Electrochemical impedance investigation of proton exchange membrane fuel cells experienced subzero temperature

Polarization losses of the fuel cells with different residual water amount frozen at subzero temperature were investigated by electrochemical impedance spectroscopy (EIS) taking into account the ohmic resistance, charge transfer process, and oxygen mass transport. The potential-dependent impedance before and after eight freeze/thaw cycles suggested that the ohmic resistance did not change, while the change of the charge transfer resistance greatly depended on the residual water amount. Among the four cells, the mass transport resistance of the cell with the largest water amount increased significantly even at the small current density region. According to the thin film-flooded agglomerate model, the interfacial charge transfer process and oxygen mass transport within the agglomerate and through the ionomer thin film in the catalyst layer both contributed to the high frequency impedance arc. From the analysis of the Tafel slopes, the mechanism of the oxygen reduction reaction (ORR) was the same after the cells experienced subzero temperature. The agglomerate diffusion changed a little in all cells and the thin film diffusion effect was obvious for the cell with the largest residual water amount. These results indicated that the slower oxygen diffusion within the catalyst layer (CL) was the main contributor for the evident performance loss after eight freeze/thaw cycles.     

Parameter sensitivity examination for a complete three-dimensional,two-phase,non-isothermal model of polymer electrolyte membrane fuel cell

Parameter sensitivity analysis is carried out for a complete three-dimensional, two-phase, non-isothermal model of polymer electrolyte membrane (PEM) fuel cell with a parallel flow field design. The model couples the two-phase flow of the multi-component reactants and liquid water, species transport, electrochemical reactions, proton and electron transport, and the electro-osmosis transport, back diffusion of water in the membrane, and energy transport. Twenty nine parameters, which are classified into the structural or transport parameters of porous layers (tortuosity, porosity, permeability, proton conductivity, electron conductivity, and thermal conductivity) as well as the electrochemical parameters (anodic and cathodic exchange current densities, anodic and cathodic transfer coefficients for anode and cathode reactions), are used to implement individual parameter investigation. The results show the parameters can be divided in to strongly sensitive, conditional sensitive and weak sensitive parameters according to its effect on the cell polarization curve. The optimization of parameters of cathode gas diffusion layer (GDL) and catalyst layer (CL) is more important to improve cell performance than that of anode GDL and CL because liquid water transport and removal affect significantly membrane hydration and reactant transport. Electrochemical parameters determine the activation potential and the slope of ohmic polarization hence these parameters can be used to fit experimental polarization curve more effectively than the other parameters.     

Parametric study of the cathode and the role of liquid saturation on the performance of a polymer electrolyte membrane fuel cell—A numerical approach

A two-dimensional two-phase steady state model of the cathode of a polymer electrolyte membrane fuel cell (PEMFC) is developed using unsaturated flow theory (UFT). A gas flow field, a gas diffusion layer (GDL), a microporous layers (MPL), a finite catalyst layer (CL), and a polymer membrane constitute the model domain. The flow of liquid water in the cathode flow channel is assumed to take place in the form of a mist. The CL is modeled using flooded spherical agglomerate characterization. Liquid water is considered in all the porous layers. For liquid water transport in the membrane, electro-osmotic drag and back diffusion are considered to be the dominating mechanisms. The void fraction in the CL is expressed in terms of practically achievable design parameters such as platinum loading, Nafion loading, CL thickness, and fraction of platinum on carbon. A number of sensitivity studies are conducted with the developed model. The optimum operating temperature of the cell is found to be 80-85 °C. The optimum porosity of the GDL for this cell is in the range of 0.7-0.8. A study by varying the design parameters of the CL shows that the cell performs better with 0.3-0.35 mg cm⁻² of platinum and 25-30 wt% of ionomer loading at high current densities. The sensitivity study shows that a multi-variable optimization study can significantly improve the cell performance. Numerical simulations are performed to study the dependence of capillary pressure on liquid saturation using various correlations. The impact of the interface saturation on the cell performance is studied. Under certain operating conditions and for certain combination of materials in the GDL and CL, it is found that the presence of a MPL can deteriorate the performance especially at high current density.     

Measurement of liquid water content in cathode gas diffusion electrode of polymer electrolyte fuel cell

Water management in cathode gas diffusion electrode (GDE) of polymer electrolyte fuel cell (PEFC) is essential for high performance operation, because liquid water condensed in porous gas diffusion layer (GDL) and catalyst layer (CL) blocks oxygen transport to active reaction sites. In this study, the average liquid water content inside the cathode GDE of a low-temperature PEFC is experimentally and quantitatively estimated by the weight measurement, and the relationship between the water accumulation rate in the cathode GDE and the cell voltage is investigated. The liquid water behavior at the cathode is also visualized using an optical diagnostic, and the effects of operating conditions and GDL structures on the water transport in the cathode GDE are discussed. It is found that the liquid water content in the cathode GDE increases remarkably after starting the fuel cell operation due to the water production at the CL. At a high current density, the cell voltage drops suddenly after starting the operation in spite of a low water content in the cathode GDE. When the GDL thickness is increased, much water accumulates near the cathode CL and the fuel cell shuts down immediately after the operation. In the final section of this paper, the structure of cathode GDL that has several grooves for water removal is proposed to prevent water flooding and improve fuel cell performance. This groove structure is effective to promote the removal of the liquid water accumulated near the active catalyst sites.     

