An approach for determining the liquid water distribution in a liquid-feed direct methanol fuel cell

In determining the liquid water distribution in the anode (or the cathode) diffusion medium of a liquid-feed direct methanol fuel cell (DMFC) with a conventional two-phase mass transport model, a current-independent liquid saturation boundary condition at the interface between the anode flow channel and diffusion layer (DL) (or at the interface between the cathode flow channel and cathode DL) needs to be assumed. The numerical results resulting from such a boundary condition cannot realistically reveal the liquid distribution in the porous region, as the liquid saturation at the interface between the flow channel and DL varies with current density. In this work, we propose a simple theoretical approach that is combined with the in situ measured water-crossover flux in the DMFC to determine the liquid saturation in the anode catalyst layer (CL) and in the cathode CL. The determined liquid saturation in the anode CL (or in the cathode CL) can then be used as a known boundary condition to determine the water distribution in the anode DL (or in the cathode DL) with a two-phase mass transport model. The numerical results show that the water distribution becomes much more realistic than those predicted with the assumed boundary condition at the interface between the flow channel and DL.     

In situ water distribution measurements in a polymer electrolyte fuel cell

The overall water vapor balance and concentration distribution in the flow channels is a critical phenomenon affecting polymer electrolyte fuel cell (PEFC) performance. This paper presents, for the first time, results of a technique to measure in situ water vapor, nitrogen and oxygen distribution within the gas channels of an operating PEFC. The use of a gas chromatograph (GC) to measure high levels of water saturation directly, without dehumidification of the flow stream, is a unique aspect of this work. Following careful calibration and instrumentation, a gas chromatograph (GC) was interfaced directly to the fuel cell at various locations along the serpentine anode and cathode flow paths of a specially designed fuel cell. The 50 cm² active area fuel cell also permits simultaneous current distribution measurements via the segmented collector plate approach. The on-line GC method allows discrete measurements of the water vapor content up to a fully saturated condition about every 2 minutes. Water vapor and other species distribution data are shown for several inlet relative humidities on the anode and cathode for different cell voltages. For the thin electrolyte membranes used (51 μm), there is little functional dependence of the anode gas channel water distribution on current output. For thin membranes, this indicates that there is little gradient in the water activity between anode and cathode, indicating diffusion can offset electro-osmotic drag under these circumstances (i<0.5 A/cm²). This technique can be used for detailed studies on water distribution and transport in the PEFC.     

Water transport characteristics of a PEM fuel cell at various operating pressures and temperatures

In this investigation, water in a single-cell proton exchange membrane (PEM) fuel cell was managed using saturated hydrogen and dry air. The experiment was conducted at temperatures of 40, 50 and 60 °C and pressures of 1 and 1.5 bar at both the anode and cathode gas inlets. The feed velocities of hydrogen and air were fixed at 3 and 6 L min⁻¹, respectively. After reaching steady-state conditions, the relative humidity along the single serpentine gas channel was measured. From the experimental data, water transport properties were characterized based on a membrane hydration model. The electro-osmotic drag coefficient, water diffusion coefficient, membrane ionic conductivity and water back-diffusion flux were significantly influenced by the water content in the membrane of the PEM fuel cell. The water content depended on the relative humidity profile along the gas channel. In this investigation, a negative value for the water back-diffusion flux was measured; thus, the transport of water from the cathode to the anode did not occur. This phenomenon was due to the large water concentration gradient between the anode and cathode. Therefore, this strategy successfully prevented flooding in the PEM fuel cell.     

Novel in situ measurements of relative humidity in a polymer electrolyte membrane fuel cell

Miniature temperature/humidity sensors are incorporated into the graphite flowplates of a single cell polymer electrolyte membrane fuel cell (PEMFC) in order to measure the humidity profile along the serpentine channels of both anode and cathode in real time. The sensors show robust performance and importantly are able to recover after saturation. The key observation is a significant increase in relative humidity along the anode gas channel due to back diffusion of water from cathode to anode. Such measurements may be used to determine the water balance in the cell under a range of operating conditions to facilitate model validation and system optimisation.     

