Cobalt molybdenum carbides as anode electrocatalyst for proton exchange membrane fuel cell

Cobalt molybdenum (Co-Mo) carbides were prepared by the carburization of Co-Mo oxides at temperatures of 723–973 K in a stream of CH₄/H₂ gas. The carburized catalysts were evaluated using a single-stack fuel cell and three-electrode cell. The results showed high activities for the anodic electrooxidation of hydrogen over the Co-Mo catalysts carburized at 873 and 923 K. The 873 K carburized Co-Mo catalyst had the highest activity and achieved 10.9% of the performance of a commercial Pt/C catalyst in a single-stack fuel cell. The XRD, TPC, TPR and XPS results showed that the Co-Mo oxycarbide in the bulk and on the surface are the active species for the hydrogen oxidation reaction.     

A gas management strategy for anode recirculation in a proton exchange membrane fuel cell

The anode configuration and gas management strategy are two of factors that affect the energy efficiency of a proton exchange membrane fuel cell. In order to improve the hydrogen utilization, unused hydrogen can be recirculated to the inlet using a pump. However, impurities diffusing from the cathode to the anode may cause the dilution of hydrogen in the anode. As a result, a gas management strategy is required for the anode recirculation configuration. In this preliminary study, a novel configuration for anode recirculation and a gas management strategy are proposed and verified by experiments. Two valves are installed in the recirculation line. The anode is operated in four modes (dead-end, recirculation, compression, and purge), and the real-time local current density (LCD) is monitored for gas management purposes. The results show that the LCD distribution is uniform during the recirculation mode and nonuniform during the dead-end and compression modes. With this configuration and gas management strategy, the cycle duration is increased by a factor of 6.5.     

Thickness effects of anode catalyst layer on reversal tolerant performance in proton exchange membrane fuel cell

Real-world driving conditions will likely cause hydrogen starvation at the anode chambers of stacks to trigger voltage reversal events, posing a tremendous challenge to the durability of proton exchange membrane fuel cells (PEMFCs). The reversal-tolerant anode (RTA), a material-based solution, that inclusion of oxygen evolution reaction (OER) catalyst into the anode is usually employed to cope with the voltage reversal issue. In this work, we investigate the impact of anode catalyst layer thickness on the voltage reversal performance of the membrane-electrode assemblies (MEAs) with conventional anodes (Pt/C catalyst) and RTAs doped with IrO₂ catalyst, a representative OER catalyst. We find that regardless of how thick the anode catalyst layer is, the conventional MEAs exhibit almost similar voltage reversal behaviors and times, only about 1 min to reach the shutdown voltage (?2.5 V). As for the RTA MEAs, a surprising thickness effect that the thinner RTA with the same IrO₂ loading shows superior voltage reversal tolerance. Notably, an ultra-thin RTA (~2 μm) exhibits the reversal tolerance time of 310 min, which is five times higher reversal tolerance time than most of the reported RTAs. We conclude that this thickness effect mainly results from the ionomer distribution on the OER catalyst. Besides, we observe that the RTA with a higher ionomer content shows the better reversal tolerance performance. Our work highlights the importance of the OER Triple-Phase-Boundary (TPB) and the need for improved electrode designs for robust RTAs.     

Flexible micro sensors for in-situ diagnosis of proton exchange membrane fuel cell

The temperature and flooding phenomenon during operation can strongly influence a proton exchange membrane fuel cell (PEMFC) performance. Non-uniform conditions exist in each segment of fuel cell. Previous studies have investigated these conditions on the mm scale using destructive methods or simulation, but none has been able to obtain exact data from within the fuel cell.     

