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.     

Microporous layer coated gas diffusion layers for enhanced performance of polymer electrolyte fuel cells

The influence of microporous layer (MPL) design parameters for gas diffusion layers (GDLs) on the performance of polymer electrolyte fuel cells (PEFCs) was clarified. Appropriate MPL design parameters vary depending on the humidification of the supplied gas. Under low humidification, decreasing both the MPL pore diameter and the content of polytetrafluoroethylene (PTFE) in the MPL is effective to prevent drying-up of the membrane electrode assembly (MEA) and enhance PEFC performance. Increasing the MPL thickness is also effective for maintaining the humidity of the MEA. However, when the MPL thickness becomes too large, oxygen transport to the electrode through the MPL is reduced, which lowers PEFC performance. Under high humidification, decreasing the MPL mean flow pore diameter to 3 μm is effective for the prevention of flooding and enhancement of PEFC performance. However, when the pore diameter becomes too small, the PEFC performance tends to decrease. Both reduction of the MPL thickness penetrated into the substrate and increase in the PTFE content to 20 mass% enhance the ability of the MPL to prevent flooding.     

The effect of through plane pore gradient GDL on the water distribution of PEMFC

The effect of through plane pore gradient of gas diffusion layer (GDL) on the performance of Polymer Electrolyte Membrane Fuel Cell is investigated experimentally. The performance with GDLs having no, medium and high pore gradient are compared at 2 different relative humidity (RH) conditions. The medium pore gradient GDL shows generally the best performance in both RH conditions. The performance difference is analyzed based on the water distribution. The water distribution is measured through the X-ray visualization. The amount of water is reduced with the pore gradient GDL. This change reduces the concentration over-potential, and thereby increases the performance at high RH condition. However, the reduction of liquid water results in dehydration of the membrane at low RH condition. This makes lower performance with high pore gradient. The highest performance is not matched with the highest pore gradient. The effect of pore gradient is distinct when water exists sufficiently.     

Development of a novel hydrophobic/hydrophilic double micro porous layer for use in a cathode gas diffusion layer in PEMFC

In this study, a gas diffusion layer (GDL) was modified to improve the water management ability of a proton exchange membrane fuel cell (PEMFC). We developed a novel hydrophobic/hydrophilic double micro porous layer (MPL) that was coated on a gas diffusion backing layer (GDBL). The water management properties, vapor and water permeability, of the GDL were measured and the performance of single cells was evaluated under two different humidification conditions, R.H. 100% and 50%. The modified GDL, which contained a hydrophilic MPL in the middle of the GDL and a hydrophobic MPL on the surface, performed better than the conventional GDL, which contained only a single hydrophobic MPL, regardless of humidity, where the performance of the single cell was significantly improved under the low humidification condition. The hydrophilic MPL, which was in the middle of the modified GDL, was shown to act as an internal humidifier due to its water absorption ability as assessed by measuring the vapor and water permeability of this layer.     

Importance of pore size in high-pressure hydrogen storage by porous carbons

Development of high-capacity hydrogen-storage systems utilizing physisorption at high pressure and low temperature is hindered by poor understanding of the pore size/shape requirements for achieving the maximum hydrogen uptake. Tuning the carbon structure and pore size of carbide-derived carbons (CDCs) with high accuracy by using different starting carbides, chlorination temperatures and activation temperatures allows rational design of carbon materials with increased hydrogen-storage capacity. Systematic experimental investigation of a large number of CDCs with controlled pore size distributions and specific surface area (SSA) shows that pores larger than ∼1.5 nm contribute little to hydrogen storage. It has been experimentally demonstrated that, just as at ambient pressure, pores of 0.6–0.7 nm in diameter provide the largest H₂ uptake per unit SSA at elevated pressures and liquid nitrogen temperatures. The effect of pore size was stronger than the effect of surface chemistry on the hydrogen uptake.     

Application of hyperdispersant to the cathode diffusion layer for direct methanol fuel cell

In this study, Nafion ionomer, as a kind of hyperdispersant, was added to polytetrafluoroethylene (PTFE) water dispersion system to suppress the size of PTFE particles in the ink of microporous layer (MPL). The agglomeration behavior of PTFE in ethanol and MPL were investigated by laser diffraction, dynamic light scattering (DLS) and metallurgical microscopes. The electronic resistance, pore size distribution, gas permeability and surface hydrophobic/hydrophilic properties were also characterized for prepared gas diffusion layers (GDLs). It was shown that PTFE water dispersion system suffered flocculating when dispersed in ethanol and this agglomeration behavior was reduced by employing Nafion ionomer. With the increase in the Nafion ionomer adopted in the MPL, not only the decreased hydrophobic property was shown in the MPL, but the decreased PTFE particle size was also achieved, which results in improved crosslink of carbon and pores themselves as well as the volume loss of pores in micron scale. The increased gas permeability and electronic conductivity of the GDL made the one employing the PTFE dispersion system with 1% Nafion content own its advantages as the cathode diffusion layer for a direct methanol fuel cell (DMFC) under near-ambient conditions.     

