The effects of non-uniform distribution of catalyst loading on polymer electrolyte membrane fuel cell performance

The catalyst layers are the most important part of the polymer electrolyte membrane (PEM) fuel cells, and the cell performance is highly related to its structure. The gas diffusion layers (GDLs) are also the essential components of the PEM fuel cell since the reactants should pass through these layers. Model prediction shows that electrical current in catalyst layer is non-uniform, influenced by the channel-land geometry. In addition, the compression effect of GDLs and water generation due to the electrochemical reaction may cause non-uniformity in porosity and, therefore, increases the non-uniformity in reactant concentration in GDL/catalyst layer interface. Simulation results suggest that non-uniform catalyst loading distribution in the catalyst layer will improve the performance of the whole catalyst layer by diminishing the variation in current density.     

Numerical analysis of the manipulated high performance catalyst layer design for polymer electrolyte membrane fuel cell

A two‐dimensional, multiphase, non‐isothermal numerical model was used to investigate the effect of the high performance catalyst layer (CL) design. Microstructure‐related parameters were studied on the basis of the agglomerate model assumption. A conventional CL design (uniform Pt/C composition, e.g., 40 wt%) was modified into two sub‐layers with two different Pt/C compositions (in this study, 40 and 80 wt%). The performance of sub‐layers with different CL designs is shown to be different. Simulation results show that substituting part of the Pt/C 40 wt% with Pt/C 80 wt% increases the cell performance. It was found that factors including proton conductivity, open circuit voltage, and sub‐layer thickness have a significant impact on overall cell performance. Different water distribution for different membrane electrode assembly designs was also observed in the simulation results. More liquid water accumulation inside the membrane electrode assembly is seen when the Pt/C 80 wt% sub‐layer is next to the gas diffusion layer. Finally, several key design parameters for the proposed high performance CL design including agglomerate radius, Nafion thin film thickness, and the Nafion volume fraction within the agglomerate in terms of CL fabrication were identified on the basis of our simulation results. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of operating conditions on durability of polymer electrolyte membrane fuel cell Pt cathode catalyst layer

In this study, we investigated the effects of humidity and oxygen reduction on the degradation of the catalyst of a polymer electrolyte membrane fuel cell (PEMFC) in a voltage cycling test. To elucidate the effect of humidity on the voltage cycling corrosion of a carbon-supported Pt catalyst with 3 nm Pt particles, voltage cycling tests based on 10,000 cycles were conducted using 100% relative humidity (RH) hydrogen as anode gas and nitrogen of varying humidities as cathode gas. The degradation rate of an electrochemical surface area (ECSA) was almost 50% under 189% RH nitrogen atmosphere and the Pt average particle diameter after 10,000 cycles under these conditions was about 2.3 times that of a particle of fresh catalyst because of the agglomeration of Pt particles.The oxygen reduction reaction (ORR) that facilitated Pt catalyst agglomeration when oxygen was employed as the cathode gas also demonstrated that Pt agglomeration was prominent in higher concentrations of oxygen. The ECSA degradation figure in 100% RH oxygen was similar to that in 189% RH nitrogen. It was concluded that liquid water, which was dropped under a supersaturated condition or generated by ORR, accelerated Pt agglomeration. In this paper, we suggest that the Pt agglomeration degradation occurs in a flooding area in a cell plane.     

Direct preparation of core-shell platinum cathode in membrane electrode assembly catalyst layer for polymer electrolyte fuel cell

Core–shell catalyst has been attracting attention as a low-Pt catalyst for PEFC cathode. However, its mass production method has not yet been established. In this paper, a novel method suitable for continuous production of low-platinum catalyst layer for PEFC is proposed. Catalyst layer of carbon-supported Pd@Pt core–shell catalyst (Pd@Pt/C) is fabricated by using Cu underpotential deposition (UPD) followed by surface-limited redox replacement (SLRR) directly to the porous catalyst layer made of Pd core (Pd/C). The distribution of Pt corresponded well with that of Pd throughout the catalyst layer, indicating that the core–shell reaction occurs in the entire catalyst layer. Pd@Pt/C shows 1.8 times higher mass activity than Pt/C, which is comparable to Pd@Pt/C prepared by conventional microgram-scale method.     

