Performance and Durability of Membrane Electrode Assemblies Based on Radiation‐Grafted FEP‐g‐Polystyrene Membranes

Membrane electrode assemblies (MEAs) based on radiation‐grafted proton exchange membranes developed at PSI have shown encouraging performance in the past in hydrogen and methanol fuelled polymer electrolyte fuel cells. In this study, the effect of the pre‐treatment of crosslinked radiation‐grafted FEP membranes prior to lamination with the electrodes on the performance of the MEAs was investigated. Two approaches were assessed separately and in combination: (1) the impregnation of the radiation‐grafted membranes with solubilised Nafion®, and (2) the use of a swollen vs. dry membrane. It is found that the combination of coating the membrane with Nafion® ionomer and hot‐pressing the MEA with the membrane in the wet state produce the best single cell performance. In the second part of the study, the durability of an MEA, based on a radiation‐grafted FEP membrane, was investigated. The performance was stable for 4,000 h at a cell temperature of 80 °C. Then, a notable degradation of the membrane, as well as the electrode material, started to occur as a consequence of either controlled or uncontrolled start‐stop cycles of the cell. It is assumed that particular conditions, to which the cell is subjected during such an event, strongly accelerate materials degradation, which leads to the premature failure of the MEA.     

Effects of curing condition of solution cast Nafion® membranes on PEMFC performance

To study the feasibility of applying solution-cast membranes to polymer electrolyte membrane fuel cells (PEMFCs), single cells prepared with solution-cast membranes were tested. The solution cast membranes were fabricated from a commercial Nafion solution under various conditions. Effects of annealing temperature on characteristics of the solution-cast membranes were investigated by measuring water uptake and ionic conductivity of the membranes. Performance of the single cells using the prepared solution cast membranes was evaluated in terms of i-V curves, Nyquist plots, and H₂ crossover current density. Based on the results, solution-cast membranes were fabricated by being cured at 150 °C for different hours to examine effects of curing time on cell performance. Finally, durability of solution-cast membranes was investigated with operating the single cells for 1,000 hr.     

Magnetic Resonance Imaging of Water in Operating Polymer Electrolyte Membrane Fuel Cells

Water management in polymer electrolyte membrane fuel cells (PEMFCs) is extremely important for the high performance and durable operation of fuel cells. Therefore, fundamental understanding of water transport involved in operating PEMFCs is necessary. This article presents a review of in situ magnetic resonance imaging (MRI) visualisation of water in operating PEMFCs, which is recognised as a powerful diagnostic tool for probing water behaviours, both in flow fields and in the membrane electrode assembly (MEA). The basic principles and hardware related to MRI visualisation are described with emphasis on the design, construction and material selection of a PEMFC for MRI experiments. The MRI results reported by several groups are outlined to illustrate the versatility and potential usefulness of in situ visualisation of water in operating PEMFCs using MRI.     

Membrane Electrode Assembly with Ultra Low Platinum Loading for Cathode Electrode of PEM Fuel Cell by Using Sputter Deposition

Cathode electrodes of proton exchange membrane fuel cells were fabricated by using Pt sputter deposition to increase the gravimetric power density (W mg_Pt⁻¹) with reduced Pt loading. Ultra low Pt‐based electrodes having Pt loading in between 0.0011 and 0.06 mg_Pt cm⁻² were prepared by a radio frequency (RF) sputter deposition method on the surface of a non‐catalyzed gas diffusion layer (GDL) substrate by changing the sputtering time (20, 90, 180, 1050 s). The effect of cathode Pt loading on the performance of membrane electrode assembly were investigated using polarization curve, impedance, H₂ crossover and cyclic voltammetry techniques. The effect of backpressure on PEMFC performance was also investigated. Sputter1050 (0.06 mg_Pt cm⁻²) exhibited the best power density at 80 °C cell temperature and without backpressure for H₂/O₂, 100 %RH (297 mW cm⁻² and 5 W mg_Pt⁻¹ at 0.6 V). On the other hand sputter90 (0.005 mg_Pt cm⁻²) showed the peak gravimetric power density (15 W mg_Pt⁻¹ and 75 mW cm⁻² at 0.6 V). The Pt utilization efficiency increased as the Pt loading decreased. Sputter20 and sputter90 electrodes yielded insufficient electrochemical surface area (ECSA), higher charge transfer and ohmic resistance, but sputter180 and sputter1050 yielded sufficient ECSA and lower charge transfer and ohmic resistance.     

