Increase of catalyst utilization in polymer electrolyte membrane fuel cells by shape-selected Pt nanoparticles

In the present work, we succeeded in supporting predominantly cuboctahedral Pt nanoparticles onto high surface area carbons while maintaining their shape. These novel catalysts were applied in a realistic fuel cell set-up for the first time and showed remarkable fuel cell performance. A 95% fraction of cuboctahedral Pt nanoparticles was synthesized using tetradecyltrimethylammonium bromide (TTAB) as a stabilizer. Transmission electron micrographs of the synthesized samples demonstrated the presence of monodispersed cuboctahedral particles of 12 nm in size. Cyclic voltammetry (CV) studies of the unsupported cuboctahedral nanoparticles revealed the presence of Pt (110) and (100) facets. The shape-selected Pt nanoparticles were let to absorb onto Vulcan carbon by a simple dispersing procedure to obtain supported shape-selected Pt nanoparticles. Only by this gentle adsorption step of the surfactant-stabilized nanoparticles on the carbonaceous support material, the nanoparticles retained their shape. Finally an MEA was fabricated using the supported shape-selected nanoparticles and tested in a realistic H₂-PEM fuel cell environment. In terms of Pt utilization, shape-selected Pt particles were found to be more effective by a factor of four in weight compared to the commercial catalyst.     

Conductivity of Nafion 117 membrane used in polymer electrolyte fuel cells

The membrane electric transport (MC) directly influences the performance of the polymer electrolyte fuel cells (PEMFC). The membrane conductivity is determined by a number of parameters such as: hydration technique, graphite cell geometry and pressure applied when the membrane electrode assembly (MEA) is joined. In addition, the membrane conductivity might be influenced by the electrode position due to the possibility of anisotropic electric conductivity.     

A dynamic model for high temperature polymer electrolyte membrane fuel cells

A dynamic one-dimensional isothermal phenomenological model was developed in order to describe the steady-state and transient behavior of high temperature polymer electrolyte membrane fuel cells (PEMFC). The model accounts for transient species mass transport at the bipolar plates and gas diffusion layers and the electric double layers charge/discharge. To record the impedance spectra, a small sinusoidal voltage perturbation was imposed to the simulator over a wide range of frequencies, and the resultant current density amplitude and phase were recorded.The steady-state behavior of the fuel cell, as well as the impedance spectra were obtained and compared to experimental data of two different fuel cells equipped with different MEAs based on phosphoric acid polybenzimidazole membrane. This approach is new and allows a deeper analysis of the controlling phenomena. The model fitted quite well the I-V curves for both systems, but fairly well the Nyquist plots. The differences observed in the Nyquist plots were attributed to proton resistance in the catalyst layer and the gas diffusion limitations to cross the phosphoric acid layer that coats the catalyst, phenomena not included in the proposed phenomenological model.     

Electrochemical analysis of hydrogen membrane fuel cells

An electrochemical analysis was conducted with respect to a hydrogen membrane fuel cell with SrZr_0.8In_0.2O_3−δ electrolyte, which is a new type of fuel cell featuring an ultra-thin proton conductor supported on a dense metal anode. Most of the voltage loss derives from the cathode and the electrolyte, and a small amount of anode polarization was observed only in regions with high current density. The cathode polarization was approximately an order of magnitude lower than that of SOFCs. Furthermore, the conductivity of the film electrolyte was almost identical to that of the sinter at 600 °C; however, it was several times as large at 400 °C. A TEM micrograph revealed that the film electrolyte consists mainly of long columnar crystals, and this crystal structure can be related to the conductivity enhancement below 600 °C.     

Parameter estimation of fuel cell polarization curve using BMO algorithm

Polarization curves of proton exchange membrane fuel cells (PEMFCs) are affected by various parameters. The relative importance and effect of each parameter on the polarization curve is different. This paper studies estimation of parameters with the most influence on the electrochemical model. In order to evaluate the obtained results, the model accuracy is compared with that model in which all the parameters are estimated. Because PEMFCs parameter estimation is a complex optimization problem, a recently invented nature-inspired algorithm, bird mating optimizer (BMO), is proposed. For this aim, two real systems, the SR-12 Modular PEM Generator and the Ballard Mark V FC, are considered. The obtained results show that when the whole parameters are estimated, the accuracy of the model increases. Also, BMO algorithm yields better results than the other studied methods in terms of precision and robustness.     