Performance of carbon-supported PtPd as catalyst for hydrogen oxidation in the anodes of proton exchange membrane fuel cells

In this work, the replacement of platinum by palladium in carbon-supported catalysts as anodes for hydrogen oxidation reaction (HOR), in proton exchange membrane fuel cells (PEMFCs), has been studied. Anodes with carbon-supported Pt, Pd, and equiatomic Pt:Pd, with various Nafion^® contents, were prepared and tested in H₂|O₂ (air) PEMFCs fed with pure or CO-contaminated hydrogen. An electrochemical study of the prepared anodes has been carried out in situ, in membrane electrode assemblies, by cyclic voltammetry and CO electrooxidation voltammetry. The analyses of the corresponding voltammograms indicate that the anode composition influences the cell performance. Single cell experiments have shown that platinum could be replaced, at least partially, saving cost with still good performance, by palladium in the hydrogen diffusion anodes of PEMFCs. The performance of the PtPd catalyst fed with CO-contaminated H₂ used in this work is comparable to Pt, thus justifying further work varying the CO concentration in the H₂ fuel to assert its CO tolerance and to study the effect of the Pt:Pd atomic ratio.     

A novel method for preparing proton exchange membrane fuel cell electrodes by the ultrasonic-spray technique

A novel ultrasonic-spray method for preparing gas diffusion electrodes (GDEs) for proton exchange membrane fuel cell (PEMFC) is described. Platinum (Pt) loaded on Nafion^®-bonded GDEs were prepared by the ultrasonic-spray method on various commercial woven and non-woven gas diffusion layers (GDLs) at several Pt loadings in the range of 0.40-0.05 mg cm⁻². The ultrasonic-sprayed GDEs were tested and compared to commercial and hand-painted GDEs. It was found that the GDEs prepared by the ultrasonic-spray method exhibited better performances compared to those prepared by the hand-painting technique, especially at low Pt loadings. GDEs fabricated by the ultrasonic-spray method with a platinum loading of 0.05 mg cm⁻² exhibited a peak power rating of 10.9 W mg⁻¹ compared to 9.8 W mg⁻¹ for hand-painted GDEs. For all experiments using various GDLs, Sigracet SGL 10BC exhibited the best performance with a peak power of 0.695 W cm⁻².     

A novel strategy based on salp swarm algorithm for extracting the maximum power of proton exchange membrane fuel cell

Cell temperature and water content of the membrane have a significant effect on the performance of fuel cells. The current-power curve of the fuel cell has a maximum power point (MPP) that is needed to be tracked. This study presents a novel strategy based on a salp swarm algorithm (SSA) for extracting the maximum power of proton-exchange membrane fuel cell (PEMFC). At first, a new formula is derived to estimate the optimal voltage of PEMFC corresponding to MPP. Then the error between the estimated voltage at MPP and the actual terminal voltage of the fuel cell is fed to a proportional-integral-derivative controller (PID). The output of the PID controller tunes the duty cycle of a boost converter to maximize the harvested power from the PEMFC. SSA determines the optimal gains of PID. Sensitivity analysis is performed with the operating fuel cell at different cell temperature and water content of the membrane. The obtained results through the proposed strategy are compared with other programmed approaches of incremental resistance method, Fuzzy-Logic, grey antlion optimizer, wolf optimizer, and mine-blast algorithm. The obtained results demonstrated high reliability and efficiency of the proposed strategy in extracting the maximum power of the PEMFC.     

A simple, analytic model of polymer electrolyte membrane fuel cell anode recirculation at operating power including nitrogen crossover

A simple, analytic model is presented that describes the steady state profile of anode nitrogen concentration in a polymer electrolyte membrane fuel cell operated with anode recirculation. The model is appropriate for fuel cells with straight gas channels and includes the effect of nitrogen crossover from cathode to anode through the membrane. The key analytic simplification in the model is that this crossover rate, when scaled to the gas flows in the channels, is small. This is a good approximation when the device is used at operating power levels. The model shows that the characteristic times for the anode nitrogen profiles to reach steady state are of the order of minutes and that the dilution effect of anode nitrogen is severe for pure recirculation. The model shows additionally that a small anode outlet bleed can significantly reduce the nitrogen dilution effect. Within the framework of the model, the energy efficiency of pure recirculation can be compared to hydrogen venting or partial anode bleeding. An optimal bleed rate is identified. The model and optimization analysis can be adapted to other fuel cell designs and operating conditions. Along with operating conditions, only two key parameters are needed: a nitrogen crossover coefficient and the marginal efficiency loss to compressors for increased anode stoichiometric gas flow.     

