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.     

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.     

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.     

Nano mineral fiber enhanced catalyst coated membranes for improving polymer electrolyte membrane fuel cell durability

In order to protect the perfluorosulfonic acid (PFSA) ionomer from an attack of contaminant metal ions as well as to enhance the mechanical stability of catalyst layers, palygorskite (PGS) is introduced into the catalyst layer of polymer electrolyte membrane fuel cells. PGS is a widely used natural nano-sized silicate mineral fiber with unique nano-sized channel structure, has a strong absorption capacity for heavy metal ions. We identify a negative influence of Fe²⁺ on PFSA membranes to make a comparative study. Subsequently catalyst coated membranes (CCMs) prepared with a PGS-Pt/C composite catalyst show a great effect in reducing Fe²⁺ ion crossover. Results display that PGS absorbs Fe²⁺ in nano-structure channels, and effectively protect PFSA ionomer in both the catalyst layer and membrane from hydroxyl radicals (OH) attack. Thus, the chemical stability of PFSA ionomer in both the catalyst layer and membrane is greatly improved. Furthermore, the enhancement of the mechanical performance of catalyst layers is discussed.     

Reduced mass transport resistance in polymer electrolyte membrane fuel cell by polyethylene glycol addition to catalyst ink

Effects of Polyethylene glycol (PEG) addition to cathode catalyst ink were investigated by changing the addition amount of PEG. Performance of the polymer electrolyte membrane fuel cells (PEMFCs) increased and then decreased at the higher current density than 1.5 A/cm² as the amount of PEG addition increased. However, durability was not changed by the addition of PEG to the catalyst ink. Three different molecular weights of PEG were compared for PEG additives to cathode catalyst ink. Performance at high current density region increased and then decreased as PEG molecular weight increases from 200 to 10000. Increased performance by addition of PEG was attributed from reduced mass transport resistance. However, addition of large molecular weight PEG to catalyst ink reduced the performance because it lowered ionomer conductivity in the catalyst layer and then reduced proton transport resistance. Increased pore size in the catalyst layer and increased hydrophilicity on the electrode were also analyzed by addition of PEG to catalyst ink.     

Microscale simulations of reaction and mass transport in cathode catalyst layer of polymer electrolyte fuel cell

The resistance of the cathode oxygen reduction reaction in polymer electrolyte fuel cells must be reduced for improving the performance. Therefore, it is important to thoroughly understand the relationship between the heterogeneous structures and the cell performance. However, it is difficult to obtain such an understanding using experimental approaches and typical uniform porous simulations. In this study, numerical analysis was used to simulate a three-dimensional catalyst layer (CL) with carbon black (CB) aggregate structures and ionomer coating models, and a cathode reaction and mass transport simulation model incorporating the heterogeneous structure was developed. Moreover, the relationship between the electrode structure and the cell performance, including the reaction distribution and output performance, was examined. The current density distribution depended on the CB structure and ionomer adhesion shape. From the viewpoint of enhancing both the Pt utilization and the mass transport performance, an adequate heterogeneous pore structure in the CL is necessary. These results were used to determine the optimal material properties for the high performance cell.     

Temperature-dependent performance of the polymer electrolyte membrane fuel cell using short-side-chain perfluorosulfonic acid ionomer

We report on polymer electrolyte membrane fuel cells (PEMFCs) that function at high temperature and low humidity conditions based on short-side-chain perfluorosulfonic acid ionomer (SSC-PFSA). The PEMFCs fabricated with both SSC-PFSA membrane and ionomer exhibit higher performances than those with long-side-chain (LSC) PFSA at temperatures higher than 100 °C. The SSC-PFSA cell delivers 2.43 times higher current density (0.524 A cm⁻¹) at a potential of 0.6 V than LSC-PFSA cell at 140 °C and 20% relative humidity (RH). Such a higher performance at the elevated temperature is confirmed from the better membrane properties that are effective for an operation of high temperature fuel cell. From the characterization technique of TGA, XRD, FT-IR, water uptake and tensile test, we found that the SSC-PFSA membrane shows thermal stability by higher crystallinity, and chemical/mechanical stability than the LSC-PFSA membrane at high temperature. These fine properties are found to be the factor for applying Aquivion™ E87-05S membrane rather than Nafion^® 212 membrane for a high temperature fuel cell.     