Capillaries for water management in polymer electrolyte membrane fuel cells

Some of the new liquid water management systems in polymer electrolyte membrane (PEM) fuel cells hold great potential in providing flood-free performance and internal humidification. However, current water management systems entail major setbacks, which either inhibit implementation into state-of-the-art architectures, such as stamped metal flow-fields, or restrict their application to certain channel configurations. Here, a novel water management strategy is presented that uses capillary arrays to control liquid water in PEMFCs. These capillaries are laser-drilled into the land of the flow-fields and allow direct removal (wicking) or supply of water (evaporation), depending on the local demand across the electrode. For a 6.25 cm² active area parallel flow-field, a ～92% improvement in maximum power density from capillary integration was demonstrated. The proposed mechanism serves as a simple and effective means of achieving robust and reliable fuel cell operation, without incurring additional parasitic losses due to the high pressure drop associated with conventional serpentine flow-fields.     

Bio-inspired flow field designs for polymer electrolyte membrane fuel cells

The branching structures found in biological systems have evolved to an optimum arrangement that distributes nutrients efficiently in the system. Since the flow fields of polymer electrolyte membrane (PEM) fuel cells serve similar functions to the nutrient transport systems in plants and animals, it is expected that flow fields with a similar hierarchical structure could optimize the transport efficiency of reactants and improve the performance of fuel cells. In this paper, a series of bio-inspired flow field designs inspired by the venation structure of a tree leaf is developed. Two different configurations, interdigitated and non-interdigitated, are considered in implementing the hierarchical structures. Murray's law, which describes the optimum configuration found in biological circulatory systems, is used to determine the flow channel widths of different generations. The bio-inspired design using Murray's law is compared to a design with constant channel width. Both numerical and experimental studies are carried out to investigate these bio-inspired designs. The mass, velocity, and pressure distributions within the channels and the gas diffusion layers, as well as the fuel cell performance, are studied for different flow field designs. The results show that the bio-inspired interdigitated designs substantially improve the fuel cell performance by 20–25% compared to the conventional designs.     

Boundary model-based reference control of blower cooled high temperature polymer electrolyte membrane fuel cells

Fuel cells have, by design, a limited effective life time, which depends on how they are operated. The general consent is that operation of the fuel cell at the extreme of the operational range, or operation of the fuel cell without sufficient reactants (a.k.a. starvation), will lower the effective life time of a fuel cell significantly. On air cooled HTPEMFCs, the blower, which supplies the fuel cell with oxygen for the chemical process, also functions as the cooling system. This makes the blower bi-functional and as a result a higher supply of oxygen is often available, hence changes in the fuel cell output can be optimised by the knowledge of how much oxygen is supplied to the fuel cell at any given time, without reducing the effective life time of a fuel cell by starvation.     

Expert diagnosis of polymer electrolyte fuel cells

Diagnosing faulty conditions of engineering systems is a highly desirable process within control structures, such that control systems may operate effectively and degrading operational states may be mitigated. The goal herein is to enhance lifetime performance and extend system availability. Difficulty arises in developing a mathematical model which can describe all working and failure modes of complex systems. However the expert's knowledge of correct and faulty operation is powerful for detecting degradation, and such knowledge can be represented through fuzzy logic. This paper presents a diagnostic system based on fuzzy logic and expert knowledge, attained from experts and experimental findings. The diagnosis is applied specifically to degradation modes in a polymer electrolyte fuel cell. The defined rules produced for the fuzzy logic model connect observed operational modes and symptoms to component degradation. The diagnosis is then tested against common automotive stress conditions to assess functionality.     