A discrete particle packing model for the formation of a catalyst layer in polymer electrolyte fuel cells

We developed a reconstruction simulation model for a catalyst layer of a polymer electrolyte fuel cell to elucidate the effect of the size and shape of the catalyst agglomerates on the cell performance. The geometry of the catalyst layer was obtained by simulating the packing of carbon black agglomerates in ink modeled as multisphere objects by the discrete element method. Electrochemical reaction and mass transfer were modeled based on the resulting three-dimensional geometry of the catalyst. Both the size and shape of the agglomerate significantly influence the catalyst structure and performance. Branched agglomerates lead to higher porosity, larger pore sizes, and better cell performance. For each agglomerate shape, there is an optimum size at which the performance is the maximum, because of the optimum trade-off relationship between the oxygen diffusion and proton conduction. Understanding the mechanism of the catalyst formation can aid the design of catalysts to improve their performance.     

Numerical study on the compression effect of gas diffusion layer on PEMFC performance

A numerical method is developed to study the effect of the compression deformation of the gas diffusion layer (GDL) on the performance of the proton exchange membrane fuel cell (PEMFC). The GDL compression deformation, caused by the clamping force, plays an important role in controlling the performance of PEMFC since the compression deformation affects the contact resistance, the GDL porosity distribution, and the cross-section area of the gas channel. In the present paper, finite element method (FEM) is used to first analyze the ohmic contact resistance between the bipolar plate and the GDL, the GDL deformation, and the GDL porosity distribution. Then, finite volume method is used to analyze the transport of the reactants and products. We investigate the effects of the GDL compression deformation, the ohmic contact resistivity, the air relative humidity, and the thickness of the catalyst layer (CL) on the performance of the PEMFC. The numerical results show that the fuel cell performance decreases with increasing compression deformation if the contact resistance is negligible, but an optimal compression deformation exists if the contact resistance is considerable.     

Microporous layer for water morphology control in PEMFC

We have used environmental scanning electron microscope to observe vapor condensation and liquid water morphology and breakthrough in porous layers of polymer electrolyte membrane fuel cell. These suggest presence of large droplets and high liquid saturation at interface of the catalyst layer (CL) and gas diffusion layer (GDL), due to jump in pore size. We develop a model for morphology of liquid phase across multiple porous layers by use of both continuum and breakthrough (percolation) treatments. Using the results of this model we show the liquid morphologies deteriorate the efficiency of electrochemical reactions in CL and increase the water saturation in GDL. Then we show that inserting a microporous layer between CL and GDL reduces both the droplet size and liquid saturation and improves the cell performance.     

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.     

A parametric study of cathode catalyst layer structural parameters on the performance of a PEM fuel cell

This paper is a computational study of the cathode catalyst layer (CL) of a proton exchange membrane fuel cell (PEMFC) and how changes in its structural parameters affect performance. The underlying mathematical model assumes homogeneous and steady-state conditions, and consists of equations that include the effects of oxygen diffusion, electrochemical reaction rates, and transport of protons and electrons through the Nafion ionomer (PEM) and solid phases. Simulations are concerned with the problem of minimizing activation overpotential for a given current density. The CL consists of four phases: ionomer, solid substrate, catalyst particles and void spaces. The void spaces are assumed to be fully flooded by liquid water so that oxygen within the CL can diffuse to reaction sites via two routes: within the flooded void spaces and dissolved within the ionomer phase. The net diffusive flux of oxygen through the cathode CL is obtained by incorporating these two diffusive fluxes via a parallel resistance type model. The effect of six structural parameters on the CL performance is considered: platinum and carbon mass loadings, ionomer volume fraction, the extent to which the gas diffusion layer (GDL) extends into the CL, the GDL porosity and CL thickness. Numerical simulations demonstrate that the cathode CL performance is most strongly affected by the ionomer volume fraction, CL thickness and carbon mass loading. These results give useful guidelines for manufactures of PEMFC catalyst layers.     

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.     

