Understanding the role of cathode structure and property on water management and electrochemical performance of a PEM fuel cell

Water management is vital for the successful development of PEM fuel cells. Water should be carefully balanced within a PEM fuel cell to meet the conflicting requirements of membrane hydration and cathode anti-flooding. In order to understand the key factors that can improve water management and fuel cell performance, the cathodes with different structures and properties are prepared and tested in this study. The experimental results show that even though no micro-porous layer (MPL) is placed between the cathode catalyst layer (CCL) and macro-porous substrate (MaPS), a hydrophobic CCL is effective to prevent cathode flooding and keep membrane hydrated. The impedance study and the analysis of the polarization curves indicate that the optimized hydrophobic micro-porous structure in the MPL or the hydrophobic CCL could be mainly responsible for the improved water management in PEM fuel cells, which functions as a watershed to provide wicking of liquid water to the MaPS and increase the membrane hydration by enhancing the back-diffusion of water from the cathode side to the anode side through the membrane.     

Estimation of flooding in PEMFC gas diffusion layer by differential pressure measurement

The flooding, especially in gas diffusion layer (GDL), is one of the critical issues to put PEMFC to practical use. However, the experimental data of the flooding in GDL is so insufficient that the optimization design related to the water management for GDL has not established. In this study we developed a method to estimate the water saturation, namely the ratio of liquid water to pore volume in GDL. We fabricated a simple interdigitated cell where the supply gas is enforced to flow under rib. This structure enables to estimate the liquid water ratio in GDL by the measurement of differential pressure through the cell. We operated the cell and measured the differential pressure, and succeeded in estimating the water saturation, which changed largely with changing cell operation condition. In addition to this deferential pressure measurement, we measured the ionic resistance in polymer electrolyte membrane by ac impedance method. We evaluated and discussed the influence of the water saturation on cell voltage.     

Innovative gas diffusion layers and their water removal characteristics in PEM fuel cell cathode

Liquid water transport is one of the key challenges regarding the water management in a proton exchange membrane (PEM) fuel cell. Conventional gas diffusion layers (GDLs) do not allow a well-organized liquid water flow from catalyst layer to gas flow channels. In this paper, three innovative GDLs with different micro-flow channels were proposed to solve liquid water flooding problems that conventional GDLs have. This paper also presents numerical investigations of air–water flow across the proposed innovative GDLs together with a serpentine gas flow channel on PEM fuel cell cathode by use of a commercial computational fluid dynamics (CFD) software package FLUENT. The results showed that different designs of GDLs will affect the liquid water flow patterns significantly, thus influencing the performance of PEM fuel cells. The detailed flow patterns of liquid water were shown. Several gas flow problems for the proposed different kinds of innovative GDLs were observed, and some useful suggestions were given through investigating the flow patterns inside the proposed GDLs.     

Proposal for an optimum water management method using two-pole simultaneous measurement

Most designers of Polymer Electrolyte Fuel Cells (PEFCs) supply the PEFC with humidified gas to prevent its membrane from drying. Because the steam generated by the electrochemical reaction is added to a humidified supply gas, the steam partial pressure in the cathode channel forces a supersaturated state. Therefore, the PEFC has water management issues, such as flooding and plugging. Many researchers have studied these issues in the cathode side using a visualization technique, and have introduced water repellency processing to the gas channel and GDL (gas diffusion layer) as a solution. However, the flooding/plugging phenomena in the cathode do not occur alone, and are influenced by the flooding/plugging phenomena in the anode channel through the membrane. Moreover, the water transport phenomenon through the membrane is affected by the locations of the flooding/plugging phenomena in each gas channel. Therefore, we aim to examine the water transport phenomenon through the membrane by the two-pole simultaneous image measurement, and to propose an optimum water management method. This work shows that the flooding/plugging phenomena on the anode side are clearly related to water transportation from the cathode side through the membrane.     

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.     

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.     

Measurement of the water transport rate in a proton exchange membrane fuel cell and the influence of the gas diffusion layer

Water management in a PEM fuel cell significantly affects the fuel cell performance and durability. The gas diffusion layer (GDL) of a PEM fuel cell plays a critical role in the water management process. In this short communication, we report a simple method to measure the water transport rate across the GDL. Water rejection rates across a GDL at different cathode air-flow rates were measured. Based on the measurement results, the fuel cell operating conditions, such as current density, temperature, air stoichiometry and relative humidity, corresponding to membrane drying and flooding conditions were identified for the particular GDL used. This method can help researchers develop GDLs for a particular fuel cell design with specific operating conditions and optimize the operation conditions for the given PEM fuel cell components.     

Visualisation of water droplets during the operation of PEM fuel cells

A transparent proton exchange membrane fuel cell (PEMFC) has been designed to enable visualisation of water droplets during its operation. Images of the formation of droplets on the surface of the gas diffusion layer (GDL) on its cathode side, which result in water accumulation and blockage to the airflow channels, were recorded using a CCD camera. Measurement of the cell current and droplet characterisation have been carried out simultaneously and the effect of the airflow and external resistive load has been quantified. The droplet images show that water accumulation occurs first in the middle channels of a serpentine reactant-flow fuel cell design and that no droplets are formed at the bends of the flow channels. Water blockage to the airflow path was caused by the overlapping of two land-touching droplets developing on each side of the channel. Flooding was found to be more susceptible to the airflow than the other test operating conditions.     

