Systematic study of short circuit activation on the performance of PEM fuel cell

During the operation of proton exchange membrane fuel cell (PEMFC), it always suffers from reversible performance loss caused by the oxidation of platinum catalyst on its electrode, which reduces the electrochemical active surface area. Short circuit method has been found to improve the performance of fuel cells by stripping of oxides and other adsorbed species from platinum, which needs systematical understanding the effective parameters of short circuit method on fuel cell performance. In this paper, the effects of different short circuit activation parameters (duration, interval, cycles, cut-off voltage, operating current) are carefully studied and analyzed during short circuit operations. In addition, the mechanism revealing how relevant parameters influence short circuit activations is deeply analyzed. The results show that five groups of activation parameters have obvious influence on the activation of fuel cell, indicating that the short-circuit activation effect can be optimized. Among these parameters, the short-circuit duration parameter have the greatest impact on activation, because the platinum hydroxides and oxides is gradually removed during short-circuit duration and results in a larger effective surface area of the platinum catalyst for the electrochemical reaction. However, the smallest impact is short-circuit interval. Another finding is that the five activation parameters are not independent, so the optimal activation parameter value needs to be analyzed in combination with the operating conditions. Finally, according to the activation principle, selection of appropriate short circuit activation parameters for application are proposed to further improve performance and fuel utilization by considering the safety of the stack.     

Fault tree analysis for PEM fuel cell degradation process modelling

For transportation applications, Proton Exchange Membrane fuel cells (PEMFC) are considered to be the most promising fuel cell technology due to their low operating temperature and pressure resulting in a possible quick start-up. However, to implement them in transportation systems, their reliability should be improved. In the present work, a single fuel cell is considered. It is composed of a membrane, catalyst layers (anode and cathode electrodes) and diffusion layers (anode and cathode electrodes). Those layers are considered as the critical components of the cell. Modelling the process degradations of those components is a great issue. In this work, Fault Tree (FT) is used for this modelling for two main reasons. At first, FT helps to model clearly and intuitively the different causal relations of the degradation mechanisms. Secondly, FT allows quantifying components specific degradations, and their effects on the global degradation of the cell. The cell is considered non repairable. Degradation modelling needs knowledge about mechanisms involving components failures. For 1000 simulations of 100 h operation in cycling conditions, the results of the FT show the most important degradations effects on the global degradation of the cell. This work also proposes degradation probability estimates for some specific events.     

Performance prediction of PEM fuel cell cathode catalyst layer using agglomerate model

Computation of Proton Exchange Membrane (PEM) fuel cell's cathode Catalyst Layer (CL) is performed using agglomerate models in this paper, and the results are compared with homogenous one. Following our earlier homogenous model for cathode CL (see Khajeh-Hosseini et al., 2010), the focus of the present study is on agglomerate model. In this study, the derivation of agglomerate model is performed in such a way that in the simplified case when agglomerate sizes shrink to zero, the homogeneous model condition is retrieved. Validations versus two sets of experimental data are performed. For example, in one of the validation cases, Case (II), it is observed that in I_tot = 3000 [A m⁻²] the homogeneous model overestimates the performance by 80%. But the agglomerate model agrees well with the validating test cases. A set of parametric studies are performed using the agglomerate model, in which the influences of some CL structural- and cell operating-parameters are studied. A sensitivity study on the cell performance is performed to rank the influence of the parameters, with rank 1 for the most influential parameter. It is observed the agglomerate sizes possess rank 1. These results give useful guidelines for manufactures of PEMFC catalyst layers.     

Effect of clamping pressure on the performance of a PEM fuel cell

Examined were the effects of the clamping pressure on the performance of a proton exchange membrane (PEM) fuel cell. The electro-physical properties of the gas diffusion layer (GDL) such as porosity, gas permeability, electrical resistance and thickness were measured using a special-designed test rig under various clamping pressure levels. Correlations for the gas permeability of the GDL were developed in terms of the clamping pressure. In addition, the contact resistance between the GDL and the bipolar (graphite) plate was measured under various clamping pressures. Results showed that at the low clamping pressure levels (e.g. <5 bar) increasing the clamping pressure reduces the interfacial resistance between the bipolar plate and the GDL that enhances the electrochemical performance of a PEM fuel cell. In contrast, at the high clamping pressure levels (e.g. >10 bar), increasing the clamping pressure not only reduces the above Ohmic resistance but also narrows down the diffusion path for mass transfer from gas channels to the catalyst layers. Comprising the above two effects did not promote the power density too much but reduce the mass-transfer limitation for high current density.     

