Material behavior of rubber sealing for proton exchange membrane fuel cells

Reliable sealing is necessary for the stable operation of proton exchange membrane fuel cell (PEMFC). In practical application, various materials have been tried in PEMFC sealing. However, the mechanical properties of these sealing materials, which play a key role in the sealing stability, have not been fully understood in PEMFC environment, especially after long-term operation. In this paper, according to the operating environment of PEMFC, sealing material experiments are carried out to explore the differences in mechanical behaviors of sealing materials, including silicone rubber (SR), fluororubber (FR), nitrile rubber (NBR) and ethylene-propylene-diene-terpolymer rubber (EPDM) and the variation of mechanical properties of these sealing materials is predicted as time goes on. The results indicate that compression rate has a great influence on sealing contact stress. SR and EPDM, with the variation of 0.15 MPa and 0.45 MPa in stress, show the best and worst mechanical stability at different compression rates, respectively. In terms of temperature, it is found that SR can adapt to different operating temperature of PEMFC and only 18% variation is found from 20 °C to 100 °C. Finally, based on Time-Temperature Superposition (TTS), high temperature experiments are conducted to predict long-term relaxation stress under PEMFC working condition. The analysis results are beneficial for choosing suitable sealing material, and it can also be applied to predict sealing ability in PEMFC.     

An analytical model for the transverse permeability of gas diffusion layer with electrical double layer effects in proton exchange membrane fuel cells

An analytical model is presented for the transverse permeability of gas diffusion layer (GDL) based on an ordered array of parallel charged circular cylinders at the steady state. The formula of calculating the permeability of the transverse direction is given by solving the fluid momentum equation in a unit cell. In the present approach, the proposed model is explicitly related to the porosity and fiber radius of fibrous porous media, the zeta potential, and the physical properties of the electrolyte solution. Besides, the effects of these parameters (the porosity, unit cell aspect ratio, fiber radius, and molar concentration) on the transverse permeability are discussed detailedly. The model predictions are compared with the previous studies in the available literature, and good agreement is found.     

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.     

Carbon film coating on gas diffusion layer for proton exchange membrane fuel cells

This study discusses a novel process to increase the performance of proton exchange membrane fuel cells (PEMFC). In order to improve the electrical conductivity and reduce the surface indentation of the carbon fibers, we modified the carbon fibers with pitch-based carbon materials (mesophase pitch and coal tar pitch). Compared with the gas diffusion backing (GDB), GDB-A240 and GDB-MP have 32% and 33% higher current densities at 0.5 V, respectively. Self-made carbon paper with the addition of a micro-porous layer (MPL) (GDL-A240 and GDL-MP) show improved performance compared with GDB-A240 and GDB-MP. The current densities of GDL-A240 and GDL-MP at 0.5 V increased by 37% and 31% compared with GDL, respectively. This study combines these two effects (carbon film and MPL coating) to promote high current density in a PEMFC.     

Effects of chlorides on the performance of proton exchange membrane fuel cells

This paper investigates the effects of cathode gases containing chloride ions on the proton exchange membrane fuel cell (PEMFC) performance. Chloride solutions are vaporized using an ultrasonic oscillator and mixed with oxygen/air. The salt concentration of the mixed gas in the cathode is set by varying the concentration of the chloride solution. Five-hour tests show that an increase in the concentration of sodium chloride did not significantly affect the cell performance of the PEMFC. It is found that variations in the concentration of chloride do not show significant influence on the cell performance at low current density operating condition. However, for high current density operating conditions and high calcium chloride concentrations, the chloride ion appears to have a considerable effect on cell performance. Experimental results of 108-h tests indicate that the fuel cell operating with air containing calcium chloride has a performance decay rate of 3.446 mV h⁻¹ under the operating condition of current density at 1 A/cm². From the measurements of the I-V polarization curves, it appears that the presence of calcium chloride in the cathode fuel gas affects the cell performance more than sodium chloride does.     

