Effect of the micro porous layer design on the dynamic performance of a proton exchange membrane fuel cell

The mass transport characteristics of a gas diffusion layer (GDL) predominantly affect the performance of a proton exchange membrane (PEM) fuel cell. However, studies examining the transient response related to the GDL are insufficient, although the dynamic behavior of a PEM fuel cell is an important issue. In this study, the effects of the design of a micro porous layer (MPL) on the transient response of a PEM fuel cell are investigated. The MPL slurry density and multiple functional layers are treated as the variable design parameter. The results show that the transient response is determined by the capillary pressure gradient through the GDL. The trade-off relation for the PEM fuel cell performance under low and high humidity conditions due to the hydrophobic GDL is mitigated by designing a reverse capillary pressure gradient in the MPL.     

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.     

Measurement of water transport rates across the gas diffusion layer in a proton exchange membrane fuel cell,and the influence of polytetrafluoroethylene content and micro-porous layer

Water management in a proton exchange membrane (PEM) fuel cell is one of the critical issues for improving fuel cell performance and durability, and water transport across the gas diffusion layer plays a key role in PEM fuel cell water management. In this work, we investigated the effects of polytetrafluoroethylene (PTFE) content and the application of a micro-porous layer (MPL) in the gas diffusion layer (GDL) on the water transport rate across the GDL. The results show that both PTFE and the MPL play a similar role of restraining water transport. The effects of different carbon loadings in the MPL on water transport were also investigated. The results demonstrate that the higher the carbon loading in the MPL, the more it reduces the water transport rate. Using the given cell hardware and components, the optimized operation conditions can be obtained based on a water balance analysis.     

PEM fuel cell performance improvement through numerical optimization of the parameters of the porous layers

A numerical model for a PEM fuel cell has been developed and used to investigate the effect of some of the key parameters of the porous layers of the fuel cell (GDL and MPL) on its performance. The model is comprehensive as it is three-dimensional, multiphase and non-isothermal and it has been well-validated with the experimental data of a 5 cm² active area-fuel cell with/without MPLs. As a result of the reduced mass transport resistance of the gaseous and liquid flow, a better performance was achieved when he GDL thickness was decreased. For the same reason, the fuel cell was shown to be significantly improved with increasing the GDL porosity by a factor of 2 and the consumption of oxygen doubled when increasing the porosity from 0.40 to 0.78. Compared to the conventional constant-porosity GDL, the graded-porosity (gradually decreasing from the flow channel to the catalyst layer) GDL was found to enhance the fuel cell performance and this is due to the better liquid water rejection. The incorporation of a realistic value for the contact resistance between the GDL and the bipolar plate slightly decreases the performance of the fuel cell. Also the results show that the addition of the MPL to the GDL is crucially important as it assists in the humidifying of the electrolyte membrane, thus improving the overall performance of the fuel cell. Finally, realistically increasing the MPL contact angle has led to a positive influence on the fuel cell performance.     

Microscopic Observations of Freezing Phenomena in PEM Fuel Cells at Cold Starts

In polymer electrolyte membrane (PEM) fuel cells, the generated water transfers from the catalyst layer to the gas channel through microchannels of different scales in a two phase flow. It is important to know details of the water transport phenomena to realize better cell performance, as the water causes flooding at high current density conditions and gives rise to startup problems at freezing temperatures. This article presents specifics of the ice formation characteristics in the catalyst layer and in the gas diffusion layer (GDL) with photos taken with an optical microscope and a cryo scanning electron microscope (cryo-SEM). The observation results show that cold starts at –10°C result in ice formation at the interface between the catalyst layer and the microporous layer (MPL) of the GDL, and that at –20°C most of the ice is formed in the catalyst layer. Water transport phenomena through the microporous layer and GDL are also a matter of interest, because the role of the MPL is not well understood from the water management angle. The article discusses the difference in the water distribution at the interface between the catalyst layer and the GDL arising from the presence of such a microporous layer.     