Assisted water management in a PEMFC with a modified flow field and its effect on performance

This work designed and tested innovative flow channels in order to improve water management in a polymer electrolyte membrane fuel cell (PEMFC). The design employed slanted channels with an angle of 20° in a flow plate to collect the liquid water that permeated from the gas diffusion layers. The effects of orientations of the slanted channels in up-slanted and down-slanted directions and relative humidity levels on the cell performance were investigated. The experimental results showed that modifying the anode flow field using down-slanted channels provided higher cell performance. Water concentration at the gas diffusion layer is reduced resulting in more back diffusion of water from the cathode to anode, thus inducing membrane hydration and improving the conductivity. Promotion of water removal by applying down-slanted channels in the cathode side did not improve the performance. This work has demonstrated that channel cross-section design alone could improve the PEM fuel cell performance. The anode down-slanted cell indeed improved the performances at extremely wet condition and the power was equally good as that without modified flow channel at less wet condition.     

Characteristics of water transport through the membrane in direct methanol fuel cells operating with neat methanol

The water required for the methanol oxidation reaction in a direct methanol fuel cell (DMFC) operating with neat methanol can be supplied by diffusion from the cathode to the anode through the membrane. In this work, we present a method that allows the water transport rate through the membrane to be in-situ determined. With this method, the effects of the design parameters of the membrane electrode assembly (MEA) and operating conditions on the water transport through the membrane are investigated. The experimental data show that the water flux by diffusion from the cathode to the anode is higher than the opposite flow flux of water due to electro-osmotic drag (EOD) at a given current density, resulting in a net water transport from the cathode to the anode. The results also show that thinning the anode gas diffusion layer (GDL) and the membrane as well as thickening the cathode GDL can enhance the water transport flux from the cathode to the anode. However, a too thin anode GDL or a too thick cathode GDL will lower the cell performance due to the increases in the water concentration loss at the anode catalyst layer (CL) and the oxygen concentration loss at the cathode CL, respectively.     

Numerical studies of liquid water behaviors in PEM fuel cell cathode considering transport across different porous layers

In this paper, a two-phase two-dimensional PEM fuel cell model, which is capable of handling liquid water transport across different porous materials, is employed for parametric studies of liquid water transport and distribution in the cathode of a PEM fuel cell. Attention is paid particularly to the coupled effects of two-phase flow and heat transfer phenomena. The effects of key operation parameters, including the outside cell boundary temperature, the cathode gas humidification condition, and the cell operation current, on the liquid water behaviors and cell performance have been examined in detail. Numerical results elucidate that increasing the fuel cell temperature would not only enhance liquid water evaporation and thus decrease the liquid saturation inside the PEM fuel cell cathode, but also change the location where liquid water is condensed or evaporated. At a cell boundary temperature of 80 °C, liquid water inside the catalyst layer and gas diffusion media under the current-collecting land would flow laterally towards the gas channel and become evaporated along an interface separating the land and channel. As the cell boundary temperature increases, the maximum current density inside the membrane would shift laterally towards the current-collecting land, a phenomenon dictated by membrane hydration. Increasing the gas humidification condition in the cathode gas channel and/or increasing the operating current of the fuel cell could offset the temperature effect on liquid water transport and distribution.     

Study of novel flow channels influence on the performance of direct methanol fuel cell

The existing flow channels like parallel and gird channels have been modified for better fuel distribution in order to boost the performance of direct methanol fuel cell. The main objective of the work is to achieve minimized pressure drop in the flow channel, uniform distribution of methanol, reduced water accumulation, and better oxygen supply. A 3D mathematical model with serpentine channel is simulated for the cell temperature of 80 °C, 0.5 M methanol concentration. The study resulted in 40 mW/cm² of power density and 190 mA/cm² of current density at the operating voltage of 0.25 V. Further, the numerical study is carried out for modified flow channels to discuss their merits and demerits on anode and cathode side. The anode serpentine channel is unmatched by the modified zigzag and pin channels by ensuring the better methanol distribution under the ribs and increased the fuel consumption. But the cathode serpentine channel is lacking in water management. The modified channels at anode offered reduced pressure drop, still uniform reactant distribution is found impossible. The modified channels at cathode outperform the serpentine channel by reducing the effect of water accumulation, and uniform oxygen supply. So the serpentine channel is retained for methanol supply, and modified channel is chosen for cathode reactant supply. In comparison to cell with only serpentine channel, the serpentine anode channel combined with cathode zigzag and pin channel enhanced power density by 17.8% and 10.2% respectively. The results revealed that the zigzag and pin channel are very effective in mitigating water accumulation and ensuring better oxygen supply at the cathode.     