Preparation of KOH‐doped PVA/PSSA Solid Polymer Electrolyte for DMFC: The Influence of TiO2 and PVP on Performance of Membranes

The development of low cost alkaline anion solid exchange membranes requires high ionic conductivity, low liquid uptake, strong mechanical properties and chemical stability. PVA/PSSA blends cross‐linked with glutaraldehyde and decorated with titanium dioxide nanoparticles introduce advantages relative to the pristine membrane of PVA and PVA/PVP membranes due to their improved electrical response and low methanol uptake/ swelling ratio allowing their use in alkaline direct methanol fuel cells.     

Benefits of Membrane Electrode Assemblies with Asymmetrical GDL Configurations for PEM Fuel Cells

Membrane electrode assemblies (MEAs), based on commercial catalyst‐coated membranes combined with various gas diffusion layers (GDLs) on anode and cathode, were studied in terms of their specific advantages for different operations regimes of proton exchange membrane fuel cells (PEMFCs.) It is verified that MEAs with optimized gas diffusion layer designs (backing and micro‐porous layers) on anode and cathode are able to provide improved cell performance combined with a largely reduced sensitivity towards changes in the relative humidity as compared to MEAs with symmetrical gas diffusion layer configuration.     

Raman Spectroscopy of an Aged Low Temperature Polymer Electrolyte Fuel Cell Membrane

The cost and durability of the membrane electrode assembly (MEA) are today limiting factors for large‐scale commercialisation of the polymer electrolyte membrane fuel cell (PEMFC). The MEA durability in a real working fuel cell (FC) is closely linked to specific operating conditions such as temperature, gas humidity, load dynamics, etc. This often results in both chemical and mechanical degradation of the ion‐conducting membrane and subsequent operation failure of the FC. In this study, Raman spectroscopy is used to identify and distinguish between two different degradation processes for a 1,500 h in situ aged FC membrane. The primary process is due to the loss of proton conducting sulphonic acid end groups over the entire membrane. The secondary process is a degradation of the fluorinated backbone concentrated to the cathode interface; making possible the collapse of carbon into the resulting voids of the membrane. Using spatially resolved Raman spectroscopy we can unambiguously observe both the localisation and the state of the carbon inside the membrane; being similar/identical to the microporous layer (MPL).     

Understanding Water Transport in Polymer Electrolyte Fuel Cells Using Coupled Continuum and Pore‐Network Models

Water management remains a critical issue for polymer electrolyte fuel cell performance and durability, especially at lower temperatures and with ultrathin electrodes. To understand and explain experimental observations better, water transport in gas diffusion layers (GDLs) with macroscopically heterogeneous morphologies was simulated using a novel coupling of continuum and pore‐network models. X‐ray computed tomography was used to extract GDL material parameters for use in the pore‐network model. The simulations were conducted to explain experimental observations associated with stacking of anode GDLs, where stacking of the anode GDLs increased the limiting current density. Through imaging, it is shown that the stacked anode GDL exhibited an interfacial region of high porosity. The coupled model shows that this morphology allowed more efficient water movement through the anode and higher temperatures at the cathode compared to the single GDL case. As a result, the cathode exhibited less flooding and hence better low temperature performance with the stacked anode GDL.     

Synthesis and characterization of poly(ether sulfone) grafted poly(styrene sulfonic acid) for proton conducting membranes

Two-step synthesis of proton-conducting poly(ether sulfone) (PES) graft copolymer electrolyte membrane is proposed. Fridel Craft alkylation reaction was used to introduce chloromethyl pendant group onto the PES polymer backbone. Later on, atom transfer radical polymerization (ATRP) was applied to synthesize a series of poly(ether sulfone) grafted poly(styrene sulfonic acid) (PES-g-PSSA). Successful chloromethyl substitution and grafting of the pendant group was characterized by the ¹H-NMR and elemental analysis. Electrochemical properties such as ion exchange capacity (IEC), water uptake and proton conductivity increased with increasing PSSA contents. Thermal gravimetric analysis (TGA) showed the thermal stability of membranes up to 270 °C. Proton conductivity for maximum amount of grafting was 0.00297 S/cm.     