Effect of PTFE content in microporous layer on water management in PEM fuel cells

The effect of hydrophobic agent (PTFE) concentration in the microporous layer on the PEM fuel cell performance was investigated using mercury porosimetry, water permeation experiment, and electrochemical polarization technique. The mercury porosimetry and water permeation experiments indicated that PTFE increases the resistance of the water flow through the GDL due to a decrease of the MPL porosity and an increase of the volume fraction of hydrophobic pores. When air was used as an oxidant, a maximum fuel cell performance was obtained for a PTFE loading of 20 wt.%. The experimental polarization curves were quantitatively analyzed to determine the polarization resistances resulting from different physical and electrochemical processes in the PEM fuel cell. The polarization analysis indicated that the optimized PTFE content results in an effective water management (i.e., a balancing of water saturations in the catalyst layer and the gas diffusion layer), thereby improving the oxygen diffusion kinetics in the membrane-electrode assembly.     

Effects of a microporous layer on the performance degradation of proton exchange membrane fuel cells through repetitive freezing

The gas diffusion layer (GDL) covered with a microporous layer (MPL) is being widely used in proton exchange membrane fuel cells (PEMFCs). However, the effect of MPL on water transport is not so clear as yet; hence, many studies are still being carried out. In this study, the effect of MPL on the performance degradation of PEMFCs is investigated in repetitive freezing conditions. Two kinds of GDL differentiated by the existence of MPL are used in this experiment. Damage on the catalyst layer due to freezing takes place earlier when GDL with MPL is used. More water in the membrane and catalyst layer captured by MPL causes permanent damage on the catalyst layer faster. More detailed information about the degradation is obtained by electrochemical impedance spectroscopy (EIS). From the point of view that MPL reduces the ohmic resistance, it is effective until 40 freezing cycles, but has no more effect thereafter. On the other hand, from the point of view that MPL enhances mass transport, it delays the increase in the mass transport resistance.     

Through-plane thermal conductivity of the microporous layer in a polymer electrolyte membrane fuel cell

Understanding the thermal properties of the microporous layer (MPL) is critical for accurate thermal analysis and improving the performance of proton exchange membrane (PEM) fuel cells operating at high current densities. In this study, the effective through-plane thermal conductivity and contact resistance of the MPL have been investigated. Gas diffusion layer (GDL) samples, coated with 5%-wt. PTFE, with and without an MPL are measured using the guarded steady-state heat flow technique described in the ASTM standard E 1225-04. Thermal contact resistance of the MPL with the iron clamping surface was found to be negligible, owing to the high surface contact area. Effective thermal conductivity and thickness of the MPL remained constant for compression pressures up to 15 bar at 0.30 W/m°K and 55 μm, respectively. The effective thermal conductivity of the GDL substrate containing 5%-wt. PTFE varied from 0.30 to 0.56 W/m°K as compression was increased from 4 to 15 bar. As a result, GDL containing MPL had a lower effective thermal conductivity at high compression than the GDL without MPL. At low compression, differences were negligible. The constant thickness of the MPL suggests that the porosity, as well as heat and mass transport properties, remain independent of the inhomogeneous compression by the bipolar plate. Despite the low effective thermal conductivity of the MPL, thermal performance of the GDL can be improved by exploiting the excellent surface contact resistance of the MPL.     

Effects of electrode wettabilities on liquid water behaviours in PEM fuel cell cathode

Liquid water transport is one of the key challenges for water management in a proton exchange membrane (PEM) fuel cell. Investigation of the air–water flow patterns inside fuel cell gas flow channels with gas diffusion layer (GDL) would provide valuable information that could be used in fuel cell design and optimization. This paper presents numerical investigations of air–water flow across an innovative GDL with catalyst layer and serpentine channel on PEM fuel cell cathode by use of a commercial Computational Fluid Dynamics (CFD) software package FLUENT. Different static contact angles (hydrophilic or hydrophobic) were applied to the electrode (GDL and catalyst layer). The results showed that different wettabilities of cathode electrode could affect liquid water flow patterns significantly, thus influencing on the performance of PEM fuel cells. The detailed flow patterns of liquid water were shown, several gas flow problems were observed, and some useful suggestions were given through investigating the flow patterns.     