A pore network study on water distribution in bi-layer gas diffusion media: Effects of inlet boundary condition and micro-porous layer properties

Water flooding in gas diffusion material (GDM) is an important limit in performance of proton exchange membrane fuel cell (PEFMC). Some efforts, such as modifying the pore structures in the GDM, have been made in order to facilitate water transport and to reduce flooding in PEMFC. Recent experimental studies have demonstrated that using a bi-layer GDM, consisting of a fine micro-porous layer (MPL) and a coarse gas diffusion layer (GDL), can be advantageous for water management in PEMFC. In this work, a pore network model with an invasion percolation algorithm is developed and used to investigate the effects of MPL properties, including thickness, wettability and connectivity, on water distribution in the bi-layer GDM from the viewpoint at the pore level. Furthermore, a reasonable inlet boundary condition is proposed to describe the actual phenomenon that the CL surface is covered with many independent water droplets which are much larger than pore sizes in MPL. Influences of water droplet size and coverage fraction are also clarified in the present study.     

Numerical modeling and experimental study of the influence of GDL properties on performance in a PEMFC

This work is to study the effect of properties of gas diffusion layer (GDL) on performance in a polymer electrolyte membrane fuel cell (PEMFC) by both numerical simulation and experiments. The 1-dimension numerical simulation using the mixture-phase model is developed to calculate polarization curve. We are able to estimate optimum GDL properties for cell performance from numerical simulation results. Various GDLs which have different properties are prepared to verify accuracy of the simulation results. The contact angle and gas permeability of GDLs are controlled by polytetrafluoroethylene (PTFE) content in micro-porous layers (MPLs). MPL slurry is prepared by homogeneous blending of carbon powder, PTFE suspension, isopropyl alcohol and glycerol. Then the slurry is coated on gas diffusion mediums (GDMs) surface with controlled thickness by blade coating method. Non-woven carbon papers which have different thicknesses of 200 μm and 380 μm are used as GDMs. The prepared GDLs are measured by surface morphology, contact angle, gas permeability and through-plane electrical resistance. Moreover, the GDLs are tested in a 25 cm² single cell at 70 °C in humidified H₂/air condition. The contact angle of GDL increases with increasing PTFE content in MPL. However, the gas permeability and through-plane electrical conductivity decrease with increasing PTFE content and thickness of GDM. These changes in properties of GDL greatly influence the cell performance. As a result, the best performance is obtained by GDL consists of 200 μm thick non-woven carbon paper as GDM and MPL contained 20 wt.% PTFE content.     

Degradation of gas diffusion layers through repetitive freezing

This work investigates the degradation of an individual gas diffusion layer (GDL) by repeated freezing cycles. The pore size distribution, gas permeability, surface structure, and contact angle on the surface of the GDL were measured in four different types of GDL: SGL paper with a microporous layer (MPL); SGL paper with 5 wt% of polytetrafluoroethylene (PTFE) loading; Toray paper without PTFE loading; and Toray paper with 20 wt% of PTFE loading. After repeated freezing cycles, the porosity of the GDL without PTFE was reduced by 27.2% due to the volumetric expansion of the GDL. The peak of the log differential intrusion moved toward a smaller pore diameter slightly because of the repeated freezing process. The crack of the MPL increased in its width and length after repeated freezing cycles. The through-plane gas permeability of the GDL with the MPL doubled after repeated freezing cycles due to the growth of the crack in the MPL, but was very small for the GDLs with Toray paper. Besides, the GDLs with PTFE loading showed a relatively larger decrease in the contact angle on the surface than the GDL without PTFE loading due to the separation of PTFE from the carbon fiber during the repeated freezing process.     

A pore network study on the role of micro-porous layer in control of liquid water distribution in gas diffusion layer

In proton exchange membrane fuel cell (PEMFC), a hydrophobic micro-porous layer (MPL) is usually placed between catalyst layer (CL) and gas diffusion layer (GDL) to reduce flooding. Recent experimental studies have demonstrated that liquid water saturation in GDL is drastically decreased in the presence of MPL. However, theoretical studies based on traditional continuum two-phase flow models suggest that MPL has no effect on liquid water distribution in GDL. In the present study, a pore network model with invasion percolation algorithm is developed and used to investigate the impacts of the presence of MPL on liquid water distribution in GDL from the viewpoint at the pore level. A uniform pressure and uniform flux boundary conditions are considered for liquid water entering the porous layer in PEMFC. The simulation results reveal that liquid water saturation in GDL is reduced in the presence of MPL, but the reduction depends on the condition of liquid water entering the porous layer in PEMFC.     