Sulfur-tolerant anode materials for solid oxide fuel cell application

This paper summarizes the degradation mechanisms for SOFC anodes in the presence of sulfur and recent developments in sulfur-tolerant anodes. There are two primary sulfur-degradation mechanisms for the anode materials: physical absorption of sulfur that blocks the hydrogen reaction sites, and chemical reaction that forms nickel sulfide. The sulfur-tolerant anodes are categorized into three kinds of materials: thiospinels and metal sulfides, metal cermets, and mixed ionic and electronic conductors. Each material has its own advantages and disadvantages, and the combined application of available materials to serve as different functional components in anodes through proper design may be effective to achieve a balance between stability and performance.     

Measurements of serpentine channel flow characteristics for a proton exchange membrane fuel cell

Flow characteristics at Re = 660–3000 in a serpentine channel are measured. A scale-up model whose channel hydraulic diameter is 50 times as large as that for a proton exchange membrane fuel cell (PEMFC) is used for the measurements. The flow conditions correspond to operating conditions for PEMFCs of 25–40 cm² at current density of 1–3 A/cm² when the fuel utilisation ratio is 0.75 and air is used for the O₂ supply. Two different porous media are used to simulate the gas diffusion layer (GDL). The results suggest that although the leakage flow rate is rather insensitive to the total flow rate, it increases significantly depending on the increase of the GDL permeability. Increasing the flow rate or the permeability enhances the sectional secondary flows and is expected to enhance mass transfer on the GDL. It is confirmed that the flow becomes turbulent around the bend even at Re = 660.     

Particle size dependence of CO tolerance of anode PtRu catalysts for polymer electrolyte fuel cells

An anode catalyst for a polymer electrolyte fuel cell must be CO-tolerant, that is, it must have the function of hydrogen oxidation in the presence of CO, because hydrogen fuel gas generated by the steam reforming process of natural gas contains a small amount of CO. In the present study, PtRu/C catalysts were prepared with control of the degree of Pt-Ru alloying and the size of PtRu particles. This control has become possible by a new method of heat treatment at the final step in the preparation of catalysts. The CO tolerances of PtRu/C catalysts with the same degree of Pt-Ru alloying and with different average sizes of PtRu particles were thus compared. Polarization curves were obtained with pure H₂ and CO/H₂ (CO concentrations of 500-2040 ppm). It was found that the CO tolerance of highly dispersed PtRu/C (high dispersion (HD)) with small PtRu particles was much higher than that of poorly dispersed PtRu/C (low dispersion (LD)) with large metal particles. The CO tolerance of PtRu/C (HD) was higher than that of any commercial PtRu/C. The high CO tolerance of PtRu/C (HD) is thought to be due to efficient concerted functions of Pt, Ru, and their alloy.     

Development of shut-down process for a proton exchange membrane fuel cell

Several different shut-down procedures were carried out to reduce the degradation of membrane electrode assembly (MEA) in a proton exchange membrane fuel cell (PEMFC). The effects of close/open state of outlets of a single cell and application of a dummy load during the shut-down on the degradation of the MEA were investigated. Also, we elucidated the relationship between the thickness of the electrolyte membrane and the degradation of the MEA for different shut-down procedures. When a thin electrolyte membrane was used, the closer of outlets mitigated the degradation during on/off operation. For the thicker electrolyte membrane, the dummy load which eliminates residual hydrogen and oxygen in the electrodes should be applied to lower the degradation.     