Cold start analysis of polymer electrolyte membrane fuel cells

Cold start is critical to the commercialization of polymer electrolyte membrane fuel cell (PEMFC) for practical applications such as backup power and automotive applications. In this study, various numerically simulated PEMFC cold start processes are analyzed. The success of the cold start process depends on the competition between how fast the cell is heated up to the freezing point temperature and how fast ice is formed and built up in the pores of the cathode catalyst layer (CL) blocking oxygen transport to the reaction sites; the success of the cold start process thus depends on the product water (i) that is absorbed into the ionomer in the CL and membrane, (ii) that is taken away in vapour form by the gas flows (can be neglected), and (iii) that is frozen into ice in the CL pores. It is found that the membrane thickness and the ionomer volume fraction in the CL play pivotal roles in reducing the amount of ice formation. A thicker membrane leads to a larger water capacity but a slower water absorption process, and increasing the ionomer volume fraction in the CL enlarges the ionomer water capacity and enhances the membrane water absorption. Starting the cell under the potentiostatic condition is confirmed to be superior to the galvanostatic condition. Heating up the external surfaces and the inlet air enhances the temperature increment of the cell. However, the external heating methods have negligible improvement in reducing the amount of ice formation. Even though heating the inlet air is more effective in increasing the cell temperature than heating the outer surfaces, the heat capacity of the inlet air is low.     

A review of polymer electrolyte membrane fuel cell stack testing

This paper presents an overview of polymer electrolyte membrane fuel cell (PEMFC) stack testing. Stack testing is critical for evaluating and demonstrating the viability and durability required for commercial applications. Single cell performance cannot be employed alone to fully derive the expected performance of PEMFC stacks, due to the non-uniformity in potential, temperature, and reactant and product flow distributions observed in stacks. In this paper, we provide a comprehensive review of the state-of-the art in PEMFC testing. We discuss the main topics of investigation, including single cell vs. stack-level performance, cell voltage uniformity, influence of operating conditions, durability and degradation, dynamic operation, and stack demonstrations. We also present opportunities for future work, including the need to verify the impact of stack size and cell voltage uniformity on performance, determine operating conditions for achieving a balance between electrical efficiency and flooding/dry-out, meet lifetime requirements through endurance testing, and develop a stronger understanding of degradation.     

Stability enhancement of polymer electrolyte membrane fuel cells based on a sulfonated poly(ether ether ketone)/poly(vinylidene fluoride) composite membrane

Most proton-conducting membranes based on sulfonated aromatic polymers exhibit significant dimensional change by hydration, and this leads to degradation of fuel cell performance on prolonged operation. In this study, as a means of improving the stability of a polymer electrolyte membrane fuel cell, composite membranes employing a porous poly(vinylidene fluoride) (PVdF) substrate and sulfonated poly(ether ether ketone) (sPEEK) electrolyte are prepared and their hydration behaviours, including water uptake and dimensional change, are examined. The electrochemical characteristics of membrane/electrode assemblies using the sPEEK/PVdF composite membrane are also analyzed. The initial cell performance is comparable with that of a cell based on a pure sPEEK membrane. Furthermore, the stability of the cell using the sPEEK/PVdF composite membrane is considerably improved during a humidity cycle test wherein hydration and dehydration are periodically repeated.     

Activation of polymer electrolyte membrane fuel cells: Mechanisms,procedures, and evaluation

Newly fabricated proton exchange membrane fuel cells (PEMFCs) need an activation process to improve the initial performance. The long activation time leads to a high cost and a low production efficiency, thus it is significant to develop rapid and non-destructive activation methods. This review summaries possible activation mechanisms, compares and analyzes various activation methods, and afterwards, proposes the design principles for activation. Some criteria for evaluating activation completion are also provided as references. Finally, the influence of several activation methods on cell durability is overviewed from present available researches. In this review, hydrogen pumping, short circuit, and cathode starvation are considered as more effective methods versus traditional approaches. The performance improvement after activation is ascribed to the change in membrane morphology, the reduction of contamination, and the optimization of catalyst layers. More importantly, five factors including high temperature, sufficient water, change in current or voltage, reductive atmosphere, and valid combination of different methods are highlighted in designing rapid activation procedures.     