A novel approach on the determination of the minimal operating efficiency of a PEM fuel cell

In this article, a novel mathematical approach is proposed to determine the minimal proton exchange membrane fuel cell efficiency below which it is not recommended to operate the fuel cell. The objective of this proposal is to minimize the annual fuel cost and the electricity cost of a proton exchange membrane (PEM) fuel cell since both terms are efficiency dependent. A new concept developed in this article might be used as a valuable mathematical tool to determine the minimal efficiency required to operate a fuel cell in a reasonable fashion in order to make the fuel cell system technically and economically feasible. Two dimensionless mathematical criteria J₁ and J₂ were proposed for the annual fuel cost and electricity cost, respectively. A minimum fuel cell efficiency of was obtained with J₁ and J₂ values of 2.7 and 0.026, respectively.     

Multi-walled carbon nanotubes decorated by platinum catalyst for high temperature PEM fuel cell

In the literature, studies on platinum catalysts deposited on multi-walled carbon nanotube (Pt/MWCNT) have been mostly focused on low temperature fuel cell (LT-PEMFC) applications. In this study, we focus the synthesis and characterization of high temperature fuel cell (HT-PEMFC) performance of Pt/MWCNT in short and long term. The structural properties of the Pt/MWCNT electrocatalyst were analyzed by XRD, TGA, SEM and TEM measurements. The Pt/MWCNTs were also characterized by electrochemical measurements for durability estimation. Laboratory scale MEA with Pt/MWCNT was prepared by ultrasonic coating technique and has been tested in situ in single HT-PEMFC. Performance curves in dry Hydrogen/Air system were obtained that demonstrated performance comparable to commercial catalysts in that HT-PEMFC. The characterizations specified that the electrocatalytic and HT-PEMFC performance of the Pt/MWCNT catalysts are higher power density (0.360 W/cm²) than Pt/C (0.310 W/cm²) at 160 °C. The results obtained show that the synthesized catalysts are suitable for high temperature applications. In addition, the stability studies of MEAs prepared with Pt/MWCNT catalyst were performed by AST tests and compared with Pt/C based MEA.     

Degradation analysis of dead-ended anode PEM fuel cell at the low and high thermal and pressure conditions

In this study, it is demonstrated that operation of dead-ended anode fuel cell at high temperature and pressure reduce the durability of membrane electrode assembly. In such a way that after 9000 degradation cycles, the maximum power density under H₂/O₂ gas feed mode for the aged MEA at high temperature and pressure is dropped by 38.8%. While the maximum power density drop is 27.1% for the aged MEA at low temperature and pressure. Comparison of the electrochemical impedance spectroscopy responses of MEAs shows that during aging process, the charge transfer resistance increase rate is more at higher temperature and pressure. This suggests the more severe destruction of catalyst layer at higher temperature and pressure and is in agreement with the obtained values of electrochemical surface area from the cyclic voltammetry test. In addition, the transmission electron microscopy and scanning electron microscopy images show the further degradation of cathode catalyst layer and more sever Pt agglomeration at higher temperature and pressure.     

Natural degradation and stimulated recovery of a proton exchange membrane fuel cell

In this paper, the stimulated recovery of a proton exchange membrane (PEM) fuel cells after natural degradation has been investigated. The performance degradation of a 63-cell PEM fuel cell stack over a storage interval of 40,000 h at temperature 24 °C and relative humidity 65% was analyzed by static and dynamical tests. The average cell voltage degradation rate was 309 μV h⁻¹, averaged over a range of currents. The performance was then partially recovered by application of a high frequency pulsing procedure after which the effective average degradation rate (from the commencement of storage to after the recovery) was approximately 170 μV h⁻¹. This indicates the existence of both recoverable and irrecoverable degradations in the fuel cell. Furthermore, the equivalent circuit model and membrane resistance were used to investigate the degradation mechanisms, suggesting that the natural degradation of the fuel cell is mainly caused by the increase of the resistance, which is most likely caused by membrane dehydration.     

Self-humidification of a PEM fuel cell using a novel Pt/SiO2/C anode catalyst

In this work, a membrane electrode assembly (MEA) for proton exchange membrane fuel cell (PEMFC) operating under no external humidification has been successfully fabricated by using a composite Pt/SiO₂/C catalyst at the anode. In the composite catalyst, amorphous silica, which originated from the hydrolysis of tetraethyl orthosilicate (TEOS), was immobilized on the surface of carbon powder to enhance the stability of silica and provide a well-humidified surrounding for proton transport in the catalyst layer. The characteristics of silica in the composite catalyst were investigated by XRD, SEM and XPS analysis. The single cell tests showed that the performance of the novel MEA was comparable to MEAs prepared using a standard commercial Pt/C catalyst with 100% external humidification, when both were operated on hydrogen and air. However, in the absence of humidification, the MEA using Pt/SiO₂/C catalyst at the anode continued to show excellent performance, while the performance of the MEA containing only the Pt/C catalyst rapidly decayed. Long-term testing for 80 h further confirmed the high performance of the non-humidified MEA prepared with the composite catalyst. Based on the experimental data, a possible self-humidifying mechanism was proposed.     