Transport phenomena within the porous cathode for a proton exchange membrane fuel cell

A two-phase, one-dimensional steady model is developed to analyze the coupled phenomena of cathode flooding and mass-transport limiting for the porous cathode electrode of a proton exchange membrane fuel cell. In the model, the catalyst layer is treated not as an interface between the membrane and gas diffusion layer, but as a separate computational domain with finite thickness and pseudo-homogenous structure. Furthermore, the liquid water transport across the porous electrode is driven by the capillary force based on Darcy's law. And the gas transport is driven by the concentration gradient based on Fick's law. Additionally, through Tafel kinetics, the transport processes of gas and liquid water are coupled. From the numerical results, it is found that although the catalyst layer is thin, it is very crucial to better understand and more correctly predict the concurrent phenomena inside the electrode, particularly, the flooding phenomena. More importantly, the saturation jump at the interface of the gas diffusion layer and catalyst layers is captured, when the continuity of the capillary pressure is imposed on the interface. Elsewise, the results show further that the flooding phenomenon in the CL is much more serious than that in the GDL, which has a significant influence on the mass transport of the reactants. Moreover, the saturation level inside the cathode is determined, to a great extent, by the surface overpotential, the absolute permeability of the porous electrode, and the boundary value of saturation at the gas diffusion layer-gas channel interface. In order to prevent effectively flooding, it should remove firstly the liquid water accumulating inside the CL and keep the boundary value of liquid saturation as low as possible.     

Water management in direct methanol fuel cells

Water management is an important challenge in portable direct methanol fuel cells. Reducing the water and methanol loss from the anode to the cathode enables the use of highly concentrated methanol solutions to achieve enhanced performances. In this work, the results of a simulation study using a previous developed model for DMFCs are presented. Particular attention is devoted to the water distribution across the cell. The influence of different parameters (such as the cathode relative humidity (RH), the methanol concentration and the membrane, catalyst layer and diffusion media thicknesses) over the water transport and on the cell performance is studied. The analytical solutions of the net water transport coefficient, for different values of the cathode relative humidity are successfully compared with recent published experimental data putting in evidence that humidified cathodes contribute to a decrease on the water crossover. As a result of the modelling results, a tailored MEA build-up with the common available commercial materials is proposed to achieve low methanol and water crossover and high power density, operating at relatively high methanol concentrations. A thick anode catalyst layer to promote methanol oxidation, a thin anode gas diffusion layer as methanol carrier to the catalyst layer and a thin polymer membrane to lower the water crossover coefficient between the anode and cathode are suggested.     

Transport Phenomena Within the Cathode for a Polymer Electrolyte Fuel Cell

A one-dimensional two-phase steady model is developed to analyze the coupled phenomena of cathode flooding and mass-transport limitation for a polymer electrolyte fuel cell. In the model, the liquid water transport in the porous electrode is driven by the capillary force based on Darcy's law, while the gas transport is driven by the concentration gradient based on Fick's law. Furthermore, the catalyst layer is treated as a separate computational domain. The capillary pressure continuity is imposed on the interface between the catalyst layer and the gas diffusion layer. Additionally, through Tafel kinetics, the mass transport and the electrochemical reaction are coupled together. The saturation jump at the interface between the gas diffusion layer and the catalyst layer is captured in the results. Meanwhile, the results further indicate that the flooding situation in the catalyst layer is much more serious than that in the gas diffusion layer. Moreover, the saturation level inside the cathode is largely related to the physical, material, and operating parameters. In order to effectively prevent flooding, one should first remove the liquid water residing inside the catalyst layer and keep the boundary value of the liquid water saturation as low as possible.     