Preparation of microporous layer for proton exchange membrane fuel cell by using polyvinylpyrrolidone aqueous solution

A new method of preparing microporous layer (MPL) for proton exchange membrane fuel cell (PEMFC) was presented in this paper. Considering the bad dispersion of PTFE aqueous suspension in the carbon slurry based on ethanol, polyvinylpyrrolidone (PVP) aqueous solution was used to prepare carbon slurry for microporous layer. The prepared gas diffusion layers (GDLs) were characterized by scanning electron microscopy, contact angle system and pore size distribution analyzer. It was found that the GDL prepared with PVP aqueous solution had higher gas permeability, as well as more homogeneous hydrophobicity. Moreover, the prepared GDLs were used in the cathode of fuel cell and evaluated with fuel cell performance and EIS analysis, and the GDL prepared with PVP aqueous solution indicated better fuel cell performance and lower ohmic resistance and mass transfer resistance.     

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.     

Interfacial transport characteristics between heterogeneous porous composite media for effective mass transfer in fuel cells

In this study, a comprehensive computational model based on a full statistical approach was developed to investigate the heterogeneous mass transport properties in the metal foam channels, gas diffusion layers (GDLs), and microporous layers (MPLs) of polymer electrolyte fuel cells (PEFCs) at the 95% confidence level. A series of channels, GDLs, and MPLs were, respectively, generated to reflect the random heterogeneous structures and transport characteristics. The critical hydrophobic pore radius in the mixed wettability GDLs was computed by applying a modified Leverett function. Furthermore, the gas transport phenomenon through a sufficient number of porous transport media was simulated using a D3Q19 (ie, three‐dimensional, 19 velocities) lattice Boltzmann method, and the corresponding mass transport characteristics were mathematically presented as a function of the porosity. The permeabilities in the channels, GDLs, and MPLs were derived from the pressure gradient and the simulated velocity distribution. It was found that the effective mass diffusion coefficient in the GDLs is mainly influenced by molecular diffusion. Nevertheless, Knudsen diffusion is the dominant mass transfer mechanism in the MPLs, because of small pore diameters. In addition, critical hydrophobic pore radius was derived using a modified Leverett function, which enables to estimate the fraction of pores larger than the critical pore radius in GDLs for effective water transport. Moreover, the interfacial areal contact ratio between two adjacent porous media (ie, channel/GDL and GDL/MPL) was calculated. The calculations indicated that the variation in the local porosity of the porous media has a significant influence on the interfacial connections. The proposed model is expected to improve the prediction performance of porous heterogeneous transport media in electrochemical energy systems and the optimization of porous media structures.     

The relevance between water release behavior and pore evolution of hard lignite during the thermal-drying process

As known, the shrinkage of coal and the pore collapsed during the drying process due to water removal. The relevance between water release behavior and pore evolution of lignite during the thermal-drying process was studied in this work. From N₂ adsorption of traditional pretreated samples and freezing wet samples, most of moisture was in the pores in the range of 26–100 nm, and results from low-field nuclear magnetic resonance (LFNMR) confirmed this conclusion that the removed moisture was in the pores with pore size smaller than 200 nm, while from the mercury intrusion porosemitry (MIP) results, the most obvious reduction of macropores was in the range of pore dimeter larger than 1 μm and there was almost no change of pore volume in the range of pore diameter smaller than 200 nm, which was completely different from traditional ideas that the pore shrunk or collapsed due to water removed. The macropores were more prone to collapse than mesopores and micropores, maybe due to its structural mechanical characteristics. And the effect of pore evolution on moisture release behavior was related to the specific drying methods and mass transfer processes.     

Effects of pore size distribution and pore-architecture assembly on drying characteristics of pore networks

Simulation of isothermal drying using two-dimensional networks comprised of interconnected cylindrical pores is presented. Transport of moisture inside pore segments was described by Fick’s law. The results have shown that the shielding of large pores by the smaller pores in the stochastic pore network, which is supposed to be representative of real porous medium, causes the lower drying rate and hence lower effective diffusion coefficient as compared to those predicted from the idealized network of pores with a single size. The strength of shielding is found to vary with the characteristics of pore size distribution as interpreted by the moisture concentration experienced by the pores, which is remarkably different amongst the pore size distributions. The inefficient transport of moisture through the stochastic pore network can be improved or even better with the suitable architecturally assembled structure. The minimum shielding archetype network, appearing very high porous at particle surface, is predicted to enhance greatly the drying rate. On the other hand, the maximum shielding network, which is small pores allocated onto the network exterior, exhibits the slowest drying rate.     