Preparation and operation of gas diffusion electrodes for high-temperature proton exchange membrane fuel cells

Gas diffusion electrodes for high-temperature PEMFC based on acid-doped polybenzimidazole membranes were prepared by a tape-casting method. The overall porosity of the electrodes was tailored in a range from 38% to 59% by introducing porogens into the supporting and/or catalyst layers. The investigated porogens include volatile ammonium oxalate, carbonate and acetate and acid-soluble zinc oxide, among which are ammonium oxalate and ZnO more effective in improving the overall electrode porosity. Effects of the electrode porosity on the fuel cell performance were investigated in terms of the cathodic limiting current density and minimum air stoichiometry, anodic limiting current and hydrogen utilization, as well as operations under different pressures and temperatures.     

Fractal model for predicting the effective binary oxygen diffusivity of the gas diffusion layer in proton exchange membrane fuel cells

We propose an analytical model to predict the effective binary oxygen diffusivity of the porous gas diffusion layer (GDL) in proton exchange membrane fuel cells (PEMFCs). In this study, we consider the fractal characteristics of the porous GDL as well as its general microstructure, and we adopt the Bosanquet equation to derive effective diffusivity. The fractal characterization of GDL enables us to model effective diffusivity in a continuous manner while taking into account the effect of pore size distribution. Comparison to two other theoretical models that are generally accepted in the simulation of PEMFCs shows similar trends in all three models, indicating that our proposed model is well founded. Furthermore, the predicted effective binary oxygen diffusivities of two samples show that after treatment with polytetrafluoroethylene (PTFE), the effective binary diffusivity of the GDL decreases. Based on the parametric effect analysis, we conclude that effective binary diffusivity is negatively correlated with tortuosity fractal dimension but positively correlated with the fractal dimension of pore area, porosity, or mean pore diameter. The proposed model facilitates fast prediction of effective diffusivity as well as multi-scale modeling of PEMFCs and thus facilitates the design of the GDLs and of PEMFCs.     

Liquid transport in gas diffusion layer of proton exchange membrane fuel cells: Effects of micro-porous layer cracks

Micro porous layer (MPL) is a carbon layer (～15 μm) that coated on the gas diffusion layer (GDL) to enhance the electrical conduction and membrane hydration of proton exchange membrane fuel cell (PEMFC). However, the liquid transport behavior from MPL to GDL and its impact on water management remain unclear. Thus, a three-dimensional volume of fluid (VOF) model is developed to investigate the effects of MPL crack properties on liquid water saturation, liquid pathway formation, and the two-phase mass transport mechanism in GDL. Firstly, a stochastic orientation method is used to reconstruct the fibrous structure of the GDL. After that, the liquid water saturation calculated from the numerical results agrees well with the experimental data. With considering the full morphology of the overlap between MPL and GDL, it's found that this overlap determines the preferred liquid emerging port of both MPL and GDL. Three crack design shapes in MPL are proposed on the base of the similarity crack formation processes of soil mud. In addition, the effects of crack shape, distance between cracks, and crack number on liquid water transport from MPL to GDL are investigated. It is found that the liquid water saturation of GDL increases with crack number and the distance between cracks, while presents little correlation to the crack shape. Hopefully, these results can help the development of PEMFC models without reconstructing full MPL morphology.     

Novel serpentine-baffle flow field design for proton exchange membrane fuel cells

An appropriate flow field in the bipolar plates of a fuel cell can effectively enhance the reactant transport rates and liquid water removal efficiency, improving cell performance. This paper proposes a novel serpentine-baffle flow field (SBFF) design to improve the cell performance compared to that for a conventional serpentine flow field (SFF). A three-dimensional model is used to analyze the reactant and product transport and the electrochemical reactions in the cell. The results show that at high operating voltages, the conventional design and the baffled design have the same performance, because the electrochemical rate is low and only a small amount of oxygen is consumed, so the oxygen transport rates for both designs are sufficient to maintain the reaction rates. However, at low operating voltages, the baffled design shows better performance than the conventional design. Analyses of the local transport phenomena in the cell indicate that the baffled design induces larger pressure differences between adjacent flow channels over the entire electrode surface than does the conventional design, enhancing under-rib convection through the electrode porous layer. The under-rib convection increases the mass transport rates of the reactants and products to and from the catalyst layer and reduces the amount of liquid water trapped in the porous electrode. The baffled design increases the limiting current density and improves the cell performance relative to conventional design.     