Effect of the cathode gas diffusion layer on the water transport behavior and the performance of passive direct methanol fuel cells operating with neat methanol

The passive operation of a direct methanol fuel cell with neat methanol requires the water that is produced at the cathode to diffuse through the membrane to the anode to compensate the methanol oxidation reaction (MOR). Hence, the anode performance of this type of fuel cell can be limited by the water transport rate from the cathode to the anode. In this work we theoretically show that the water transport from the cathode to the anode depends primarily on the design of the cathode gas diffusion layer (GDL). We investigate experimentally the effects of the design parameters of the cathode GDL, including the PTFE (polytetrafluoroethylene) content in the backing layer (BL), and the carbon loading and the PTFE content in the microporous layer (MPL) on the water transport and the performance of the passive DMFC with the help of a reference electrode. The results indicate that on one hand, these parameters can be adjusted to decrease the water concentration loss of the anode performance, but on the other hand, they can also cause an increase in the oxygen concentration loss of the cathode performance. Hence, an optimal balance in minimizing the both concentration losses is the key to maximize the cell performance.     

Study on the effect of humidity and stoichiometry on the water saturation of PEM fuel cells

This paper investigates the effects of relative humidity (RH) and stoichiometry of reactants on the water saturation and local transport process in proton exchange membrane fuel cells. A two‐dimensional model was developed, taking into account the effect of the formation of liquid water on the reactant transport. The results indicate that the reactant RH and stoichiometry significantly affect cell performance. At a constant anode RH = 100%, a lower cathode RH maintains membrane hydration to give better cell performance. At a constant cathode RH = 100%, a lower anode RH not only provides more hydrogen to the catalyst layer to participate in the electrochemical reaction but also increases the difference in the water concentrations between the anode and cathode. This enhances the back‐diffusion of water from the cathode to the anode, reducing possible flooding for better cell performance. Higher anodic stoichiometry results in the reduction of cathodic water saturation by increasing water back‐diffusion, thereby enhancing fuel cell performance. Higher cathodic stoichiometry also reduces water saturation by drying more liquid water to increase cathode local current density. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of primary parameters on the performance of PEM fuel cell

A one-dimensional, steady-state and isothermal model for a proton exchange membrane (PEM) fuel cell has been developed to investigate the effects of various parameters such as the molar fraction of nitrogen gas, relative humidity, temperature, pressure, membrane thickness, anode and cathode stoichiometric flow ratio and the distribution of oxygen in the cathode catalyst while water transfer in membrane is produced by diffusion, pressure gradient and electro-osmotic drag. The most critical problems to overcome in the proton exchange membrane (PEM) fuel cell technology are the water and thermal management. The results show that the cell performance increases as operating pressure and temperature are increased. The performance of cell can decrease by decreasing the relative humidity of inlet gases and increasing the membrane thickness. Increasing the anode and cathode stoichiometric flow ratio can also improve the cell performance. As the oxygen concentration becomes zero in about 8 percent depth of cathode catalyst layer, the thickness of cathode catalyst layer can be reduced 92 percent without any potential loss in output voltage. The cathode activation loss also becomes high by increasing the molar fraction of nitrogen gas. The modeling results agree very well with experimental results.     

Numerical simulation of exchange membrane fuel cells in different operating conditions

A two-dimensional, steady state model for proton exchange membrane fuel cell (PEMFC) is presented. The model is used to describe the effect operation conditions (current density, pressure and water content) on the water transport, ohmic resistance and water distribution in the membrane and performance of PEMFC. This model considers the transport of species and water along the porous media: gas diffusion layers (GDL) anode and cathode, and the membrane of PEMFC fuel cell.     

Experimental investigation of liquid water formation and transport in a transparent single-serpentine PEM fuel cell

Liquid water formation and transport were investigated by direct experimental visualization in an operational transparent single-serpentine PEM fuel cell. We examined the effectiveness of various gas diffusion layer (GDL) materials in removing water away from the cathode and through the flow field over a range of operating conditions. Complete polarization curves as well as time evolution studies after step changes in current draw were obtained with simultaneous liquid water visualization within the transparent cell. The level of cathode flow field flooding, under the same operating conditions and cell current, was recognized as a criterion for the water removal capacity of the GDL materials. When compared at the same current density (i.e. water production rate), higher amount of liquid water in the cathode channel indicated that water had been efficiently removed from the catalyst layer.