Understanding and approaches for the durability issues of Pt-based catalysts for PEM fuel cell

The state-of-art understanding of durability issues (the degradation reasons and mechanisms, the influence of working conditions, etc.) of Pt-based catalysts for proton exchange membrane fuel cell (PEMFC) and the approaches for improving and studying catalyst durability are reviewed. Both carbon support and catalytic metals degrade under PEMFC conditions, respectively, through the oxidation of carbon and the agglomerate and the detachment from support materials of catalytic metals, especially under unnormal working conditions; furthermore, the degradation of carbon support and catalytic metals interact with and exacerbate one another. The working temperature, humidity, cell voltage (the electrode potential and the mode applied on the electrode), etc. can influence the catalyst durability. Carbons with high graphitization degree as support materials and alloying Pt with some other metals are proved to be effective ways to improve the catalyst durability. Time-effective and reliable methods for studying catalyst durability are indispensable for developing PEMFC catalysts.     

Effects of atmospheric aerosol on the performance of environmentally sustainable passive air-breathing PEM fuel cells

The effects of different airborne particulate contaminants (oxalic acid, soot, ammonium sulfate, and sodium chloride) and the gaseous air impurity NO_x on the performance of a passive air-breathing proton exchange membrane fuel cell (AB-PEMFC) were investigated by introducing the pollutants into the oxidant air fed to a small AB-PEMFC module. All contamination data were corrected for variations in air temperature and relative humidity. While 10 ppmv NO_x degraded fuel cell performance by 22% within 4 h and showed partial recovery of 70% within another 11 h, the effects of the aerosol particles were considerably less severe. Only oxalic acid and ammonium sulfate exhibited significant performance degradation with upper limits of 24% 1000 h⁻¹ and 3% 1000 h⁻¹, respectively. Sodium chloride as well as soot particles did not cause any significant performance decline. Because diffusion is the main transport mechanism for aerosol particles into a passive AB-PEMFC, only a minor fraction of the total particle mass can actually deposit inside these fuel cells resulting in rather low effects even under very high aerosol loadings. Therefore, aerosol related effects seem negligible under ambient conditions.     

Carbon support oxidation in PEM fuel cell cathodes

Oxidation of the cathode carbon catalyst support in polymer electrolyte fuel cells (PEMFC) has been examined. For this purpose platinum supported electrodes and pure carbon electrodes were fabricated and tested in membrane-electrode-assemblies (MEAs) in air and nitrogen atmosphere. The in situ experiments account for the fuel cell environment characterized by the presence of a solid electrolyte and water in the gas and liquid phases. Cell potential transients occurring during automotive fuel cell operation were simulated by dynamic measurements. Corrosion rates were calculated from CO₂ and CO concentrations in the cathode exhaust measured by non-dispersive infrared spectroscopy (NDIR). Results from these potentiodynamic measurements indicate that different potential regimes relevant for carbon oxidation can be distinguished. Carbon corrosion rates were found to be higher under dynamic operation and to strongly depend on electrode history. These characteristics make it difficult to predict corrosion rates accurately in an automotive drive cycle.     

NUMERICAL analysis of the effects of current collector plate geometry on performance in a cylindrical PEM fuel cell

In this study, a numerical analysis was conducted to investigate the effects of current collector plate geometry on performance in a cylindrical PEM (Proton Exchange Membrane) fuel cell. For this purpose, 2 anode and cathode current collector plate geometries for each helix channel and straight channel were designed. Current collector plates with different geometries were combined with different sequences, and four different main model fuel cell geometries were created. Accordingly, anode and cathode current collector plates for Model-1, Model-2, Model-3, and Model-4 geometries were determined as straight-straight, helix-helix, straight-helix, and helix-straight, respectively. Using these model geometries, simulations were conducted for three different operating pressures, four different operating flow rates, and ten different operating voltages. It was observed that when helix flow channels were used instead of straight flow channels in current collection plate geometries, the flow density increased by approximately 63.18%. The results also revealed that the current density increased by approximately 206.9% when the fuel cell operating pressure increased. In addition, the power density increased as the operating pressure increased. As the gas flow to anode and cathode increased, a 19.05% increase in the current increase in the pressure difference was observed. As a result, the helix flow channel usage performed better than the straight flow channel for the parameters adopted in this study.     