Electromagnetic-carbon surface treatment of composite bipolar plate for high-efficiency polymer electrolyte membrane fuel cells

Polymer electrolyte membrane (PEM) or proton-exchange membrane fuel cell systems are environmentally friendly power sources for many applications. Bipolar plates are essential components of a PEM fuel cell. Recently, composite bipolar plates have received considerable interest due to their superior performance. The most important properties of bipolar plates are electrical resistance and contact resistance, which are largely dependent on the surface morphology of the bipolar plate, because low electrical resistance improves the efficiency of PEM fuel cells. In this study, a selective surface preparation technology is developed using an electromagnetic field and carbon black (electromagnetic-carbon surface treatment). The carbon black is heated by an electromagnetic field on the surface of the bipolar plate with a high rate of temperature rise. The non-electrically conducting surface resin is removed, without damaging the carbon fibre to give a low electrical resistance. It is found that the surface-treated composite bipolar plate has a lower electrical resistance than those of conventional composite bipolar plates, and that the electromagnetic-carbon surface treatment can be applied for production of the composite bipolar plates in a fast and efficient process.     

Electrochemical analysis of polymer electrolyte membrane fuel cell operated with dry-air feed

Electrochemical analysis of a commercial polymer electrolyte membrane fuel cell (PEMFC), operated at varying cathode relative humidity (RH) and current density, has been conducted to understand the factors that affect power performance when the PEMFC is operated with a dry-air feed. With a change in the cathode RH from 80 to 4%, the electrochemical area and double-layer capacitance of the cathode are reduced by 9 and 8%, respectively. This indicates that exclusion of the catalyst layer (CL) of the cathode from proton access occurs to some extent at low RH. It does not, however, explain the observed increase in activation loss. For the dry-air feed, the ionic resistances of the membrane and cathode CL are comparable in magnitude. Impedance analyses show that drying of the cathode at low RH and low current density leads not only to an increase in the ionic resistance of the CL, but also to increases in both charge-transfer and mass-transfer resistances. The simultaneous decrease in all the resistance components with decrease in the air permeability of the cathode diffusion layer highlights the importance of cathode design for operation with dry-air feed.     

Power source research at USC: Development of advanced electrocatalysts for polymer electrolyte membrane fuel cells

This paper provides an overview on the development of advanced fuel cell cathode catalysts at University of South Carolina (USC) with the emphasis on the stability of non-precious metal and Pt alloy catalysts. Nitrogen-modified carbon composite (NMCC) catalysts were developed for the oxygen reduction reaction (ORR) through the pyrolysis of cobalt (iron)-nitrogen chelate followed by the treatment combination of pyrolysis, acid leaching, and re-pyrolysis. A promising stability was observed for 1050 h fuel cell operation under current density of 200 mA cm⁻² as evidenced by a potential decay rate as low as 40 μV h⁻¹. The performance degradation mechanism of the NMCC-based fuel cell is discussed. Pt and PtPd hybrid catalysts are developed that use a NMCC, which is itself active for the ORR, instead of a conventional carbon black support. The stability test at 1 A cm⁻² indicated that the Pt/NMCC hybrid catalyst (new Pt-Co/C) is more stable than the conventional Pt-Co/C without the Co leaching out. The PEM fuel cell accelerated stress test (AST) for supports and catalysts demonstrated that their stability changes in the order: Pt₃Pd₁/NMCC hybrid catalyst > Pt/NMCC hybrid catalyst > conventional Pt/C catalyst. Moreover, the hybrid catalysts exhibit higher mass activity than the Pt/C catalysts.     

A polytetrafluoroethylene/quaternized polysulfone membrane for high temperature polymer electrolyte membrane fuel cells

A polytetrafluoroethylene (PTFE)/quaternized polysulfone (QNPSU) composite membrane has been fabricated for use in proton exchange membrane fuel cells (PEMFCs). The composite membrane is made by immobilizing a QNPSU solution into a hydrophobic porous PTFE membrane. The structure of the composite membrane is examined by SEM and EDX. The ionic conductivity of the PTFE/QNPSU membrane, at a relative humidity lower than 0.5% and a temperature of 180 °C, is greater than 0.3 S cm⁻¹, when loaded with 400% H₃PO₄. A hydrogen fuel cell with this membrane operating at 2.0 atmosphere absolute (atma) pressure and 175 °C gives voltages >0.4 V at current densities of 1.0 A cm⁻² using oxygen.     