Numerical study of a new cathode flow-field design with a sub-channel for a parallel flow-field polymer electrolyte membrane fuel cell

The cathode flow-field design of a polymer electrolyte membrane (PEM) fuel cell is crucial to its performance, because it determines the distribution of reactants and the removal of liquid water from the fuel cell. In this study, the cathode flow-field of a parallel flow-field PEM fuel cell was optimized using a sub-channel. The main-channel was fed with moist air, whereas the sub-channel was fed with dry air. The influences of the sub-channel flow rate (SFR, the amount of air from the sub-channel inlet as a percentage of the total cathode flow rate) and the inlet positions (SIP, where the sub-channel inlets were placed along the cathode channel) on fuel cell performance were numerically evaluated using a three-dimensional, two-phase fuel cell model. The results indicated that the SFR and SIP had significant impacts on the distribution of the feed air, removal of liquid water, and fuel cell performance. It was found that when the SIP was located at about 30% along the length of the channel from main-channel inlet and the SFR was about 70%, the PEM fuel cell exhibited much better performance than seen with a conventional design.     

Effect of platinum amount in carbon supported platinum catalyst on performance of polymer electrolyte membrane fuel cell

The performance of polymer electrolyte membrane fuel cells fabricated with different catalyst loadings (20, 40 and 60 wt.% on a carbon support) was examined. The membrane electrode assembly (MEA) of the catalyst coated membrane (CCM) type was fabricated without a hot-pressing process using a spray coating method with a Pt loading of 0.2 mg cm⁻². The surface was examined using scanning electron microscopy. The catalysts with different loadings were characterized by X-ray diffraction and cyclic voltammetry. The single cell performance with the fabricated MEAs was evaluated and electrochemical impedance spectroscopy was used to characterize the fuel cell. The best performance of 742 mA cm⁻² at a cell voltage of 0.6 V was obtained using 40 wt.% Pt/C in both the anode and cathode.     

Effects of cathode catalyst layer design parameters on cold start behavior of polymer electrolyte fuel cells (PEFCs)

We present a theoretical study on the effects of key catalyst layer (CL) design parameters on the cold start behavior of a polymer electrolyte fuel cell (PEFC) using a three-dimensional transient cold start model developed in a previous study 1 and 2. Among several CL design parameters, we adopt the ionomer fraction (?_I) and weight ratio of Pt to carbon support (wt%_Pt–C) in the cathode CL as CL design variables for this study. Therefore, other design parameters such as CL thickness and the oxygen reduction reaction (ORR) kinetic parameter are accordingly adjusted due to changes in ?_I and wt%_Pt–C for cold start simulations. The calculated results confirm that these two design parameters provide control of the ice storage capacity and water absorption potential of the cathode CL, and consequently have a substantial influence on the cold start behavior of a PEFC. We provide a guideline to design and optimize a cathode CL and membrane electrode assembly (MEA) for improved PEFC cold start capability.     

Direct three-dimensional reconstruction of a nanoporous catalyst layer for a polymer electrolyte fuel cell

The direct three-dimensional reconstruction of a polymer electrolyte fuel cell cathode catalyst layer from focused ion beam/scanning electron microscope (FIB/SEM) images is presented. The carbon and pore distribution is shown and quantitatively analysed. A new catalyst layer sample (Fumapem-F950/HiSpec13100) is sliced with FIB and a series of SEM images is taken. The images are registered, segmented and a three-dimensional stack is reconstructed. The three-dimensional carbon and pore distribution is shown. Based on the reconstruction the pore size distribution is evaluated. The total porosity and the unconnected pores space is analysed. The fully segmented 2D images are provided as supplemental material to this paper for future analysis and modeling work.     

Comparative studies of polymer electrolyte membrane fuel cell stack and single cell

The polymer electrolyte membrane fuel cell (PEMFC) was investigated comparatively as a single cell and a 30-cell stack. Various types of Nafion membranes, such as Nafion 117, 115, 112 and 105, were tested as electrolyte within the single cell and at different temperatures, among which Nafion 112 gave the optimal result. The 30-cell stack was evaluated at different humidities and temperatures. The potential–current and power–current curves, both for single cell and the stack, were analyzed by computer simulation, whereby the kinetic and mass-transfer parameters were calculated. The long-term performance of the stack and the water production during long-term operation were also measured.     

New materials for polymer electrolyte membrane fuel cell current collectors

Polymer Electrolyte Membrane Fuel cells for automotive applications need to have high power density, and be inexpensive and robust to compete effectively with the internal combustion engine. Development of membranes and new electrodes and catalysts have increased power significantly, but further improvements may be achieved by the use of new materials and construction techniques in the manufacture of the bipolar plates. To show this, a variety of materials have been fabricated into flow field plates, both metallic and graphitic, and single fuel cell tests were conducted to determine the performance of each material. Maximum power was obtained with materials which had lowest contact resistance and good electrical conductivity. The performance of the best material was characterised as a function of cell compression and flow field geometry.     