An inverse geometry design problem in optimizing the shape of the gas channel for a proton exchange membrane fuel cell

The inverse design problem technique presented in this paper is intended for optimizing the shape of the gas channel at the cathode side in a proton exchange membrane fuel cell (PEMFC). The technique uses the desired current densities located on a carbon plate near the outlet of the channel at the cathode side as a starting point. The desired current density distributions can be obtained by modifying the current density distributions of the existing PEMFC with rectangular gas channels. The geometry of the redesigned gas channel is generated using a B-spline curve method, which enables the shape of the fuel channel to be completely specified using only a small number of control points, thus applying the technique of parameter estimation for the inverse design problem. Results show that by utilizing the redesigned optimal gas channel, the total current of the PEMFC can be increased, and at the same time the phenomenon of saturated water accumulation in the channel can be greatly reduced.     

Study on ice-melting performance of gradient gas diffusion layer in proton exchange membrane fuel cell

In this study, a three-dimensional model was established using the lattice Boltzmann method (LBM) to study the internal ice melting process of the gas diffusion layer (GDL) of the proton exchange membrane fuel cell (PEMFC). The single-point second-order curved boundary condition was adopted. The effects of GDL carbon fiber number, growth slope of the number of carbon fibers and carbon fiber diameter on ice melting were studied. The results were revealed that the temperature in the middle and lower part of the gradient distribution GDL is significantly higher than that of the no-gradient GDL. With the increase of the growth slope of the number of carbon fiber, the temperature and melting rate gradually increase, and the position of the solid-liquid interface gradually decreases. The decrease in the number of carbon fibers has a similar effect as the increase in the growth slope of the number of carbon fibers. In addition, as the diameter of the carbon fiber increases, the position of the solid-liquid interface gradually decreases first and then increases.     

Three-dimensional two-phase flow model of proton exchange membrane fuel cell with parallel gas distributors

A non-isothermal, steady-state, three-dimensional (3D), two-phase, multicomponent transport model is developed for proton exchange membrane (PEM) fuel cell with parallel gas distributors. A key feature of this work is that a detailed membrane model is developed for the liquid water transport with a two-mode water transfer condition, accounting for the non-equilibrium humidification of membrane with the replacement of an equilibrium assumption. Another key feature is that water transport processes inside electrodes are coupled and the balance of water flux is insured between anode and cathode during the modeling. The model is validated by the comparison of predicted cell polarization curve with experimental data. The simulation is performed for water vapor concentration field of reactant gases, water content distribution in the membrane, liquid water velocity field and liquid water saturation distribution inside the cathode. The net water flux and net water transport coefficient values are obtained at different current densities in this work, which are seldom discussed in other modeling works. The temperature distribution inside the cell is also simulated by this model.     

Fractal model for prediction of effective thermal conductivity of gas diffusion layer in proton exchange membrane fuel cell

The process of heat transfer within porous media is usually considered as a transport through large numbers of straight channels with uniform pore sizes. For the prediction of effective thermal conductivity of gas diffusion layer (GDL), morphological properties such as the tortuosity of channels and pore-size distribution of this porous layer should be considered. Thus in this article, novel parallel and series-parallel prediction models of effective thermal conductivity for the GDL in proton exchange membrane fuel cell (PEMFC) have been derived by fractal theoretical characterization of the real microstructure of GDL. The prediction of fractal parallel model for carbon paper, a basal material of the GDL, is in good agreement with the reference value supplied by Toray Inc. The prediction results from the proposed models are also reasonable because they are distributed between the upper and lower bounds. Parametric effect has been investigated by using the presented models in dimensionless formalism. It can be concluded that dimensionless effective thermal conductivity (k^′eff${k^{\prime }}_{\text{eff}}$) has a positive correlation with effective porosity (?) or the pore-area fractal dimension (D_p) when k_s/k_g < 1; whereas it has a negative correlation with ? or D_p when k_s/k_g > 1 and with tortuous fractal dimension (D_t) whether k_s/k_g < 1 or not. Furthermore, these fractal models have been modified by considering the effect of polytetrafluoroethylene (PTFE) incorporated into the pore spaces of carbon paper, and the corresponding model prediction shows that there is an increase in the effective thermal conductivity due to the filling of PTFE that has high thermal conductivity.     