Effect of PEM fuel cell exhaust water conductivity on catalyst degradation using thermal degradation resistant polymer membranes

In this paper energy dispersive spectroscopy, X-ray diffraction and Williamson-Hall grain size/strain characterization techniques were used to determine the effect exhaust water electrical conductivity, heating and electrical current had on Proton Exchange Membrane electrocatalyst degradation and the underlying mechanism. Quartz containing polybenzimidazole polymer had 6 nm of platinum sputter-coated and while 50 to 400 cycles of either 0.7 mA or 30 mA current were applied. Results showed between 38% (overall) and 100% (locally) platinum removal using 0.7 mA (400 cycles) or 30 mA (50 cycles) using water with 5 vol% acetic acid. The acetic acid increased the water's electrical conductivity and helped transport quartz to the sample surface to interact with the platinum. This interaction increased quartz's lattice strain to 1.4% and resulted in detached platinum. Furthermore, similar results may occur using membranes formulated with acid side chains, which can leach during thermal decomposition and destroy stack performance.     

Effective factors improving catalyst layers of PEM fuel cell

Cathode catalyst layer has an important role on water management across the membrane electrode assembly (MEA). Effect of Pt percentage in commercial catalyst and Pt loading from the viewpoint of activity and water management on performance was investigated. Physical and electrochemical characteristics of conventional and hydrophobic catalyst layers were compared. Performance results revealed that power density of conventional catalyst layers (CLs) increased from 0.28 to 0.64 W/cm² at 0.45 V with the increase in Pt amount in commercial catalyst from 20% to 70% Pt/C for H₂/Air feed. In the case of H₂/O₂ feed, power density of CLs increased from 0.64 to 1.29 W/cm² at 0.45 V for conventional catalyst layers prepared with Tanaka. Increasing Pt load from 0.4 to 1.2 mg/cm², improved kinetic activity at low current density region in both feeding conditions. Scattering electron microscopy (SEM) images revealed that thickness of the catalyst layers (CLs) increases by increasing Pt load. Electrochemical impedance spectroscopy (EIS) results revealed that thinner CLs have lower charge transfer resistance than thicker CLs. Inclusion of 30 wt % Polytetrafluoroethylene (PTFE) nanoparticles in catalyst ink enhanced cell performance for the electrodes manufactured with 20% Pt/C at higher current densities. However, in the case of 70% Pt/C, performance enhancement was not observed. Cyclic voltammetry (CV) results revealed that 20% Pt/C had higher (77 m²/g) electrochemical surface area (ESA) than 70% Pt/C (65 m²/g). In terms of hydrophobic powders, ESA of 30PTFE prepared with 70% Pt/C was higher than 30PTFE prepared with 20 %Pt/C. X-Ray Diffractometer (XRD) results showed that diameter of Pt particles of 20% Pt/C was 2.5 nm, whereas, it was 3.5 nm for 70% Pt/C, which confirms CV results. Nitrogen physisorption results revealed that primary pores of hydrophobic catalyst powder prepared with 70% Pt/C was almost filled (99%) with Nafion and PTFE.     

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.     

Improved PEM fuel cell performance with hydrophobic catalyst layers

Flooding of catalyst layers is one of the major issues, which effects performance of low temperature proton exchange membrane fuel cells (PEMFC). Rendering catalyst layers hydrophobic one may improve the performance of PEMFC depending on Pt percentage in the catalyst and Polytetrafluoroethylene (PTFE) loading on the electrode. In this study, effect of hydrophobicity in catalyst layers on performance has been investigated by comparing performances of membrane electrode assemblies prepared with 48% Pt/C. Ultrasonic coating technique was used to manufacture highly efficient electrodes. Power density at 0.45 V increased by the addition of PTFE, from 0.95 to 1.01 W/cm² with H₂/O₂ feed; while it slightly increased from 0.52 W/cm² to 0.53 W/cm² with H₂/Air feed. Addition of PTFE to catalyst layers while keeping Pt loading constant, enhanced performance providing improved water management. Kinetic activity increased by decreasing Nafion loading from 0.37 mg/cm² to 0.25 mg/cm² while introducing PTFE (0.12 mg/cm²) to the electrode. Electrochemical impedance spectroscopy (EIS) results proved that charge transfer resistance decreased with hydrophobic catalyst layers for H₂/O₂ feed. This is attributed to enhanced water management due to PTFE presence.     

The effect of platinum in a Nafion membrane on the durability of the membrane under fuel cell conditions

The effect of platinum on free radical generation and membrane degradation in proton exchange membrane (PEM) fuel cells is investigated using three typical cell configurations. Examinations of the fluoride emission rates (FERs) under different testing conditions indicate that platinum deposited in the membrane plays an important role as a catalytic center for the formation of H₂O₂ and HO free radicals, leading to PEM degradation. The chemical durability of the membranes is tested in accelerated Fenton tests. It confirms the formation of free radicals in the presence of platinum in the decomposition of H₂O₂ by colorimetric method with dimethyl sulfoxide (DMSO) as the trapping agent. In addition, structural and morphological changes of the membranes are characterized using FT-IR spectroscopy and scanning electron microscopy (SEM).