质子交换膜燃料电池建模及水热传输特性分析

针对质子交换膜燃料电池(PEMFC)水管理开展了研究,建立了一维非等温两相流解析模型,研究了不同电流密度、微孔层接触角和不同加湿方案对电池内部水分布和温度分布的影响,提出了更好的进气加湿方案。结果表明:电流密度增大会导致阳极拖干、阴极水淹加剧,导致电池各部分温度上升。因各层材料亲水性不同,在交界面处能观察到液态水阶跃现象。增大微孔层接触角促进阴极液态水反扩散到阳极,一定程度上缓解阳极变干,但过大的接触角可能导致阴极水淹加剧。通过采取"阳极充分加湿、阴极低加湿"的进气加湿方案可以有效提高电池性能,并且能在一定程度改善电池内部受热,提高电池使用寿命。     

Liquid water distribution in hydrophobic gas-diffusion layers with interconnect rib geometry: An invasion-percolation pore network analysis

Water distribution in gas diffusion layers (GDLs) of polymer electrolyte membrane fuel cells (PEMFCs) is determined by the pore morphology of the GDL as well as the flow conditions between the GDL and the gas flow field, where interconnect ribs and gas channels are placed side-by-side. The present study employs a steady state pore network model based on the invasion-percolation (IP) process to investigate the water transport in the under-rib region, in the under-channel region, and in between those regions inside the GDL. The interconnect rib partially blocks the outlet surface of the GDL, which forces water transport paths from the under-rib region to grow towards the gas channel through an extra IP process. The pore network model predicts spatially non-uniform water distributions inside the GDL due to the interconnect ribs, especially with an increased saturation level in the under-rib region. Parametric studies are also conducted to investigate the effects of several geometrical factors, such as width of the rib and the channel, thickness of the GDL, and water intruding condition at the inlet surface of the GDL.     

Effect of compression on pore size distribution and porosity of PEM fuel cell catalyst layers

In this study, effects of compression (up to 5 MPa) on pore size distribution (PSD) and porosity of catalyst layers (CL) are investigated using a developed model for deformation of CL under compression. The model is based on effective medium theory and uses a representative geometry (unit cell) to simplify the complex and random porous structure of CL. In this model, different sizes are found for unit cells which are based on CL PSD measurement; this means that unit cell size has distribution since PSD is used as an input to the model. The model has been validated with experimental data in our previous publications. Effect of compression on four different CL samples is studied using the developed model and change of pore diameter is found as function of compression. The change of pore size is different for each sample and dependents on CL initial porosity, PSD, and ink properties. PSD and porosity, which are the indications of microstructure of CL, are found after compression up to 5 MPa. Larger pores show the most change, which causes the void volume percentage of smaller pores to increase, even though the number of pores remain the same. It is also found that the diameter of secondary pores can be decreased by up to 50% depending on CL microstructure, which is significant.     

Liquid and oxygen transport in defective bilayer gas diffusion material of proton exchange membrane fuel cell

In this paper, pore network simulations are carried out to explore the effects of micro porous layer (MPL) and its crack location on the liquid and oxygen transport in the gas diffusion material (GDM) of proton exchange membrane fuel cell (PEMFC). The constructed network is composed of cubic pores connected by throats of square cross section. The GDM is partially screened by the land, and the MPL is assumed to have a crack. When the MPL crack is considered under the land in the model, the predicted results agree with experimental findings regarding the effect of MPL on the liquid saturation and distribution in the GDM. This indicates that the liquid may prefer to flow through the MPL crack under the land. The role of MPL in the fuel cell performance is revealed to be dependent on the oxygen effective diffusivity of MPL and GDL. Therefore, caution should be taken before employing the MPL to improve the cell performance. Based on the present studies, some guidelines are gained for the GDM design and optimization.     

Effect of PTFE loading of gas diffusion layers on the performance of proton exchange membrane fuel cells running at high‐efficiency operating conditions

In this paper, the effects of microporous layer (MPL) addition and polytetrafluoroethylene (PTFE) loading of gas diffusion layers (GDLs) on the overall performance of the proton exchange membrane fuel cell have been investigated. The focus was on fuel cells that operate at relatively low current densities where the power demand is low, but the efficiency is of concern. The results show that, in the activation loss‐controlled region, the performance of the fuel cell operating with moderately PTFE‐treated carbon substrates is superior over that operating with coated GDLs. This is due to the addition of the MPL which lengthens the diffusion paths and significantly reduces the mass transport properties. Conversely, in the ohmic loss‐controlled region, the fuel cell with coated GDLs performs better than those with carbon substrates. This is explained by the enhanced contact of the GDL with the adjacent components after the MPL addition, which outweighs the negative effects associated with the activation loss‐controlled region. Also, it was found that the fuel cell performance becomes lower if the GDL is treated with a relatively high PTFE loading in either the carbon substrate (due to the decrease in the porosity of the GDL) or the MPL. Copyright © 2012 John Wiley & Sons, Ltd.