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

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

The influence of polymer electrolyte fuel cell cathode degradation on the electrode polarization

The electrode of polymer electrolyte fuel cell (PEFC) consists of the porous catalyst layer and gas diffusion layer (GDL). Quantitative evaluation of the influence of these porous layers’ degradation on the cell performance was attempted. The cell was assembled by using the catalyst layer or GDL, which had been corroded ex situ, as the cathode and the cell performance was characterized. The oxygen diffusion polarizations of the catalyst layer and that of the GDL were evaluated from the polarization curves. The polarization curves before and after a long-term operation were also analyzed by the same way, and the influences of the degradation of catalyst layer and GDL were evaluated. The increase of the gaseous diffusion loss in the catalyst layer was found to cause the cell performance loss mainly from the analysis of the simulated corrosion test and the long-term operation cell.     

Enhancing liquid water transport by laser perforation of a GDL in a PEM fuel cell

The presence of liquid water in a polymer electrolyte membrane fuel cell hinders gas diffusion to the active sites, which results in large concentration overpotentials and instability of the fuel cell performance. In this paper, a new customized gas diffusion layer (GDL) is presented that enhances liquid water transport from the electrode to the gas channels and therefore lowers mass transport losses of oxygen through the porous media. The GDL is systematically modified by laser-perforation with respect to the flow field design. The holes are characterized by SEM images. The performance of the laser-treated GDL was investigated in a small test fuel cell with a reference electrode by voltammetry and chronoamperometry measurements and compared to corresponding data with a non-modified GDL. Voltammetry experiments with different humidification levels of the inlet gases were conducted. In all cases, the cathode overpotential with the perforated GDL clearly shows reduced saturation which can be seen in a lower overpotential in the region limited by mass transport resulting in a higher limiting current density. The investigated current response of the chronoamperometry measurements clearly shows a better dynamic and overall performance of the test cell with the perforated GDL.     

Impact of the anode operating conditions on the liquid water distribution in the cathode gas diffusion layer

Previous experimental results indicate that the humidification conditions at the anode have an impact on the liquid water distribution in the cathode gas diffusion layer. Numerical simulations are developed to reproduce and analyze this effect. Results consistent with the experimental results are first obtained by playing with the partition coefficients of an advanced pore network model computing the liquid water formation and transfer in the cathode gas diffusion layer (GDL) for a large range of operating conditions. Then, a model for the full anode – cathode assembly is developed by combining the pore network model of the cathode GDL and a 1D model describing the heat and water transfer in the various components of the anode-cathode assembly. This enables one to generalize the dry – wet regime diagram introduced in a previous work by incorporating the effect of the humidity condition at the anode.     

Design of low-humidification PEMFC by using cell simulator and its power generation verification test

As long as the perfluorinated proton exchange membrane (PEM) is used for the electrolyte, both the cell performance and life are highly dependent upon the water content in the electrolyte. On the other hand, pre-humidification of fuel and oxidant gases complicates the PEMFC system and prevents it from possible cost reduction measures. In this study, in order to maintain a membrane electrode assembly (MEA) with a satisfactory water content by only the water produced in catalyst layer through the electrode reaction without prior humidification of both the fuel and oxidant gases, a novel gas diffusion layer (GDL) was fabricated. This was achieved by coating a water management layer (WML) onto a traditional GDL in order to place the WML between the traditional GDL and the catalyst layer of the PEMFC. This study describes the significant balance of water with WML in the fuel cell using both simulation and experimental analysis.     

The effects of porosity distribution variation on PEM fuel cell performance

Gas diffusion layers (GDL) are one of the important parts of the PEM fuel cell as they serve to transport the reactant gases to the catalyst layer. Porosity of this layer has a large effect on the PEM fuel cell performance. The spatial variation in porosity arises due to two effects: (1) compression of the electrode on the solid landing areas and (2) water produced at the cathode side of gas diffusion layers. Both of these factors change the porosity of gas diffusion layers and affect the fuel cell performance. To implement this performance analysis, a mathematical model which considers oxygen and hydrogen mass fraction in gas diffusion layer and the electrical current density in the catalyst layer, and the fuel cell potentials are investigated. The porosity variation in the GDL is calculated by considering the applied pressure and the amount of the water generated in the cell. The validity of the model is approved by comparing the computed results with experimental data. The obtained results show that the decrease in the average porosity causes the reduction in oxygen consumption, so that a lower electrical current density is generated. It is also shown that when the electrical current density is low, the porosity variation in gas diffusion layer has no significant influence on the level of polarization whereas at higher current density the influence is very significant. The porosity variation causes non-uniformity in the mass transport which in turn reduces the current density and a lower fuel cell performance is obtained.     

