Investigation of a cost-effective strategy for polymer electrolyte membrane fuel cells: High power density operation

Polymer electrolyte membrane (PEM) fuel cell technology needs to overcome the cost barrier in order to compete with the internal combustion engines (ICEs) for transportation application. A viable approach is to raise fuel cell's power output without increasing its size and Pt loading in the catalyst layers (CLs). In this strategy, the cost per kW power output can be proportionally reduced due to the increased power density. This paper examines this strategy by exploring several important aspects that influence fuel cell performance under high power or current density using a three-dimensional (3-D) fuel cell model. It is shown that local CLs may be subject to low oxygen concentration under a high current density of 2 A/cm², causing low reaction rate near the outlet, especially under the land. Additionally, the oxygen reduction reaction (ORR) rate may be subject to a large through-plane variation under 2 A/cm², raising ohmic voltage loss in the CL. Two additional cases are investigated to improve fuel cell performance under 2 A/cm²: one has a 5 times thinner CL with the same ORR kinetics per membrane electrode assembly (MEA) area and the other has a 5 times thinner CL with 5 times higher ORR kinetics. The results show the output voltage is raised approximately from 0.5 V to 0.554 V in the former CL case and further to 0.606 V for the latter CL. To enable high-efficiency operation (e.g. >50%), thinner CLs with high ORR kinetics and GDLs with better transport properties are one research and development (R&D) direction.     

Pore-scale numerical study of multiphase reactive transport processes in cathode catalyst layers of proton exchange membrane fuel cells

understanding interactions between multiphase flow and reactive transport processes in catalyst layers (CL) of proton exchange membrane fuel cells is crucial for obtaining better performance and lower cost. In this study, a pore-scale model is developed to simulate coupled processes occurring in CLs, including oxygen diffusion, electrochemical reaction, and air-liquid two phase flow. Simulation conducted in an idealized local CL structures shows that the pore-scale model successfully captures dynamic behaviors of liquid water including generation, growth and subsequent migration, as well as the interaction between multiphase flow and reactive transport. Pore-scale simulation is then conducted in hydrophobic CLs with complicated structures where carbon, platinum, ionomer and pores are resolved. It is found that filling modes of the liquid water in the CLs are different. Before forming the continuous flow paths in CLs, liquid water presents as tiny droplets in pores surrounding relative large pores. After the continuous flow paths are formed, liquid water dynamic behaviors follow the capillary fingering mechanism. The multiphase flow and reactive transport processes are closely coupled with each other, and as liquid water saturation increases the reaction rate decreases. Increasing the hydrophobicity can alleviate the water flooding, accelerate the water breakthrough, and facilitate the water evaporation.     

Compressive behaviour of thin catalyst layers. Part II - Model development and validation

In the second part of this study, a new analytical model for catalyst layers (CLs) compression is developed using effective medium theory, using a geometric “unit cell”, to accurately predict the deformation of CLs under compression. Based on SEM images, a representative unit cell is proposed using microstructural properties of CL such as porosity, pore size distribution, and ionomer to carbon weight ratio (I/C) to simplify the random complex structure of CLs. Deformation of the ionomer film that covers carbon agglomerates is found to be the main deformation compared to other mechanisms such as Hertzian compliance of carbon particles and deformation of agglomerates. The present model is validated using the experimental results obtained for five different CL designs, presented in Part 1 of this study. The analytical model is capable of predicting the non-linear compressive behaviour of CLs with a reasonable accuracy since a continuous change of CL porosity is considered in the model. The proposed geometrical model has also been used for other properties of CL in our group and successfully predicted thermal conductivity and gas diffusivity of CL.     

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.     

A novel anode catalyst layer with multilayer and pore structure for improving the performance of a direct methanol fuel cell

A novel anode catalyst layer (CL) has been prepared by ultrasonic‐spray process which combines directly spraying method and catalyst‐coated membrane switchover method, and heated‐stereoscopic process has been used to enhance bond force between CLs and proton exchange membrane in this paper. The scanning electron microscopy, electrochemical impedance spectra and polarization curves show that: the anode outer CL with pores and meshwork structure has increased the electrochemical active surface area and retained the transfer of protons and electrons, and the anode inner CL with compact structure has prevented methanol crossover. And the gradient catalysis for methanol electrochemical catalytic oxidation reaction has been achieved. The open circuit voltage has reached 0.697 V, and the performance has increased from 116.8 mW cm^?2 of traditional membrane electrode assembly (MEA) to 202.6 mWcm^?2 of novel MEA at 80°C. Copyright © 2012 John Wiley & Sons, Ltd.     