A critical review of cooling techniques in proton exchange membrane fuel cell stacks

Effective cooling is critical for safe and efficient operation of proton exchange membrane fuel cell (PEMFC) stacks with high power. The narrow range of operating temperature and the small temperature differences between the stack and the ambient introduce significant challenges in the design of a cooling system. To promote the development of effective cooling strategies, cooling techniques reported in technical research publications and patents are reviewed in this paper. Firstly, the characteristics of the heat generation and cooling requirements in a PEMFC stack are introduced. Then the advantages, challenges and progress of various cooling techniques, including (i) cooling with heat spreaders (using high thermal conductivity materials or heat pipes), (ii) cooling with separate air flow, (iii) cooling with liquid (water or antifreeze coolant), and (iv) cooling with phase change (evaporative cooling and cooling through boiling), are systematically reviewed. Finally, further research needs in this area are identified.     

Different flow fields,operation modes and designs for proton exchange membrane fuel cells with dead-ended anode

Water and nitrogen can accumulate in the anode channel in proton exchange membrane fuel cells (PEMFCs) with dead-ended anode (DEA) and can affect cell performance significantly. In this paper, the cell performance characteristics in DEA PEMFCs with three different anode flow fields under two operating modes are studied through measuring the cell voltages and local current densities. The effect of the anode exit reservoir is also studied for the three different anode flow fields. The experimental results show that the interdigitated flow field has the most stable cell performance under both constant pressure and pressure swing supply modes. Parallel and serpentine flow fields lead to very non-uniform local current distributions under constant pressure supply mode and experience severe fluctuations and spikes in local current densities under pressure swing supply mode. The results also show that anode pressure swing supply mode can achieve more stable cell performance than anode constant pressure supply mode for parallel and serpentine anode flow fields. The anode exit reservoir can significantly improve cell performance stability for parallel and serpentine flow fields, but has no significant effect on interdigitated flow fields. Besides, the results further show that PEMFCs with DEA can maintain very stable operation with anode serpentine flow field and an anode exit reservoir under pressure swing operation.     

Experimentally and numerically investigating cell performance and localized characteristics for a high-temperature proton exchange membrane fuel cell

This paper is to experimentally and numerically investigate the cell performance and the localized characteristics associated with a high-temperature proton exchange membrane fuel cell (PEMFC). Three experiments are carried out in order to study the performance of the PEMFC with different operating conditions and to validate the numerical simulation model. The model proposed herein is a three-dimensional (3-D) computational fluid dynamics (CFD) non-isothermal model that essentially consists of thermal–hydraulic equations and electrochemical model. The performance curves of the PEMFC predicted by the present model agree with the experimental measured data. In addition, both the experiments and the predictions precisely demonstrate the enhanced effects of inlet gas temperature and system pressure on the PEMFC performance. Based on the simulation results, the localized characteristics within a PEMFC can be reasonably captured. These parameters include the fuel gas distribution, liquid water saturation distribution, membrane conductivity distribution, temperature variation, and current density distribution etc. As the PEMFC is operated at the higher current density, the fuel gas would be insufficiently supplied to the catalyst layer, consequently causing the decline in the generation of power density. This phenomenon is so called mass transfer limitation, which can be precisely simulated by the present CFD model.     

Design of an integrated power system using a proton exchange membrane fuel cell

Integrated power systems could be a solution to provide energy to remote communities based on the use of renewable energies (such as wind or sun). This work proposed the design of one of those systems including alkaline water electrolysers, storage tanks and a proton exchange membrane fuel cell for generating of 53 kW (working at 60% of its maximum power). Electrode sizes and the quantity of unit cells proposed in this work were the same as those suggested in the research work by Yang et al., where a phosphoric acid fuel cell was built and studied. The results obtained in that research allowed comparing energy efficiency by scaling a laboratory prototype. The dimensions of the alkaline water electrolysers are the result of satisfying the necessity of fuel and oxidant. The energy consumption results from extrapolating laboratory devices. The integrated power system has a storage tank capacity of 16 h.     