Preparation and Characterisation of Novel Composites Based on a Radiation Grafted Membrane for Fuel Cells

Novel composites for fuel cells were prepared via two different methods using a radiation grafted membrane, prepared from poly(ethylene‐alt‐tetrafluoroethylene) (ETFE) and styrene, and commercial Nafion®112 as the substrates. The first method was based on chemical polymerisation of pyrrole (Py) on the membrane followed by platinum (Pt) deposition by chemical reduction. The second method was based on direct deposition of Pt on the membrane by several steps of initial composite formation and surface electrodeposition. Polypyrrole (PPy) was coated as a layer only on the surface of the membrane. The thickness of PPy layer, proton conductivity of the composites and Pt loading could be controlled with Py polymerisation time. Moreover, the deposition of Pt on the surface as the granular particles was achieved by the first method while Pt deposition occurred as the aggregates of particles on the surface of the membrane by the second method which yielded wavy and rough surfaces. The first method offered a simple, quick, reproducible and effective procedure, yet some of the Pt particles peeled off from the surface of the composites. The second method required complex, multistep and tedious procedure with a high amount of Pt precursor, while Pt particles were more stable in this case.     

Development and Evaluation of Gas Diffusion Layer Using Paraffin Wax Carbon for Proton Exchange Membrane Fuel Cells

A gas diffusion layer (GDL) with carbon prepared from paraffin wax was developed for the first time to impart hydrophobicity and porosity for fuel cell application. It is also intended to reduce the non‐functional binder content in the microporous layer and to achieve optimum performance. The topography of the GDL was examined using 3D digital microscope. Membrane electrodes assemblies (MEAs) fabricated with GDLs of paraffin wax carbon (PWC) based microporous layer were evaluated in proton exchange membrane fuel cell between 50 and 100% RH conditions using H₂ and O₂ at ambient pressure. The fuel cell performance of the GDLs fabricated with Pureblack carbon was also evaluated under identical operating conditions for comparison. It was observed that the MEA with GDLs containing PWC showed excellent fuel cell performance at all RH conditions at 80 °C both with H₂/O₂.     

Mathematical Model of Proton Exchange Membrane Fuel Cell with Consideration of Water Management

One‐dimensional model on the membrane electrode assembly (MEA) of proton exchange membrane fuel cell is proposed, where the membrane hydration/dehydration and the possible water flooding of the respective cathode and anode gas diffusion layers are considered. A novel approach of phase‐equilibrium approximation is proposed to trace the water front and the detailed saturation profile once water emerges in either anode or cathode gas diffusion layer. The approach is validated by a semi‐analytical method published earlier. The novel approach is applicable to the polarization regime from open circuit voltage to the limiting current density under practical operation conditions. Oxygen diffusion is limited by water accumulation in the cathode gas diffusion layer as current increases, caused by excessive water generation at the cathode catalyst layer and the electro‐osmotic drag across the membrane. The existence of liquid water in the anode gas diffusion layer is predicted at low current densities if high degrees of humidification in both anode and cathode feeds are employed. The influences of inlet relative humidity, imposed pressure drop, and cell temperature are correlated well with the cell performance. In addition, the overpotentials attributed from individual components of the MEA are delineated against the cell current densities.     

The Effect of Methanol Crossover on the Cathode Overpotential of DMFCs

The effects of methanol crossover on cathode overpotential of direct methanol fuel cells (DMFCs) were investigated by focusing on a mixed potential effect and surface poisoning of the catalyst. Experiments using different membranes and catalyst loadings were performed and compared with a semi‐quantitative model to discuss the main cause of the cathode overpotential. When the measured methanol crossover increased, cathode overpotential increased at particular threshold values, which were 150 mA cm^–2 at 0.3 mg cm^–2 of cathode platinum (Pt) loading and above 200 mA cm^–2 at 1.1 mg cm^–2. The modelling results also supported this tendency, and showed that Pt surface was poisoned to a great extent above the threshold methanol crossover where the cathode overpotential increased sharply, while the cathode overpotential remained low and was explained solely by the mixed potential below the threshold value. The threshold methanol crossover can be regarded as the acceptable value, below which the cathode overpotential from methanol crossover remains low, and was related with the Pt loading in the cathode. The reduction of methanol crossover through membranes below the acceptable values will contribute greatly to a decrease in the cathode overpotential and to the reduction of catalyst loadings.     