The influence of graphitization on the thermal conductivity of catalyst layers and temperature gradients in proton exchange membrane fuel cells

As the proton exchange membrane fuel cell (PEMFC) has improved its performance and power density, the efficiency has remained unchanged. With around half the reaction enthalpy released as heat, thermal gradients grow. To improve the understanding of such gradients, PEMFC component thermal conductivity has been increasingly investigated over the last ten years, and the catalyst layer (CL) is one of the components where thermal conductivity values are still scarce. CLs in PEMFC are where the electrochemical reactions occur and most of the heat is released. The thermal conductivity in this region affects the heat distribution significantly within a PEMFC. Thermal conductivities for a graphitized and a non-graphitized CL were measured for compaction pressures in the range of 3 and 23 bar. The graphitized CL has a thermal conductivity of 0.12 ± 0.05 WK^–1m^–1, whilst the non-graphitized CL conductivity is 0.061 ± 0.006 WK^–1m^–1, both at 10 bar compaction pressure. These results suggest that the graphitization of the catalyst material causes a doubling of the thermal conductivity of the CL. This important finding bridges the very few existing studies. Additionally, a 2D thermal model was constructed to represent the impact of the results on the temperature distribution inside a fuel cell.     

Optimization of catalyst-coated membranes for enhancing performance in proton exchange membrane electrolyzer cells

To achieve large-scale application of proton exchange membrane electrolyzer cells (PEMECs) for hydrogen production, it is highly desirable to reduce the manufacturing cost while enhancing cell performance. In the PEMPECs, a catalyst-coated membrane (CCM) is the vital component where electrochemical reactions and mass transport mainly occur. The fabrication methods and catalyst layer (CL) structure can significantly affect the cell performance. Herein, for the first time, a comparative study of CCM fabrications with decal transfer and direct spray deposition methods have been conducted by both ex-situ materials characterization and in-situ performance testing in PEMECs. It is found CCMs that are fabricated with a direct spray deposition method display enhanced cell performance compared to CCMs fabricated with a decal transfer method, mainly due to the largely reduced ohmic resistance and improved mass transport. More importantly, cell performance can be greatly enhanced by simply regulating the Nafion ionomer content at the anode CL. The optimal Nafion ionomer content of 10 wt% gives the best cell performance at 80 °C with a low cell voltage of 1.887 V at 2 A cm^?2, outperforming the commercial CCM and most other previous publications. Our study provides a valuable guidance for fabrication and optimization of CCMs with significantly enhanced performance and reduced cost for practical application of the PEMECs.     

The influence of surface finishing on the electrocatalytic properties of nickel for the oxygen evolution reaction (OER) in alkaline solution

The oxygen evolution reaction (OER) was investigated at 60 °C in 15wt% NaOH solution on nickel electrodes. Different surface treatments such as sandblasting and/or chemical pickling were employed. Fresh and aged electrodes were subjected to electrochemical measurements. The galvanostatic electrochemical ageing was performed for 21 days, applying an anodic current equal to 150mA cm⁻². From the Tafel plots for the OER, two well-defined Tafel slopes were observed for all the electrodes, before and after the electrochemical ageing. This behaviour is due to the transformation of Ni(OH)₂ to β-NiOOH, which is the “right type of oxide” for the oxygen evolution reaction. The kinetic parameters obtained on the electrodes with different surface finishing show that the sandblasted/pickled nickel substrate loses its electrocatalytic properties for the OER early on in the experiment.     

Poroelastic PEM fuel cell catalyst layer and its implication in predicting the effect of mechanical load on flow and transport properties