Pore network modeling of cathode catalyst layer of proton exchange membrane fuel cell

In this paper, a pore network model is developed to investigate the coupled transport and reaction processes in the cathode catalyst layer (CCL) of proton exchange membrane fuel cell (PEMFC). The developed model is validated by comparing the predicted polarization curve with the experimental data, and the parametric studies are carried out to elucidate the effects of CCL design parameters. With the decrease of the CCL thickness and the Nafion content, the cell voltage reduces at the low current density but increases when the current density is higher. The cell performance is also improved by increasing the proton conductivity of the Nafion film in the CCL. As compared to the CCL of uniformly distributed Nafion, the CCL with the Nafion volume decreasing along the thickness direction exhibits better performance at the high current density.     

Chelating agent assisted heat treatment of carbon supported cobalt oxide nanoparticle for use as cathode catalyst of polymer electrolyte membrane fuel cell (PEMFC)

Cobalt-based catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cell (PEMFC) have been successfully incorporated cobalt oxide (Co₃O₄) onto Vulcan XC-72 carbon powder by thermal decomposition of Co-ethylenediamine complex (ethylenediamine, NH₂CH₂CH₂NH₂, denoted en) at 850 °C. The catalysts were prepared by adsorbing the cobalt complexes [Co(en)(H₂O)₄]³⁺, [Co(en)₂(H₂O)₂]³⁺ and [Co(en)₃]³⁺ on commercial XC-72 carbon black supports, loading amount of Co with respect to carbon black was about 2%, the resulting materials have been pyrolyzed under nitrogen atmosphere to create CoO_x/C catalysts, donated as E1, E2, and E3, respectively. The composite materials were characterized using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). Chemical compositions of prepared catalysts were determined using inductively-coupled plasma-atomic emission spectroscopy (ICP-AES). The catalytic activities for ORR have been analyzed by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The electrocatalytic activity for oxygen reduction of E2 is superior to that of E1 and E3. Membrane electrode assemblies (MEAs) containing the synthesized CoO_x/C cathode catalysts were fabricated and evaluated by single cell tests. The E2 cathode performed better than that of E1 and E3 cathode. This can be attributed to the enhanced activity for ORR, in agreement with the composition of the catalyst that CoO co-existed with Co₃O₄. The maximum power density 73 mW cm⁻² was obtained at 0.3 V with a current density of 240 mA cm⁻² for E2 and the normalized power density of E2 is larger than that that of commercial 20 wt.% Pt/C-ETEK.     

Improvement of cell performance in catalyst layers with silica-coated Pt/carbon catalysts for polymer electrolyte fuel cells

Carbon-supported Pt catalysts (Pt/Cs) for use of cathode catalyst layers (CLs) for PEFCs were covered with silica layers in order to improve performance. CLs with low ratio of ionomer to carbon (I/C) for Pt/C and silica-coated Pt/C were fabricated using an inkjet printing (denoted as Pt/C(IJ) and SiO₂-Pt/C(IJ)) to reduce oxygen diffusion resistance. Compared to Pt/C(IJ), SiO₂-Pt/C(IJ) ink maintained good dispersion and high stability under the lower I/C. The performance of SiO₂-Pt/C(IJ) was significantly higher than Pt/C(IJ) at 0.6 V under all humidity conditions. In particular, the performance of SiO₂-Pt/C(IJ) under low humidity conditions showed noticeable improvement regardless of current density area. From FIB-SEM, it was confirmed that the morphologies and porosities of both catalysts were the same. Thus, these results indicate that oxygen diffusion resistance, related to structure of CLs, hardly affects the performance, whereas improved performance is attributed to increased proton conductivity by silica layers containing hydrophilic groups.     

Dependence of the performance of a high-temperature polymer electrolyte fuel cell on phosphoric acid-doped polybenzimidazole ionomer content in cathode catalyst layer

Phosphoric acid-doped polybenzimidazole is used as a fuel cell membrane and an ionomer in the catalyst layer of a high-temperature polymer electrolyte fuel cell. Single-cell tests are performed to find the optimum ionomer content in the cathode catalyst layer. To determine the effects of the ionomer in the catalyst layer, the potential loss in the cell is separated into activation, ohmic and concentration losses. Each of these losses is examined by means of impedance and morphological analyses. With the weight ratio of ionomer to Pt/C of 1:4 (20 wt.% ionomer in catalyst layer), the fuel cell shows the lowest ohmic resistance. The activation loss in the fuel cell is lowest when the ratio is 1:9 (10 wt.% ionomer in the catalyst layer). The cell performance is dependent on this ratio, and the best cell performance is obtained with a ratio of 1:4.     