A Sulfophenylated Polysulfone as the DMFC Electrolyte Membrane – an Evaluation of Methanol Permeability and Cell Performance

A sulfophenylated polysulfone (PSU‐sph), carrying 0.8 sulfonic acid units per repeating unit of the polymer, is evaluated as a membrane electrolyte for DMFC applications. The liquid uptake, methanol transport characteristics, electrolyte conductivity, and fuel cell performance are investigated. The methanol transport and DMFC performance results are compared to those of Nafion® 117. The PSU‐sph membrane investigated shows superior qualities with regard to methanol crossover, with a methanol permeability of approximately 25% compared to that of Nafion®. The conductivity was measured to be 15% compared to that of Nafion®. However, this could not fully account for the internal resistance of the cell, implying that the contact resistance between the electrodes and electrolyte is higher when PSU‐sph is used, probably because the electrodes are developed for use with Nafion® membranes. The stability of the PSU‐sph membrane seems promising, with very low degradation observed over a period of 72 hours. It was concluded that although the mass transport properties of the PSU‐sph membrane sample investigated were superior, it could not match the performance of Nafion® 117 in a DMFC application. However, a higher degree of sulfonation may have a significant positive effect on cell performance. The results also showed that a fully intergrated MEA is needed to fully assess new menbrane materials.     

Investigation of a Novel Catalyst Coated Membrane Method to Prepare Low‐Platinum‐Loading Membrane Electrode Assemblies for PEMFCs

In this work, a novel catalyst coated membrane (CCM) approach–a catalyst‐sprayed membrane under irradiation (CSMUI)–was developed to prepare MEAs for proton exchange membrane fuel cell (PEMFC) application. Catalyst ink was sprayed directly onto the membrane and an infrared light was used simultaneously to evaporate the solvents. The resultant MEAs prepared by this method yielded very high performance. Based on this approach, the preparation of low‐platinum‐content MEAs was investigated. It was found that for the anode, even if the platinum loading was decreased from 0.2 to 0.03 mg cm^–2, only a very small performance decrease was observed; for the cathode, when the platinum loading was decreased from 0.3 to 0.15 mg cm^–2, just a 5% decrease was detected at 0.7 V, but a 35% decrease was observed when the loading was decreased from 0.15 to 0.06 mg cm^–2. These results indicate that this approach is much better than the catalyst coated gas diffusion layer (GDL) method, especially for the preparation of low‐platinum‐content MEAs. SEM and EIS measurements indicated ample interfacial contact between the catalyst layer and the membrane.     

CO Tolerance of Commercial Pt and PtRu Gas Diffusion Electrodes in Polymer Electrolyte Fuel Cells

The CO tolerance of commercial Pt and PtRu anode electrodes from different suppliers (E‐Tek and Tanaka) has been examined in polymer electrolyte fuel cells (PEFC) using AC‐impedance spectroscopy along steady‐state current‐voltage curves. A simple mathematical model has been derived in order to extract important kinetic parameters for CO poisoning on different anode electrodes. The Tanaka PtRu (40:60) electrode demonstrated the best CO tolerance under the selected operating conditions. Inductive behavior in the low frequency region of the impedance spectra for the E‐Tek Pt and PtRu electrode proved to be characteristic for CO poisoning. However, the impedance spectra of the Tanaka PtRu electrode did not show any inductive behavior and its CO surface coverage, extracted by fitting the experimental data to the model, was lower than the surface CO coverage of the E‐Tek electrodes.     