Prediction of local current distribution in polymer electrolyte membrane fuel cell with artificial neural network

In the development process of a fuel cell, understanding the local current distribution is essentially required to achieve better performance and durability. Therefore, many developers apply a segmented fuel cell to observe current distribution under various operating conditions. With the application, experimental data is collected. This study suggests a utilization method for this collected data to develop a local current prediction model. The details of this neural network-based prediction model are introduced, including the pretreatment of the data. In the pretreatment process, current residual values are used for better prediction performance. As a result, the model predicted local current values with a 2.98% error. With the model, the effects of pressure, temperature, cathode relative humidity, and cathode flow rate on local current distribution trends are analyzed. Since the non-uniform current distribution of a fuel cell often leads to low performances or fast local degradation, the optimal operating condition to achieve current uniformity is acquired with an additional model. This model is developed by switching inputs and outputs of the local current prediction model. With the model application, the uniform current distribution is achieved with a standard deviation of 0.039 A/cm² under the current load at 1 Acm^?2.     

Effect of anode iridium oxide content on the electrochemical performance and resistance to cell reversal potential of polymer electrolyte membrane fuel cells

An ideal polymer electrolyte membrane fuel cell (PEMFC) is one that continuously generates electricity as long as hydrogen and oxygen (or air) are supplied to its anode and cathode, respectively. However, internal and/or external conditions could bring about the degradation of its electrodes, which are composed of nanoparticle catalysts. Particularly, when the hydrogen supply to the anode is disrupted, a reverse voltage is generated. This phenomenon, which seriously degrades the anode catalyst, is referred to as cell reversal. To prevent its occurrence, iridium oxide (IrO₂) particles were added to the anode in the membrane-electrode assembly of the PEMFC single-cells. After 100 cell reversal cycles, the single-cell voltage profiles of the anode with Pt/C only and the anodes with Pt/C and various IrO₂ contents were obtained. Additionally, the cell reversal-induced degradation phenomenon was also confirmed electrochemically and physically, and the use of anodes with various IrO₂ contents was also discussed.     

Tunable aggregation of short-side-chain perfluorinated sulfonic acid ionomers for the catalyst layer in polymer electrolyte membrane fuel cells

We control the aggregation of short-side-chain (SSC) perfluorinated sulfonic acid (PFSA) ionomers for catalyst-layer (CL) inks by using a dispersion solvent of dipropylene glycol (DPG) and water. By increasing the fraction of PFSA backbone preferable DPG content in a dispersion solvent, the size of SSC-PFSA aggregates decreases exponentially from microscale to nanoscale, affecting the catalyst-ionomer agglomerates’ size and distribution in the CL inks. The surface morphology and porosity properties of the resulting CL are investigated, and the fuel cell performances are studied at two different humidity conditions (50 and 100% RH). Compared to the previous study with long-side-chain (LSC) PFSA ionomers, the SSC-PFSA ionomers show the optimized performance at higher DPG content, where the solvating power is intermediate for SSC-PFSA ionomers having shorter hydrophilic side chain than LSC-PFSA ionomers.     