Performance equations for a polymer electrolyte membrane fuel cell with unsaturated cathode feed

A mathematical formulation for the cathode of a membrane electrode assembly of a polymer electrolyte membrane fuel cell is proposed, in which the effect of unsaturated vapor feed in the cathode is considered. This mechanistic model formulates the water saturation front within the gas diffusion layer with an explicit analytical expression as a function of operating conditions. The multi-phase flows of gaseous species and liquid water are correlated with the established capillary pressure equilibrium in the medium. In addition, less than fully hydrated water contents in the polymer electrolyte and catalyst layers are considered, and are integrated with the relevant liquid and vapor transfers in the gas diffusion layer. The developed performance equations take into account the influences of all pertinent material properties on cell performance using first principles. The mathematical approach is logical and concise in terms of revealing the underlying physical significance in comparison with many other empirical data fitting models.     

A review of polymer electrolyte membrane fuel cell stack testing

This paper presents an overview of polymer electrolyte membrane fuel cell (PEMFC) stack testing. Stack testing is critical for evaluating and demonstrating the viability and durability required for commercial applications. Single cell performance cannot be employed alone to fully derive the expected performance of PEMFC stacks, due to the non-uniformity in potential, temperature, and reactant and product flow distributions observed in stacks. In this paper, we provide a comprehensive review of the state-of-the art in PEMFC testing. We discuss the main topics of investigation, including single cell vs. stack-level performance, cell voltage uniformity, influence of operating conditions, durability and degradation, dynamic operation, and stack demonstrations. We also present opportunities for future work, including the need to verify the impact of stack size and cell voltage uniformity on performance, determine operating conditions for achieving a balance between electrical efficiency and flooding/dry-out, meet lifetime requirements through endurance testing, and develop a stronger understanding of degradation.     

Experimental study of the effect of dissolution on the gas diffusion layer in polymer electrolyte membrane fuel cells

The gas diffusion layer (GDL) is important for maintaining the performance of polymer electrolyte membrane (PEM) fuel cells, as its main function is to provide the cells with a path for fuel and water. In this study, the mechanical degradation process of the GDL was investigated using a leaching test to observe the effect of water dissolution. The amount of GDL degradation was measured using various methods, such as static contact angle measurements and scanning electron microscopy. After 2000 h of testing, the GDL showed structural damage and a loss of hydrophobicity. The carbon-paper-type GDL showed weaker characteristics than the carbon-felt-type GDL after dissolution because of the structural differences, and the fuel cell performance of the leached GDL showed a greater voltage drop than that of the fresh GDL. Contrary to what is generally believed, the hydrophobicity loss of GDL was not caused by the decomposition of polytetrafluoroethylene (PTFE).     

Effects of gas-diffusion layer properties on the performance of the cathode for high-temperature polymer electrolyte membrane fuel cell

The role of the gas-diffusion layer (GDL) in high-temperature polymer electrolyte fuel cell (HT-PEMFC) differs from that in low-temperature PEMFC GDL due to operating conditions and environment. Determining the GDL's structural parameters that affect its transport properties, and how these properties impact HT-PEMFC performance was urgently required. Four commercial GDLs were employed in HT-PEMFC cathode's GDE and was examined using X-μCT, mercury intrusion porosimetry, and an optical microscope to analyze structural parameters and characteristics. Fractal theory was applied to comprehend the gas transmission property of GDL, and the validity of the theory was confirmed through ex-situ through-plane gas permeability measurement. The analysis indicated that the porosity of GDL influenced by the crack region of the MPL has more impact on the GDL's gas transmission than its thickness. After that, we established a correlation between HT-PEMFC cathode performance and GDL porosity and theoretical gas transmission properties using R² coefficient of determination.     

Optimal catalyst layer structure of polymer electrolyte membrane fuel cell

In a membrane electrode assembly (MEA) of polymer electrolyte membrane fuel cells, the structure and morphology of catalyst layers are important to reduce electrochemical resistance and thus obtain high single cell performance. In this study, the catalyst layers fabricated by two catalyst coating methods, spraying method and screen printing method, were characterized by the microscopic images of catalyst layer surface, pore distributions, and electrochemical performances to study the effective MEA fabrication process. For this purpose, a micro-porous layer (MPL) was applied to two different coating methods intending to increase single cell performances by enhancing mass transport. Here, the morphology and structure of catalyst layers were controlled by different catalyst coating methods without varying the ionomer ratio. In particular, MEA fabricated by a screen printing method in a catalyst coated substrate showed uniformly dispersed pores for maximum mass transport. This catalyst layer on micro porous layer resulted in lower ohmic resistance of 0.087 Ω cm² and low mass transport resistance because of enhanced adhesion between catalyst layers and a membrane and improved mass transport of fuel and vapors. Consequently, higher electrochemical performance of current density of 1000 mA cm^-2 at 0.6 V and 1600 mAcm⁻² under 0.5 V came from these low electrochemical resistances comparing the catalyst layer fabricated by a spraying method on membranes because adhesion between catalyst layers and a membrane was much enhanced by screen printing method.