Visualization of the anode channel was used to investigate the influence of the microporous layer (MPL) on water transport. No liquid water was observed in the anode flow field unless cathode GDLs had an MPL. MPL on the cathode side creates a pressure barrier for water produced at the catalyst layer. Water is pushed across the membrane to the anode side, resulting in anode flow field flooding close to the H₂ exit.     

Numerical studies on the geometrical characterization of serpentine flow-field for efficient PEMFC

Geometrical characterization of the serpentine flow-field is one of the key issues to be solved to enhance the performance of PEMFC in relation to pressure drop, discharge of condensed water, maximization of cell voltage, and uniformity of current density over the entire surface area. Three different channel heights and widths were compared with the base flow-field design of the serpentine channel whose width is 1 mm and 0.34 mm in height, each through a detailed numerical study of the distribution of temperature, pressure, water content, and local current density. As the channel height increases higher than the base design, the total pressure drop decreases and results in reduced load of BOP and accumulation of liquid water at the outlet of both anode and cathode. The accumulation of anode liquid water at the outlet caused by back diffusion is accelerated as the channel height increases. As the channel width expands wider than the base design, the pressure drop is lowered and the removal rate of liquid water becomes faster. The effect of the channel width increase on the water removal is greater than that of the channel height increase. Which can influence the dehydration and temperature of the MEA and thus cell performance and lifetime of PEMFC. The results obtained in this work are expected to be applied in developing an efficient serpentine flow-field channel with sub-channels and by-passes.     

Reactants flow behavior and water management for different current densities in PEMFC

Computational fluid dynamics analysis was carried out to investigate the reactants flow behavior and water management for proton exchange membrane fuel cell (PEMFC). A complete three-dimensional model was chosen for single straight channel geometry considering both anode and cathode humidification. Phase transformation was included in the model to predict the water vapor and liquid water distributions and the overall performance of the cell for different current densities. The simulated results showed that for fully humidified conditions hydrogen mole fraction increases along the anode channel with increasing current density, however, at higher current densities it decreases monotonically. Different anode and cathode humidified conditions results showed that the cell performance was sufficiently influenced by anode humidification. The reactants and water distribution and membrane conductivity in the cell depended on anode humidification and the related water management. The cathode channel–GDL (Gas Diffusion Layer) interface experiences higher temperature and reduces the liquid water formation at the cathode channel. Indeed, at higher current densities the water accumulated in the shoulder area and exposed higher local current density than the channel area. Higher anode with lower cathode humidified combination showed that the cell had best performance based on water and thermal management and caused higher velocity in the cathode channel. The model was validated through the available literature.     

Treatment of two-phase flow in cathode gas channel for an improved one-dimensional proton exchange membrane fuel cell model

It has been reported recently that water flooding in the cathode gas channel has significant effects on the characteristics of a proton exchange membrane fuel cell. A better understanding of this phenomenon with the aid of an accurate model is necessary for improving the water management and performance of fuel cell. However, this phenomenon is often not considered in the previous one-dimensional models where zero or a constant liquid water saturation level is assumed at the interface between gas diffusion layer and gas channel. In view of this, a one-dimensional fuel cell model that includes the effects of two-phase flow in the gas channel is proposed. The liquid water saturation along the cathode gas channel is estimated by adopting Darcy’s law to describe the convective flow of liquid water under various inlet conditions, i.e. air pressure, relative humidity and air stoichiometry. The averaged capillary pressure of gas channel calculated from the liquid water saturation is used as the boundary value at the interface to couple the cathode gas channel model to the membrane electrode assembly model. Through the coupling of the two modeling domains, the water distribution inside the membrane electrode assembly is associated with the inlet conditions. The simulation results, which are verified against experimental data and simulation results from a published computational fluid dynamics model, indicate that the effects of relative humidity and stoichiometry of inlet air are crucial to the overall fuel cell performance. The proposed model gives a more accurate treatment of the water transport in the cathode region, which enables an improved water management through an understanding of the effects of inlet conditions on the fuel cell performance.     

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.