Influence of catalyst layer polybenzimidazole molecular weight on the polybenzimidazole-based proton exchange membrane fuel cell performance

The catalyst layer (CL) of a polybenzimidazole (PBI) membrane electrode assembly (MEA) consists of Pt–C (Pt on a carbon support), PBI, and H₃PO₄. Two series of catalyst ink solutions each containing Pt–C, N,N′-dimethyl acetamide, and PBIs comprising four different molecular weights (MWs) (i.e., M_w = 1.1 × 10⁴, 4.4 × 10⁴, 9.0 × 10⁴, and 17.4 × 10⁴ g mol⁻¹) are used to fabricate CLs. One catalyst ink solution series is mixed with LiCl, while the other solution series lacks LiCl. We demonstrate that the CL prepared using a lower MW PBI has a higher electrochemical surface area, lower charge transfer resistance, and higher fuel cell performance. The addition of LiCl enhances the dispersion of the high MW PBIs in the catalyst ink solution and acts as a foaming agent in CL, thus improving fuel cell performance. However, LiCl exerts small influence on the fuel cell performance of the MEAs fabricated using low MW PBIs.     

The use of MWCNT to enhance oxygen reduction reaction and adhesion strength between catalyst layer and gas diffusion layer in polymer electrolyte membrane fuel cell

The pore structure and pore volume of catalyst layer (CL) were controlled by utilizing multi-walled carbon nanotube (MWCNT). According to the increase in MWCNT ratio in CL, the primary pore (below 100 nm) volume concerning with the phosphoric acid penetration to the reaction site was decreased and the secondary pore (approximately 1 μm) volume relating with oxygen gas transportation was increased, respectively. However, the excessive addition of MWCNT was detrimental to electrochemical properties due to the difficulty of phosphoric acid penetration to the reaction site and the opposite influx of phosphoric acid to the secondary pore. Furthermore, the adhesion strength between CL and gas diffusion layer (GDL) was improved by only 10% addition of MWCNT. Therefore, it is suggested that the ratio of MWCNT in CL can be key role for obtaining the optimized pore volume, enhanced adhesion strength, and good performance of polymer electrolyte membrane fuel cell (PEMFC).     

Improving open-cathode polymer electrolyte membrane fuel cell performance using multi-hole separators

We developed a new separator with a multi-hole structure (MHS) in the rib region for open-cathode polymer electrolyte membrane fuel cell (OC-PEMFC) stack to improve performance. The electrochemical current–voltage performance results clearly demonstrate that the performance of the OC-PEMFC stack using the MHS design was higher than that using the conventional parallel design at high current regions (i.e., over 7 A). The current increased by 11.24% at 12 V (i.e., 0.6 V/cell). The effects of supplying additional oxygen and removing generated water were identified as factors improving the performance. The individual cell voltages demonstrate that the initial value of standard deviation for the OC-PEMFC stack using MHS was somewhat high, but it exhibited better uniformity at higher current regions.     

Characterization of interfacial morphology in polymer electrolyte fuel cells: Micro-porous layer and catalyst layer surfaces

The interface between the micro-porous layer (MPL) and the catalyst layer (CL) can have an impact on thermal, electrical and two-phase mass transport in a polymer electrolyte fuel cell (PEFC). However, there is scant information available regarding the true morphology of the MPL and CL surfaces. In this work, optical profilometry is used to characterize the MPL and CL surfaces at the sub-micron level scale to gain a better understanding of the surface morphology. Selected MPL and CL surfaces were sputtered with a thin layer of gold to enhance the surface reflectivity for improved data acquisition. The results show that, for the materials tested, the MPL surface has a relatively higher roughness than the CL surface, indicating the potential dominance of the MPL surface morphology on the local transport and interfacial contact across the MPL|CL interface. The level of roughness can be on the order of 10 μm peak height, which is significant in comparison to other length scales involved in transport, and can result in significant interfacial water storage capacity (approximately 6-18% of the total water content in a PEFC [37]) along this interface. Another surface characteristic that can have a profound influence on multi-phase transport is the existence of deep cracks along the MPL and CL surfaces. The cracks on MPL and CL surfaces are observed to differ significantly in terms of their orientation, size, shape, depth and density. The areal crack density of the CL tested is calculated to be 3.4 ± 0.2%, while the areal crack density of the MPL is found to vary from 2.8% to 8.9%. The results of this study can be useful to understand the true nature of the interfacial transport in PEFCs.     

