrate and the hydrophobic microporous layer is controllably prepared to elevate the cell performance under dry conditions. The membrane electrode assembly (MEA) with 0.25 mg cm⁻² SWCNT loading exhibits a current density of 0.69 A cm⁻² at 0.6 V, which is 392.8% higher than that of the counterpart without the SWCNT interlayer at the same relative humidity. Moreover, the SWCNT interlayer with rational pore structure and proper wettability dramatically improves the water retention capacity of MEA, thus enhancing the low-humidity performance of MEA. The structure design of GDL provides an effective strategy for self-humidifying PEMFC control optimization.     

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.     

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.     

Gas diffusion layer deformation and its effect on the transport characteristics and performance of proton exchange membrane fuel cell

Cell/stack assembly force can strongly affect the transport characteristics and performance of a proton exchange membrane fuel cell (PEMFC) through causing the structural deformation. In this study, a mathematical model has been developed to investigate the effect of the assembly force for different gas diffusion layers (GDL) and membranes. The results indicate that the predominant deformation of the cell structure occurs in the porous GDL due to its weak mechanical strength. Thicker GDLs result into lower water content in the GDL structure, and can sustain a larger assembly force without the risk of “electrode flooding”; while thinner GDLs have higher water content, can maintain the hydration required for the membrane, and yield a better cell performance with less sensitivity to the variations in the assembly force. Thinner membranes yield better cell performance, but the cell performance is more sensitive to the changes in the assembly force. A combination of thin GDL and membrane is beneficial for better cell performance with reasonable sensitivity to the assembly force. For thinner GDLs, an optimal assembly force exists beyond which the cell performance is reduced; and practical cell assembly force will limit the GDL thickness.     

Influence of anisotropic bending stiffness of gas diffusion layers on the electrochemical performances of polymer electrolyte membrane fuel cells

The effects of gas diffusion layer’s (GDL’s) anisotropic bending stiffness on the electrochemical performances of polymer electrolyte membrane fuel cells have been investigated for carbon fiber-felt and -paper GDLs. The bending stiffness values of all GDLs in the machine direction are higher than those in the cross-machine direction. We have prepared GDL sheet samples such that the machine direction of GDL roll is aligned with the major flow field direction of a metallic bipolar plate at angles of 0° (parallel: ‘0° GDL’) and 90° (perpendicular: ‘90° GDL’). The I–V performances of all the 5-cell stacks with 90° GDLs are higher than those with 0° GDLs. All the 5-cell stacks with 90° GDLs show lower values of high-frequency resistance (HFR) than those with 0° GDLs. However, the gas pressure differences at both anode and cathode of 5-cell stacks with 90° GDLs appear to be similar to or slightly lower than those with 0° GDLs, making the lower HFR as a dominant factor for the improved I–V performances. This may result from the reduced intrusion of 90° GDLs into gas channels than 0° GDLs as observed by less thickness reduction under compression of 90° GDLs. A 45° GDL (skew alignment) also shows better performances than the 0° GDL.     

气体扩散层结构对PEMFC性能影响二维数值模拟

质子交换膜燃料电池在运行过程中反应物从流道传输至催化层时会经过气体扩散层,气体扩散层即 可用来传输反应气体,又用来排出反应物生成的水,所以探究气体扩散层的结构对参加反应的物质及生成物 传输的影响规律有助于了解其分布情况。通过数值模拟比较了穿孔型、树状型和不规则形状气体扩散层在不 同孔隙率下顺流流动时对电池性能的影响情况。计算结果表明,气体扩散层结构严重影响质子交换膜燃料电 池性能,三种不同形状的气体扩散层对应的电性能随孔隙率的变化规律各不相同,到达催化层表面氧气的含 量受扩散层结构影响比氢气大,气体扩散层结构对阴极侧生成物水含量的影响不可忽略。