Effects of an MPL on water and thermal management in a PEMFC

In this study, the effects of adding a microporous layer (MPL) as well as the impact of its physical properties on polymer electrolyte fuel cell (PEMFC) performance with serpentine flow channels were investigated. In addition, numerical simulations were performed to reveal the effect of relative humidity and operating temperature. It is indicated that adding an extra between the gas diffusion layer (GDL) and catalyst layer (CL), a discontinuity in the liquid saturation shows up at their interface because of differences in the wetting properties of the layers. In addition, results show that a higher MPL porosity causes the liquid water saturation to decrease and the cell performance is improved. A larger MPL thickness reduces the cell performance. The effects of MPL on temperature distribution and thermal transport of the membrane prove that the MPL in addition to being a water management layer also improves the thermal management of the PEMFC.     

Optimization of polytetrafluoroethylene content in cathode gas diffusion layer by the evaluation of compression effect on the performance of a proton exchange membrane fuel cell

This research investigates the optimal polytetrafluoroethylene (PTFE) content in the cathode gas diffusion layer (GDL) by evaluating the effect of compression on the performance of a proton exchange membrane (PEM) fuel cell. A special test fixture is designed to control the compression ratio, and thus the effect of compression on cell performance can be measured in situ. GDLs with and without a microporous layer (MPL) coating are considered. Electrochemical impedance spectroscopy (EIS) is used to diagnose the variations in ohmic resistance, charge transfer resistance and mass transport resistance with compression ratio. The results show that the optimal PTFE content, at which the maximum peak power density occurs, is about 5 wt% with a compression ratio of 30% for a GDL without an MPL coating. For a GDL with an MPL coating, the optimal PTFE content in the MPL is found to be 30% at a compression ratio of 30%.     

Anode water removal and cathode gas diffusion layer flooding in a proton exchange membrane fuel cell

Anode water removal (AWR) is studied as a diagnostic tool to assess cathode gas diffusion layer (GDL) flooding in PEM fuel cells. This method uses a dry hydrogen stream to remove product water from the cathode, showing ideal fuel cell performance in the absence of GDL mass transfer limitations related to water. When cathode GDL flooding is limiting, the cell voltage increases as the hydrogen stoichiometry is increased. Several cathode GDLs were studied to determine the effect of microporous layer (MPL) and PTFE coating. The largest voltage gains occur with the use of cathode GDLs without an MPL since these GDLs are prone to higher liquid water saturation. Multiple GDLs are studied on the cathode side to exacerbate GDL flooding conditions to further confirm the mechanism of the AWR process. Increased temperature and lower cathode RH allow for greater overall water removal so the voltage improvement occurs faster, though this leads to quicker membrane dehydration.     

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

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

Analysis of transient response of a unit proton-exchange membrane fuel cell with a degraded gas diffusion layer

The transient response characteristics and durability problems of proton-exchange membrane fuel cells are important issues for the application of PEM fuel cells to automotive systems. The gas diffusion layer is the key component of the fuel cell because it directly influences the mass transport mechanism. In this study, the effects of GDL degradation on the transient response of the PEM fuel cell are systematically studied using transient response analysis under different stoichiometric ratios and humidity conditions. With GDLs aged by the accelerated stress test, the effects of hydrophobicity and structural changes due to carbon loss in the GDL on the transient response of PEM fuel cells are determined. The cell voltage is measured according to the sudden current density change. The degraded GDLs that had uneven hydrophobicity distributions cause local water flooding inside the GDL and induce lower and unstable voltage responses after load changes.     

Degradations in porous components of a proton exchange membrane fuel cell under freeze-thaw cycles: Morphology and microstructure effects