Numerical modeling and analysis of micro-porous layer effects in polymer electrolyte fuel cells

It is well known that a micro-porous layer (MPL) plays a crucial role in the water management of polymer electrolyte fuel cells (PEFCs), and thereby, significantly stabilizes and improves cell performance. To ascertain the exact roles of MPLs, a numerical MPL model is developed in this study and incorporated with comprehensive, multi-dimensional, multi-phase fuel-cell models that have been devised earlier. The effects of different porous properties and liquid-entry pressures between an MPL and a gas diffusion layer (GDL) are examined via fully three-dimensional numerical simulations. First, when the differences in pore properties and wettability between the MPL and GDL are taken into account but the difference in the entry pressures is ignored, the numerical MPL model captures a discontinuity in liquid saturation at the GDL|MPL interface. The simulation does not, however, capture the beneficial effects of an MPL on cell performance, predicting even lower performance than in the case of no MPL. On the other hand, when a high liquid-entry pressure in an MPL is additionally considered, the numerical MPL model predicts a liquid-free MPL and successfully demonstrates the phenomenon that the high liquid-entry pressure of the MPL prevents any liquid water from entering the MPL. Consequently, it is found from the simulation results that a liquid-free MPL significantly enhances the back-flow of water across the membrane into the anode, which, in turn, helps to avoid membrane dehydration and alleviate the level of GDL flooding. As a result, the model successfully reports the beneficial effects of MPLs on PEFC performance and predicts higher performance in the presence of MPLs (e.g., an increase of 67 mV at 1.5 A cm⁻²). This study provides a fundamental explanation of the function of MPLs and quantifies the influence of their porous properties and the liquid-entry pressure on water transport and cell performance.     

Electrochemical impedance diagnosis of micro porous layer in polymer electrolyte membrane fuel cell electrodes

In the present study, Electrochemical Impedance Spectroscopy (EIS) is used to evaluate two different types of gas diffusion electrodes for Polymer Electrolyte Membrane Fuel Cells (PEMFC). The over potential losses due to the components are determined without any reference electrode using symmetric gas supply of hydrogen or oxygen at various conditions viz., open circuit potential (OCP), various load up to 0.7 A cm⁻², and various humidity conditions. Though it is very clear that the cathode impedance is a major contributor for voltage loss, it is observed that the two type of electrodes with different micro-porous layers (DSGDL and SSGDL), show different behavior with respect to operating conditions like dry gas operation, humid condition etc., The DSGDL is favorable for operating the cell at higher temperature and relative humidity while SSGDL is favorable under dry gas operation. However at higher current density and with humidity, Nernst diffusion plays a major contribution. The Nernst diffusion coefficient decreases with increasing current density for DSGDL and increasing for SSGDL, suggesting that the gas diffusion electrodes need to be engineered depending on the operating conditions and current density.     

Simulation of nanostructured electrodes for polymer electrolyte membrane fuel cells

Aligned carbon nanotubes (CNTs) with Pt uniformly deposited on them are being considered in fabricating the catalyst layer of polymer electrolyte membrane (PEM) fuel cell electrodes. When coated with a proton conducting polymer (e.g., Nafion) on the Pt/CNTs, each Pt/CNT acts as a nanoelectrode and a collection of such nanoelectrodes constitutes the proposed nanostructured electrodes. Computer modeling was performed for the cathode side, in which both multicomponent and Knudsen diffusion were taken into account. The effect of the nanoelectrode lengths was also studied with catalyst layer thicknesses of 2, 4, 6, and 10 μm. It was observed that shorter lengths produce better electrode performance due to lower diffusion barriers and better catalyst utilization. The effect of spacing between the nanoelectrodes was studied. Simulation results showed the need to have sufficiently large gas pores, i.e., large spacing, for good oxygen transport. However, this is at the cost of obtaining large electrode currents due to reduction of the number of nanoelectrodes per unit geometrical area of the nanostructured electrode. An optimization of the nanostructured electrodes was obtained when the spacing was at about 400 nm that produced the best limiting current density.