Durability improvement at high current density by graphene networks on PEM fuel cell

This study presents a novel structure of catalyst layers of membrane electrode assemblies (MEAs) by adding graphene to platinum on carbon black (Pt/C) to improve the durability at high current density operation (3 A cm⁻²). Graphene displays outstanding low electrical resistance and has the advantage of high electron mobility. It is also used in lithium ion batteries to improve electrical performance such as high rate charge/discharge capability and cycle-life stability. In this study, three MEAs are compared, and graphene is used as an excellent conductive additive in catalyst layers for better electrons transport at high current density operation. The MEA coated Pt/C mixed with 0.1 wt% graphene shows best durability for 0.3 V h⁻¹ which is almost 3.7 times better than that of without graphene additive (1.1 V h⁻¹). The graphene additive effectively extends the durability of the MEA. Furthermore, the MEAs are analyzed by AC impedance. The impedance arc of the MEA coated with Pt/C only is getting worse, but those two coated with graphene show similar and smaller impedance arcs after high current density operation for 80 h.     

Enhancement of polymer electrolyte membrane fuel cell performance by boiling a membrane electrode assembly in sulfuric acid solution

A catalyst-coated membrane (CCM) as used in the membrane electrode assembly (MEA) of a polymer electrolyte membrane fuel cell is treated by dilute sulfuric acid solution (0.5 M) at boiling temperature for 1 h. This treatment improves the single-cell performance of the CCM without further addition of Pt catalyst. The changed microstructure and electrochemical properties of the catalyst layer are investigated by field emission scanning electron microscopy with energy dispersive X-ray, mercury intrusion porosimetry, waterdrop contact angle measurement, Fourier transform-infrared spectrometry in attenuated total reflection mode, electrochemical impedance spectroscopy, and cyclic voltammetry. The results indicate that this pretreatment enhances MEA performance by changing the microstructure of the catalyst layer and thus changing the degree of hydration, and by modifying the Pt surface, thus enhancing the oxygen reduction reaction.     

Electronic conductivity of catalyst layers of polymer electrolyte membrane fuel cells: Through-plane vs. in-plane

In this work, novel procedures are developed to measure in-plane and through-plane electronic conductivities of catalyst layers (CLs) for polymer electrolyte membrane fuel cells. The developed procedures are used in a parametric study on different CL designs to investigate effects of different composition and fabrication parameters, including ionomer to carbon weight ratio (I/C ratio), dry milling time of the catalyst powder, and drying temperature of the catalyst ink. Results show that CLs have anisotropic electronic conductivity with through-plane values being three orders of magnitude lower than the in-plane values. The reason for this anisotropy is speculated to be alignment of fibrillar nanostructures of ionomer by large shear forces during coating, which could result in better carbon-carbon contact in the in-plane direction. A simple order of magnitude analysis shows the significance of poor through-plane conduction for fuel cell performance.     

Influence of local porosity and local permeability on the performances of a polymer electrolyte membrane fuel cell

In the literature, many models and studies focused on the steady-state aspect of fuel cell systems while their dynamic transient behavior is still a wide area of research. In the present paper, we study the effects of mechanical solicitations on the performance of a proton exchange membrane fuel cell as well as the coupling between the physico-chemical phenomena and the mechanical behavior. We first develop a finite element method to analyze the local porosity distribution and the local permeability distribution inside the gas diffusion layer induced by different pressures applied on deformable graphite or steel bipolar plates. Then, a multi-physical approach is carried out, taking into account the chemical phenomena and the effects of the mechanical compression of the fuel cell, more precisely the deformation of the gas diffusion layer, the changes in the physical properties and the mass transfer in the gas diffusion layer. The effects of this varying porosity and permeability fields on the polarization and on the power density curves are reported, and the local current density is also investigated. Unlike other studies, our model accounts for a porosity field that varies locally in order to correctly simulate the effect of an inhomogeneous compression in the cell.