Structure failure of the sealing in the assembly process for proton exchange membrane fuel cells

Sealing stability in proton exchange membrane fuel cell (PEMFC) is critical to the performance and safety of stacks. However, sealing structure failure (SSF), which leads to the leakage of reactant gases, often occurs in the assembly process or start-up operation for PEMFCs. This study aims to investigate the effects of geometrical structure and material parameters of sealing components on the sealing structure failure. Slippage angle and slippage distance are adopted to evaluate the risk of SSF. Finite element (FE) simulations are conducted with consideration of the assembly process and start-up operation. Experiments are carried out to validate the accuracy of the FE model. Influences of parameters of gasket, membrane electrode assembly (MEA) frame, sealing groove shape of bipolar plate (BPP), and gas pressure are discussed in detail. Meanwhile, the risks of SSF for the stack by using metallic and graphite BPPs are compared. It is demonstrated that material properties and geometrical parameters of sealing components in PEMFC have great effects on SSF. The methodology developed is beneficial to the understanding of the SSF, and it can also be applied to guide the design of PEMFC stack assembly process to keep a good sealing reliability.     

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

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

Nafion/PTFE/silicate membranes for high-temperature proton exchange membrane fuel cells

Fuel cell performance of membrane electrode assemblies (MEAs) prepared from poly(tetrafluoroethylene)/Nafion/silicate (PNS) membrane and Nafion-112 membrane were investigated. Due to the low conductivity of PTFE and silicate, PNS had a higher proton resistance than Nafion-112. However, in this work we show that PNS performs better than Nafion-112 for a high current density operation with a low inlet gas humidity. As the PEMFCs were operated at with 100% RH, the results showed the maximum power density (PD_max) of PNS was: at with both H₂ and O₂ flow rates of 300 ml/min, and at with H₂ flow rate of 360 ml/min and O₂ flow rate of 600 ml/min, which were much higher than the at of Nafion-112 with both H₂ and O₂ flow rates of 300 ml/min. The PD_max of PNS was: , , and at as the operating temperature and inlet gas humidity were set at with 67.7% RH, with 46.8% RH, and with 33.1% RH, respectively. However, no output power was detected for Nafion-112 MEA when the cell was operated at a temperature higher than and an inlet gas humidity lower than 67.7% RH. The high PEMFC performance of PNS at high current density and low humidity is attributed to the presence of silicate in the PNS membrane, which enhances water uptake and reduces electro-osmosis water loss at a high current density.     

Microstructured membranes for improving transport resistances in proton exchange membrane fuel cells

Proton exchange membrane fuel cells (PEMFCs) have been identified as one of the most promising renewable energy system for use in automotive applications. However, due to the wide range of weather conditions around the world, the PEMFCs must be stable for operating under these variable conditions. One of the inefficiencies of PEMFCs in automotive applications is during vehicle warm-up, where the low hydration level within the PEMFC can lead to a low performance of the fuel cell. In this study, a proton exchange membrane (PEM) was prepared with regular, microstructured features tuned over a range of aspect ratios. These microstructured membranes were incorporated into MEAs and analyzed for their membrane, proton, and oxygen transport resistances. These fuel cells were tested under different conditions to simulate vehicle start-up, normal operating conditions, and hot operating conditions. It was determined that microstructured PEMs improved performance over planar PEMs under both the start-up and hot conditions. Despite the improved performance of the microstructured PEMs, a high hydrogen cross-over and short-circuit current were also observed for these samples. Adjusting the preparation techniques and tuning the dimensions of the microstructures may provide avenues for further optimization of PEMFC performance.     

A novel three-dimensional, two-phase and non-isothermal numerical model for proton exchange membrane fuel cell

A three-dimensional, two-phase and non-isothermal model of a proton exchange membrane fuel cell (PEMFC) based on the previously developed model is established using the two-fluid method. This two-phase model considers the liquid water transport in both cathode and anode sides and accounts for the intrinsic heat transfer between the reactant fluids and the solid matrices. The latent heat of water condensation/evaporation is considered in the present model. The numerical results demonstrate that the lower cathode humidity is beneficial for cell performance. In the anode side, the water vapor can be condensed at high current density because the water vapor transport is less than the hydrogen consumption rate. Near the catalyst layer, the reactant fluid temperature is higher than the solid matrix temperature, and far from the catalyst layer, the temperature difference between the reactant fluid and the solid matrix decreases. Near the channel, the reactant fluid temperature is lower than the solid matrix temperature.