Enhancement of water retention in the membrane electrode assembly for direct methanol fuel cells operating with neat methanol

It is desirable to operate a direct methanol fuel cell (DMFC) with neat methanol to maximize the specific energy of the DMFC system, and hence increasing its runtime. A way to achieve the neat-methanol operation is to passively transport the water produced at the cathode through the membrane to the anode to facilitate the methanol oxidation reaction (MOR). To achieve a performance of the MOR similar to that under the conventional diluted methanol operation, both the water transport rate and the local water concentration in the anode catalyst layer (CL) are required to be sufficiently high. In this work, a thin layer consisting of nanosized SiO₂ particles and Nafion ionomer (referred to as a water retention layer hereafter) is coated onto each side of the membrane. Taking advantage of the hygroscopic nature of SiO₂, the cathode water retention layer can help maintain the water produced from the cathode at a higher concentration level to enhance the water transport to the anode, while the anode retention layer can retain the water that is transported from the cathode. As a result, a higher water transport rate and a higher water concentration at the anode CL can be achieved. The formed membrane electrode assembly (MEA) with the added water retention layers is tested in a passive DMFC and the results show that this MEA design yields a much higher power density than the MEA without water retention layers does.     

The effects of water and microstructure on the performance of polymer electrolyte fuel cells

In this paper, we present a comprehensive non-isothermal, one-dimensional model of the cathode side of a Polymer Electrolyte Fuel Cell. We explicitly include the catalyst layer, gas diffusion layer and the membrane. The catalyst layer and gas diffusion layer are characterized by several measurable microstructural parameters. We model all three phases of water, with a view to capturing the effect that each has on the performance of the cell. A comparison with experiment is presented, demonstrating excellent agreement, particularly with regard to the effects of water activity in the channels and how it impacts flooding and membrane hydration. We present several results pertaining to the effects of water on the current density (or cell voltage), demonstrating the role of micro-structure, liquid water removal from the channel, water activity, membrane and gas diffusion layer thickness and channel temperature. These results provide an indication of the changes that are required to achieve optimal performance through improved water management and MEA-component design. Moreover, with its level of detail, the model we develop forms an excellent basis for a multi-dimensional model of the entire membrane electrode assembly.     

Effects of ratio variation in substrate and micro porous layer penetration on polymer exchange membrane fuel cell performance

A gas diffusion layer (GDL) facilitates the diffusion of reactant gas and the discharge of the generated water. The GDL performs various functions, such as conducting heat and electrons generated by electrochemical reactions and providing mechanical support for the catalyst layer. In this study, the effects of ratio variation in the substrate and microporous layer (MPL) penetration region on the proton exchange membrane fuel cell (PEMFC) performance were investigated. Furthermore, the reasons for these performance tendencies are explained based on the thermogravimetric analysis, contact angle, scanning electron microscopy, mercury porosimetry, electrical resistance, electrochemical impedance spectroscopy, and capillary pressure gradient. The experimental results indicate that the MPL penetration ratio within 15–20% of the total GDL thickness and the combined ratio of the MPL and MPL penetration within 35–40% is the best for the overall PEMFC performance. In addition, when the substrate ratio is excessively low, water flooding substantially occurs in the substrate, and this accumulated water functions as a back pressure, causing severe capillary condensation in the MPL penetration region and thus depriving the supply of the reactant gas.     

Water balance simulations of a polymer-electrolyte membrane fuel cell using a two-fluid model

A previously published computational multi-phase model of a polymer-electrolyte membrane fuel cell cathode has been extended in order to account for the anode side and the electrolyte membrane. The model has been applied to study the water balance of a fuel cell during operation under various humidification conditions. It was found that the specific surface area of the electrolyte in the catalyst layers close to the membrane is of critical importance for the overall water balance. Applying a high specific electrolyte surface area close to the membrane (a water-uptake layer) can prevent drying out of the anode and flooding at the cathode while the average membrane water content is only weakly affected. The results also indicate that in contrast to common presumption membrane dehydration may occur at either anode or cathode side, entirely depending on the direction of the net water transport because the predominant transport mechanism is diffusion. Consequently, operating conditions with a high net water transport from anode to cathode should be avoided as it is important to keep the cathode catalyst layer well humidified in order to prevent high protonic losses. Addition of the micro-porous layer did not affect the overall water balance or membrane water content in our study.     

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.     

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.     