In this study, porous components of a proton exchange membrane (PEM) fuel cell, i.e., single-layer gas diffusion layer (GDL, carbon paper), double-layer GDL (microporous layer (MPL) deposited carbon papers), and catalyzed electrodes, are subjected to 60 repetitive freeze-thaw cycles between −40 °C and 30 °C under water-submerged conditions; and their morphological and microstructural characteristics are investigated at each 15 cycles and compared with those of virgin materials. The results indicate that consecutive cycling of temperature causes different degradation patterns in different components. The single-layer GDL shows a unique degradation mechanism, in which macro-scale pores volumetrically expand, and relatively small-scale hollows and cracks form on the polymeric binder and carbon fiber interfaces, respectively. For the double-layer GDL, large-scale surface cracks form on the MPL surface after 15 cycles, and the morphology and microstructure degradation gains momentum with the formation of these cracks, and upon completion of 30 cycles, large-scale carbon/hydrophobic agent flakes start to detach from the surface. For the catalyzed electrodes, due to their inherently cracked surface, the catalyst layers (CLs) degrade first through expansion of the cracks in the in- and through-plane directions, and then through swelling and agglomeration of the ionomer; and combination of these two patterns triggers detachment of large CL flakes from the surface, negatively affecting the microstructure.     

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.     

Experimental analysis of a degraded open-cathode PEM fuel cell stack

The well-known challenges to overcome in PEM fuel cell research are their relatively low durability and the high costs for the platinum catalysts. This work focuses on degradation mechanisms that are present in open-cathode PEM fuel cell systems and their links to the decaying fuel cell performance. Therefore a degraded, open-cathode, 20 cell, PEM fuel cell stack was analyzed by means of in-situ and ex-situ techniques. Voltage transients during external perturbations, such as changing temperature, humidity and stoichiometry show that degradation affects individual cells quite differently towards the end of life of the stack. Cells located close to the endplates of the stack show the biggest performance decay. Electrochemical impedance spectroscopy (EIS) data present non-reversible catalyst layer degradation but negligible membrane degradation of several cells. Post-mortem, ex-situ experiments, such as cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) show a significant active area loss of the first cells within the stack due to Pt dissolution, oxidation and agglomeration. Scanning electron microscope (SEM) images of the degraded cells in comparison with the normally working cells in the stack show severe carbon corrosion of the cathode catalyst layers.     

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

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

3D classification of polymer electrolyte membrane fuel cell materials from in-situ X-ray tomographic datasets

To conduct simulations of transport properties within fuel cell materials 3D-data are required as input. For a functional simulation of flow and thermal characteristics the morphological features of the gas diffusion layer (GDL) materials must be well-defined. In this regard, the distribution of the distinct substances in the GDL, each of which is represented by a different parameter set, plays a decisive role. By means of synchrotron X-Ray computed tomography a fuel cell equipped with SGL® 28BC GDL material is recorded in 3D. The segmentation of the solid structural components and the identification of water agglomerations in the components are fulfilled by image processing techniques. This step is often realized using a lot of simplifications, like the reduction to only one or two different materials or idealized structural characteristics. In the presented work 8 different phases are defined according to the cell materials, which are the catalyst layer, the carbon fibers, the Teflon (PTFE)-binder, the micro porous layer (MPL), the flow field ribs, the pore spaces as well as the water in pore spaces of the GDL substrate and in the MPL. The image processing steps used for the classification of each voxel into these phases are described in detail in this work. Benefiting from this classification methodology, the macroscopic properties of the GDL materials such as water saturation, diffusivity, thermal and electrical conductivity can be obtained in simulations.     

Liquid and oxygen transport through bilayer gas diffusion materials of proton exchange membrane fuel cells

In proton exchange membrane fuel cells (PEMFCs), a hydrophobic micro-porous layer (MPL) is usually placed between the catalyst layer (CL) and the conventional gas diffusion layer (GDL) to relieve the flooding. In this paper, a pore network model is developed to investigate how the MPL structure affects the liquid and oxygen transport properties of the bilayer gas diffusion material (GDM) consisting of fine MPL and coarse GDL. The regular three-dimensional pore network constructed to represent the bilayer GDM are composed of the cubic pores that are connected by the narrow throats of square cross section. Based on this model, the capillary pressure, liquid permeability, and oxygen effective diffusivity as a function of GDM liquid saturation are determined. Parameter studies are performed to elucidate the influences of MPL thickness and of MPL crack width. Also analyzed are the liquid distributions in different structural GDMs at the moment of breakthrough. The results reveal a liquid saturation jump at the MPL/GDL interface in the plain bilayer GDM, but a liquid saturation drop in the defective bilayer GDM.