A review of modified metal bipolar plates for proton exchange membrane fuel cells

In recent years, the proton exchange membrane fuel cell (PEMFC) has been widely studied due to its high energy efficiency and non-polluting products. As a key component of PEMFC, bipolar plates (BPPs) play an important role in isolating reaction gas, distributing flow field, collecting electrons and conducting heat. Metal BPPs have excellent manufacturing performance, low cost, and mechanical strength. Therefore, it is considered to be a powerful substitute for traditional graphite BPP. The surface modification of metal BPP is essential for its application in PEMFC. In this review, the latest developments in popular coatings were reviewed from the perspective of corrosion resistance, conductivity and contact angle of metal BPPs in PEMFC environments. The strengths and weaknesses of different surface modification methods were analyzed. Meanwhile,the development trend of future commercialization was also considered.     

A numerical investigation on multi-phase transport phenomena in a proton exchange membrane fuel cell stack

In this study, the simulation of a fuel cell stack is performed by applying a general numerical model with VOF method that has been successfully applied to single PEMFC model to investigate the fluid dynamics, mass transport, flooding phenomenon and the effects of liquid water on the stack performance. The performance of three single cells in series connection in the fuel cell stack is examined according to the presence of liquid water in different single cells. The distributions of fluid flow, species concentration and the current density are presented to illustrate the effects of liquid water on the performance of each single cell. The numerical results locate that the low distributions of species in the flooding cell certainly degrade the performance of this cell. Moreover, it can be seen that the performance of the flooding cell will significantly affect the whole stack performance since the values of average current density must be identical in all single cells.     

A study on novel pulse preparation and electrocatalytic activities of Pt/C-Nafion electrodes for proton exchange membrane fuel cell

To aim at reducing the platinum loading and increasing the utilization of platinum in PEMFC electrode, a new pulse electrodeposition technique for preparing proton exchange membrane fuel cell (PEMFC) electrodes has been developed in this paper. This method combines coating Pt seeds on the C-Nafion substrate and introducing polyethylene glycol (PEG) into the deposition solution. SEM images of the samples show that Pt seeds and PEG take an important role in the morphology of the Pt deposit. The surface area and average particle size of Pt were determined by charge integration under the hydrogen desorption peaks of cyclic voltammetry. The electrocatalytic activities of these electrodes towards oxygen reduction reaction (ORR) were investigated by using rotating disc electrode (RDE). The Pt catalyst which was prepared by Pt seeds and PEG, its active surface area and electrocatalytic activity towards ORR were improved remarkably. And the optimized electrode displayed higher catalytic activity than a conventional electrode made from commercial Pt/C catalyst. The possible reasons for the effects of Pt seeds and PEG on the higher catalytic activity of prepared Pt catalysts have been preliminarily discussed.     

Enhancing the CO tolerance of PEMFC MEAs by combining sputter-deposited and direct-printed composite anode catalyst layers

Two composite electrode structures for proton exchange membrane fuel cells, comprising an outer and an inner catalyst layer, are proposed to improve the CO tolerance and utilization efficiency of the catalyst. These two composite anodes have structures I and II, and are prepared by a combination of direct printing and magnetron sputtering deposition. The only difference between them is the third layer of the outer catalyst layer, which is a layer of deposited _Pt29${\mathrm{Pt}}_{29}$–_Ru71${\mathrm{Ru}}_{71}$ alloy nanoparticles in structure II and a screen-printed _Pt50–_Ru50${\mathrm{Pt}}_{50}–{\mathrm{Ru}}_{50}$ layer in structure I. The loadings of each layer at the anode for these two membrane electrode assemblies (MEAs) are identical. The electrode performance and CO tolerance of the proposed catalyst layer structure are compared to those of the conventional structure. The roles of the outer and inner catalyst layers in improving the CO tolerance and utilization efficiency of the catalyst are studied. The results indicate that the structure II anode catalyst layer outperforms the conventional structure, with a higher utilization efficiency of the catalyst and a similar CO tolerance. The structure I anode catalyst layer has a greater CO tolerance and outperforms the conventional and Huag's structures in 50 ppm CO-containing hydrogen fuels and pure hydrogen fuel. The filtering effect of the outer catalyst layer improves the CO tolerance. The electron probe micro-analysis result reveals that the composite anode has an effective catalyst distribution. This proposed composite MEA is expected to have the advantage of ease of process and is suited for mass production.