Gas diffusion layer design focusing on the structure of the contact face with catalyst layer against water flooding in polymer electrolyte fuel cell

High humidity must be maintained inside polymer electrolyte fuel cells to achieve high ion conductivity. However, water condensation blocks the diffusion of the reaction gas in the gas diffusion layer under water saturation conditions which are produced by the product water. This effect is known as flooding and causes a sudden drop in the cell voltage. Therefore, advanced water management is required in such fuel cells. Internal water management is generally carried out by making adjustments to the gas diffusion layer. This study reports that the extremely highly flood-resistant gas diffusion layer has been developed, based on simple carbon paper. It was experimentally revealed that flooding is controlled by a gas diffusion layer with a smaller pore-structure facing the catalyst layer and it is one of the governing factors for flooding in the gas diffusion layer.     

Simulation on water transportation in gas diffusion layer of a PEM fuel cell: Influence of non-uniform PTFE distribution

Proton exchange membrane fuel cells (PEMFCs) are promising clean power sources with high energy conversion efficiency, fast startup, and no pollutant emission. The generated water in the cathode can cause water flooding of the catalyst layer (CL), which in turn can significantly decrease the fuel cell performance. To address this significant issue of PEMFC, a new gas diffusion layer (GDL) with non-uniform distribution of PTFE is proposed for water removal from the CL. The feasibility of this new GDL design is numerically evaluated by a Lattice-Boltzmann Method (LBM)-based two-phase flow model. The porous structure of the new GDL design is numerically reconstructed, followed by LBM simulations of the water transport in GDL. Three types of different wetting conditions are considered. It is found that liquid water transported 7.87% more with a single row of wetted solids and 13.36% more with two rows of wetted solids. The results clearly demonstrate that the liquid water can be effectively removed from the GDL by proper arrangement of hydrophilic solids in the GDL.     

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

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

Effects of porosity distribution variation on the liquid water flux through gas diffusion layers of PEM fuel cells

Flooding of the membrane electrode assembly (MEA) and dehydrating of the polymer electrolyte membrane have been the key problems to be solved for polymer electrolyte membrane fuel cells (PEMFCs). So far, almost no papers published have focused on studies of the liquid water flux through differently structured gas diffusion layers (GDLs). For gas diffusion layers including structures of uniform porosity, changes in porosity (GDL with microporous layer (MPL)) and gradient change porosity, using a one-dimensional model, the liquid saturation distribution is analyzed based on the assumption of a fixed liquid water flux through the GDL. And then the liquid water flux through the GDL is calculated based on the assumption of a fixed liquid saturation difference between the interfaces of the catalyst layer/GDL and the GDL/gas channel. Our results show that under steady-state conditions, the liquid water flux through the GDL increases as contact angle and porosity increase and as the GDL thickness decreases. When a MPL is placed between the catalyst layer and the GDL, the liquid saturation is redistributed across the MPL and GDL. This improves the liquid water draining performance. The liquid water flux through the GDL increases as the MPL porosity increases and the MPL thickness decreases. When the total thickness of the GDL and MPL is kept constant and when the MPL is thinned to 3 μm, the liquid water flux increases considerably, i.e. flooding of MEA is difficult. A GDL with a gradient of porosity is more favorable for liquid water discharge from catalyst layer into the gas channel; for the GDLs with the same equivalent porosity, the larger the gradient is, the more easily the liquid water is discharged. Of the computed cases, a GDL with a linear porosity 0.4x + 0.4 is the best.     

Effect of air flow on liquid water transport through a hydrophobic gas diffusion layer of a polymer electrolyte membrane fuel cell

The transport of liquid water through an idealized 2-D reconstructed gas diffusion layer (GDL) of a polymer electrolyte membrane (PEM) fuel cell is computed subject to hydrophobic boundary condition at the fibre–fluid interface. The effect of air flow, as would occur in parallel/serpentine/interdigitated type of flow fields, on the liquid water transport through the GDL, ejection into the channel in the form of water droplets and subsequent removal of the droplets has been simulated. Results show that typically water flow through the fibrous GDL occurs through a fingering and channelling type of mechanism. The presence of cross-flow of air has an effect both on the path created within the GDL and on the ejection of water into the channel in the form of droplets. A faster rate of liquid water evacuation through the GDL (i.e., more frequent ejection of water droplets) as well as less flooding of the void space results from the presence of cross-flow. These results agree qualitatively with experimental observations reported in the literature.     

Effects of cathode gas diffusion layer design on polymer electrolyte membrane fuel cell water management and performance

The effects of a microporous layer (MPL) on performance and water management of polymer electrolyte fuel cells are investigated. The presence of an MPL on the cathode side is found to slightly improve performance, although the voltage gain is less significant than that obtained by wetter reactants. The effect of the MPL on water management depends on the cathode inlet-gas humidity. Differences in water crossover rate are insignificant for wet cathode feed (RH = 75%), while they are significant for dry feed (RH = 25%). A model based on transport resistance of the MPL is proposed to explain the experimental trends observed. Modeling results suggest that the presence of the MPL on the cathode side causes a reduction of the water flux from the cathode catalyst layer to the flow channels, effectively promoting water back diffusion through the membrane. Higher cathode humidity reduces the driving force for water transport from the electrode to the gas channels, also reducing the importance of the water transport resistance due to the presence of the MPL.