This study experimentally and numerically investigates the polymer electrolyte fuel cell (PEFC) catalyst layers (CLs) to analyze the coupled pore-fluid diffusion and resultant stress distribution. In the study, effect of nanoporosity on mechanical strength is explored by analyzing the CL structure based on the elastic modulus and the yield strength scaling laws of open-cell foams. A finite element analysis of the CL is performed by adopting the biphasic consolidation theory. The biphasic theory in combination with the transient consolidation principle of a porous body is formulated to account for the variation in the external loading conditions as well as the internal pore pressure. The CLs are observed to have the elastoplastic ionomer matrix and anisotropic nanoporosity, which are responsible for the localized plastic densification on indentation. The indentation behavior of the CLs appears to respond similar to the conventional low-density nanoporous foams leading to the localized nonlinear response of contact stiffness. The mechanical properties were found to be insensitive to the constituents’ (Pt and Carbon) concentration gradation over the CL thickness. In the numerical results, effect of porosity loss on the transport properties is discussed to highlight the importance of estimating the stress levels. It is outlined from the present study that under critical loading conditions, the yield limits of the CL play a crucial role in estimating the extent of transport losses. The effective proton conductivity and oxygen diffusivity losses are dependent on the macroscopic strength of the ionomer and the effective electronic conductivity loss is a function of intrinsic strength of the CL, which is also responsible for the overall durability of the CL.     

The effects of different dimensional carbon additives on performance of PEMFC with low-Pt loading cathode catalytic layers

The addition of carbon additives to the catalytic layers (CLs) with low-Pt loadings significantly improves the cell performance of proton exchange membrane fuel cells. However, the structure-activity relationship between the different dimensional carbon materials in CLs and the cell performance is still unknown. In the present work, three different dimensional carbon materials have been added into the cathode CLs with low Pt loading. The addition of one-dimensional carbon nanotubes and zero-dimensional XC-72R significantly enhanced the power density of the fuel cell because of the improved Pt dispersion and porous structures of the CL. This resulted in enhanced gas transfer and water removal accessibility. Nevertheless, the tortuous transfer path of gas and water after the presence of graphene nanosheet in the CL results in increased mass transfer resistance, although it reduces the charge transfer of the CL due to the improved catalyst utilization at low current density regions of polarization curves.     

Optimization of catalyst ink composition for the preparation of a membrane electrode assembly in a proton exchange membrane fuel cell using the decal transfer

For low interfacial resistance and feasibility of forming catalyst layer (CL), decal transfer (DT) is considered as one of the most effective methods for preparing a membrane electrode assembly. However, optimization of the catalyst ink composition is necessary, because of the complexity of the CL. Here, 1-propanol is adsorbed onto the CL coated onto the decal, as a swelling agent, for complete transfer of the CL onto Nafion membrane. Using this methodology, flat and complete DT is achieved at the hot-pressing conditions of 60 °C and 5 MPa. For optimization, the solvent-to-carbon ratio (SCR) and Nafion-to-carbon ratio (NCR) are controlled to achieve improved cell performance. In this study, by considering the morphology of CL and the cell performance when CL is annealed at temperatures sufficiently below the boiling point of the solvent, optimized SCR and NCR values of approximately 12.0 and 0.65, respectively, are obtained. In addition, microstructure, thickness and various electrochemical properties of the CLs are examined in detail.     

Optimization of gas diffusion electrode for polybenzimidazole-based high temperature proton exchange membrane fuel cell: Evaluation of polymer binders in catalyst layer

Gas diffusion electrodes (GDEs) prepared with various polymer binders in their catalyst layers (CLs) were investigated to optimize the performance of phosphoric acid doped polybenzimidazole (PBI)-based high temperature proton exchange membrane fuel cells (HT-PEMFCs). The properties of these binders in the CLs were evaluated by structure characterization, electrochemical analysis, single cell polarization and durability test. The results showed that polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF) are more attractive as CL binders than conventional PBI or Nafion binder. At ambient pressure and 160 °C, the maximum power density can reach ∼ 0.61 W cm⁻² (PTFE GDE), and the current density at 0.6 V is up to ca. 0.52 A cm⁻² (PVDF GDE), with H₂/air and a platinum loading of 0.5 mg cm⁻² on these electrodes. Also, both GDEs showed good stability for fuel cell operation in a short term durability test.     

Numerical analysis on transport properties of self-humidifying dual catalyst layer via 3-D reconstruction technique

Developing a fuel cell model with fundamental structural properties such as distribution of pore size, geometrical network of individual phase, and volume-specific interfacial area are critical in evaluating the accurate cell performance. Therefore, herein, by Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) tomography, three-dimensional (3-D) microstructure of CLs is reconstructed from two real-time samples: (i) High tortuosity humidifying catalyst layer (HTH CL) and (ii) standard catalyst layer. From the reconstructed microstructure, water imbibition behavior at different levels of capillary pressure is simulated and the effective transport properties such as gas permeability, gas diffusivity, surface area and water permeability are derived as well. By coupling the effective structural and transport properties, a 2D model is developed to predict the performances of the two CLs, at relative humidity (RH) levels of 20% and 100%. Since the effective transport properties are derived from real-time samples, this 2D model is expected to have a greater accuracy in predicting the fuel cell performance. Finally, the mechanism of self-humidifying MEA at lower and higher RH conditions (20% RH and 100% RH) is demonstrated as a function of liquid water saturation in the cathode CL and water dry-out in the anode CL.     