Three-dimensional multiphase modeling of alkaline anion exchange membrane fuel cell

Alkaline anion exchange membrane (AAEM) fuel cell is becoming more attractive because of its outstanding merits, such as fast electrochemical kinetics and low dependence on non-precious catalyst. In this study, a three-dimensional multiphase non-isothermal AAEM fuel cell model is developed. The modeling results show that the performance is improved with more anode humidification, but the improvement becomes less significant at higher humidification levels. The humidification level of anode can change the water removal mechanisms: at partial humidification, water is removed as vapor; and for full humidification, water is removed as liquid. Cathode humidification is even more critical than anode. Liquid water supply in cathode has a positive effect on performance, especially at high current densities. With more liquid water supply in cathode, liquid water starts moving from channel to CL, rather than being removed from CL. Liquid water supply in cathode is needed to balance the water amounts in anode and cathode. Decreasing the membrane thickness generally improves the cell performance, and the improvement is even enhanced with thinner membranes, due to the faster water diffusion between anode and cathode, which reduces the mass transport losses.     

Influences of assembly pressure and flow channel size on performances of proton exchange membrane fuel cells based on a multi-model

In this work, assembly pressure and flow channel size on proton exchange membrane fuel cell performance are optimized by means of a multi-model. Based on stress-strain data of the SGL-22BB GDL obtained from its initial compression experiments, Young's modulus with different ranges of assembly pressure fits well through modeling. A mechanical model is established to analyze influences of assembly pressure on various gas diffusion layer parameters. Moreover, a CFD calculation model with different assembly pressures, channel width, and channel depth are established to calculate PEMFC performances. Furthermore, a BP neural network model is utilized to explore optimal combination of assembly pressure, channel width and channel depth. Finally, the CFD model is used to validate effect of size optimization on PEMFC performance. Results indicate that gap change of GDL below bipolar ribs is more remarkable than that below channels under action of the assembly pressure, making liquid water easily transported under high porosity, which is conducive to liquid water to the channels, reduces the accumulation of liquid water under the ribs, and enhances water removal in the PEMFC. Affected by the assembly force, change of GDL porosity affects its diffusion rate, permeability and other parameters, which is not conducive to mass transfer in GDL. Optimizing the depth and different dimensions through width of the flow field can effectively compensate for this effect. Therefore, the PEMFC performance can be enhanced through the comprehensive optimization of the assembly force, flow channel width and flow channel depth. The optimal parameter is obtained when assembly pressure, channel width and channel depth are set as 0.6 MPa, 0.8 mm, and 0.8 mm, respectively. The parameter optimization enhances the mass transfer, impedance, and electrochemical characteristics of PEMFC. Besides, it effectively enhances the quality transfer efficiency inside GDL, prevents flooding, and reduces concentration loss and ohmic loss.     

Application of water barrier layers in a proton exchange membrane fuel cell for improved water management at low humidity conditions

This study discusses the use of an additional layer in the cathode side of a proton exchange membrane fuel cell (PEMFC) for improved water management at dry conditions. The performance of fuel cells deteriorates significantly when low to no gas humidification is used. This study demonstrates that adding a non-porous material with perforations, such as stainless steel, between the cathode flow field plate and the gas diffusion layer (GDL) improves the water saturation in the cathode GDL and catalyst layer, increases the water content in the anode, and keeps the membrane hydrated. The slight voltage drop in the performance as a result of transport limitations is justifiable since the overall durability of the cell at these extreme conditions is enhanced. The results show that the perforated layer(s) enhances the operational life of the PEMFC under completely dry conditions. These extreme conditions (dry gases without humidification, 90 kPa, 75 °C) were used to accelerate the failure modes in the fuel cells.     

Performance analysis of a PEM fuel cell cathode with multiple catalyst layers

The cathode catalyst layer (CL) of a PEM fuel cell (PEMFC) plays an important role in the performance of the cell because of the rate limiting mechanisms that take place in it. For enhancing the performance of a PEMFC, the use of multiple, ultra thin CLs instead of a single CL is considered in the present work. Since the concentration of oxygen decreases in a CL from the diffusion medium-CL interface towards the polymer membrane, the CL adjacent to the diffusion medium should be of higher porosity than the other CLs. Similarly, the CL adjacent to the polymer membrane should contain more ionomer than the other CLs. Furthermore, liquid water should be removed without causing significant mass transport and/or ohmic losses. Therefore, the design parameters of a CL can be varied spatially to minimize losses in a PEMFC. However, such a continuously graded CL is difficult to manufacture due to lack of commercially available techniques and associated costs. As an alternative, a combination of layers can be synthesized where each layer is manufactured with different design parameters. This approach provides the opportunity to optimize the design parameters of each layer. With this objective in mind, a detailed steady state model of a PEMFC cathode with multiple layers is developed. The model considers liquid water in all the layers. The catalyst layer microstructure is modeled as a network of spherical agglomerates. For improved water management, a thin micro-porous layer is considered between the gas diffusion layer (GDL) and the first catalyst layer. The performance curves for various combinations of the design parameters are shown and the results are analyzed. The results show that there exists an optimum combination of design parameters for each catalyst layer that can significantly improve the performance of a PEMFC.