Current Advances in Polymer Electrolyte Fuel Cells Based on the Promotional Role of Under‐rib Convection

Literature data on the promotional role of under‐rib convection for polymer electrolyte fuel cells (PEFCs) fueled by hydrogen and methanol are structured and analyzed, thus providing a guide to improving fuel cell performance through the optimization of flow field interaction. Data are presented for both physical and electrochemical performance showing reactant mass transport, electrochemical reaction, water behavior, and power density enhanced by under‐rib convection. Performance improvement studies ranging from single cell to stack are presented for measuring the performance of real operating conditions and large‐scale setups. The flow field optimization techniques by under‐rib convection are derived from the collected data over a wide range of experiments and modeling studies with a variety of components including both single cell and stack arrangements. Numerical models for PEFCs are presented with an emphasis on mass transfer and electrochemical reaction inside the fuel cell. The models are primarily used here as a tool in the parametric analysis of significant design features and to permit the design of the experiment. Enhanced flow field design that utilizes the promotional role of under‐rib convection can contribute to commercializing PEFCs.     

Synthesis and Properties of Random Copolymers of Functionalised Polybenzimidazoles for High Temperature Fuel Cells

A series of polybenzimidazoles (PBIs) incorporating main chain sulphonic acid groups were synthesised as random copolymers with p‐PBI in varying ratios using polyphosphoric acid (PPA) as both the polymerisation solvent and polycondensation reagent. The PPA process was used to produce high molecular weight phosphoric acid (PA) doped PBI gel membranes in a one‐step procedure. These membranes exhibit excellent mechanical properties (0.528–2.51 MPa tensile stress and 130–300% tensile strain) even at high acid doping levels [20–40 mol PA/PRU (polymer repeat unit)] and high conductivities (0.148–0.291 S cm^–1) at elevated temperatures (>100 °C) with no external humidification, depending on copolymer composition. Fuel cell testing was conducted with hydrogen fuel and air or oxygen oxidants for all membrane compositions at temperatures greater than 100 °C without external feed gas humidification. Initial studies showed a maximum fuel performance of 0.675 V for the 25 mol% s‐PBI/75 mol% p‐PBI random copolymer at 180 °C and 0.2 A cm^–2 with hydrogen and air, and 0.747 V for the same copolymer at 180 °C and 0.2 A cm^–2 with hydrogen and oxygen.     

Thermo‐Mechanical Response of Fuel Cell Electrodes: Constitutive Model and Application in Studying the Structural Response of Polymer Electrolyte Fuel Cell

The characterization of the mechanical properties of fuel cell electrodes through the experimental techniques is a complex task due to the low thickness, constituents' heterogeneous composition, and fragile nature of the film. We present a preliminary investigation on the thermomechanical response of fuel cell catalyst layer (CL) obtained through the numerical experiment. Since the Nafion ionomer is one of the constituents' of the CL, a modified micromechanically motivated viscoplastic model is adopted to characterize the Nafion ionomer in terms of reduced density factor to account for the void content. The catalyst agglomerates are taken as inclusions in the ionomer matrix to form a composite unit which is used to plot the true stress–true strain response. Practicality of this work is tested by implementing the electrode layer as a separate component in the single fuel cell unit cell model. A remarkable difference in the magnitude of stress levels in the membrane is observed under thermal and hydrated conditions with the presence and absence of electrode layer in the simulation domain. The present work will assist in improved understanding of the localized stress distribution in the membrane, which is essential to understand its mechanical endurance.     

Effects of Temperature and Catalyst Type on Chemical Degradation of Radiation Grafted Membranes in PEFCs

Proton exchange membranes prepared by radiation grafting are a promising alternative material to perfluoroalkyl sulfonic acid (PFSA) for fuel cell application. The temperature effect on the chemical degradation of radiation grafted membranes is evaluated by testing styrene grafted and sulfonated membranes at elevated temperatures (90 to 110 °C) and open circuit voltage (OCV) conditions. The results show that the increased temperature can markedly enhance membrane degradation, as expected, which is similar to the case of PFSA membranes. Moreover, elevated operating temperature leads to brown discoloration of the tested membrane, which may be attributed to the formation of a large conjugated π‐electron system in the membrane chemical structure. The OCV tests in which the styrene grafted membranes were tested at 80 °C with different kinds of catalyst (Pt/C and Pt black, respectively) in the gas diffusion electrodes (GDE) show that the membrane combined with Pt black GDEs exhibited a significantly lower degradation rate than that combined with Pt/C GDEs. The influence of differences in the amount of contaminants and the possibility of H₂O₂ formation between these two types of catalyst are put forward to explain this phenomenon.