Stochastic reconstruction and a scaling method to determine effective transport coefficients of a proton exchange membrane fuel cell catalyst layer

This work uses a method for the stochastic reconstruction of catalyst layers (CLs) proposing a scaling method to determine effective transport properties in proton exchange membrane fuel cell (PEMFC). The algorithm that generates the numerical grid makes use of available information before and after manufacturing the CL. The structures so generated are characterized statistically by two-point correlation functions and by the resultant pore size distribution. As an example of this method, the continuity equation for charge transport is solved directly on the three-dimensional grid of finite control volumes (FCVs), to determine effective electrical and proton conductivities of different structures. The stochastic reconstruction and the electrical and proton conductivity of a 45 μm side size cubic sample of a CL, represented by more than 3.3 × 10¹² FVCs were realized in a much shorter time compared with non-scaling methods.Variables studied in an example of CL structure were: (i) volume fraction of dispersed electrolyte, (ii) total CL porosity and (iii) pore size distribution. Results for the conduction efficiency for this example are also presented.     

Effects of open-circuit operation on membrane and catalyst layer degradation in proton exchange membrane fuel cells

Durability issues have been attracting a great deal of attention in hydrogen/air proton exchange membrane (PEM) fuel cell research. In the present work, membrane electrode assembly (MEA) degradation under open circuit (OC) conditions was carried out for more than 250 h. By means of several on-line electrochemical measurements, the performance of the fuel cell was analysed at different times during the degradation process. The results indicate that structural changes in the PEM and catalyst layers (CLs) are the main reasons for the decline in performance during OC operation. The results also show that degradation due to platinum oxidation or catalyst contamination can be partially recovered by a subsequent potential cycling process, whereas the same cycling process cannot recover the membrane degradation.     

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).     

Evaluation of the boiling effect on oxygen evolution reaction using a three-electrode cell

The high initial cost of polymer electrolyte membrane water electrolyzers (PEMWEs) has delayed their widespread commercialization. A possible means to reduce cost is by reducing the overvoltage and increasing the current density to reduce the electrode area. This study proposes a novel method in which boiling is superimposed on the oxygen evolution reaction (OER) to decrease electrolysis voltage. The vapor bubbles formed by boiling are expected to decrease the concentration overvoltage. The boiling effect was experimentally analyzed using a three-electrode cell. Although a general catalyst layer (CL) was formed on a working electrode (WE) bar, the structure of the working electrode (WE) bar was special, in which a 10-W heater was embedded and made boiling on the electrode under 1 bar condition. Increasing the electrode temperature under static OER current density slightly decreased the OER potential. However, an abrupt decrease in potential was observed when the temperature was scaled over the boiling temperature. Moreover, this abrupt decrease substantially intensified when, similar to a practical PEMWE, a porous transfer layer (PTL) and flow channel were assembled on the CL. These experimental results suggest that boiling can reduce the concentration overvoltage by reducing the oxygen concentration on the CL, especially when the mass transport resistance caused by the PTL is considerable. Innovatively and simply utilizing boiling, as proposed here, can enhance the oxygen transfer and contribute to reducing the initial cost of PEMWEs.     

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.     

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.     

Effect of rotating disk electrode conditions on oxygen evolution reaction activity of Ir nanoparticle catalysts and comparison with membrane and electrode assemblies

In this study, we investigated the parameters of the rotating disk electrode (RDE) affecting the activity evaluations for the oxygen evolution reaction (OER). To precisely obtain the activation polarization, the impacts of RDE parameters on the measured OER activity are examined using various iridium catalysts. The potential range, catalyst loading on the disk electrode and anions in the electrolyte have a significant impact on the catalytic activity. The OER activities of the Ir catalysts under the optimized RDE conditions are compared with those determined using a labo-scale electrolyzer test cell and membrane and electrode assembly (MEA). The OER activity of MEA after stabilization is consistent with that of the RDE results. Therefore, the RDE half-cell with proper evaluation condition should be a useful and rapid initial catalyst screening method to estimate the OER activity in the MEA.