A novel design of solid-state NaBH4 composite as a hydrogen source for 2 W PEMFC applications

Hydrolysis of sodium borohydride (NaBH₄) is a promising method for on-board hydrogen supply to polymer electrolyte membrane fuel cells (PEMFC). This article presents an attempt to design a novel solid-state NaBH₄ composite, which is made up of NaBH₄ powder, Co²⁺/IR-120 catalyst and silicone rubber, for hydrogen generator. The silicone rubber can act as a stabilizer in the solid-state NaBH₄ composite because of its surface hydrophobicity leading to reduced diffusion rate of water into the composite. The solid-state NaBH₄ composite can produce hydrogen stably near 25 mL min⁻¹ for at least 2 h without employment of any mechanical control system. Using the hydrogen generated from the solid-state NaBH₄ composite, a 2 W PEMFC stack is successfully operated to power a cellular phone.     

Connected evaluation of polymer electrolyte membrane fuel cell with dehydrogenation reactor of liquid organic hydrogen carrier

Recently, hydrogen energy technologies attract attention as power systems. To develop hydrogen energy systems, hydrogen storage methods with high storage density and good safety are required. Liquid organic hydrogen carrier (LOHC) is one of the novel hydrogen storage technologies. LOHC has advantages of high storage density, good safety, and easy handling. In this study, a polymer electrolyte membrane fuel cell (PEMFC) stack is operated with hydrogen released from LOHC to evaluate the feasibility of the connected operation of the PEMFC stack and LOHC dehydrogenation reactor. Dibenzyltoluene (H0-DBT) is used as a LOHC material, and the dehydrogenation of perhydro dibenzyltoluene (H18-DBT) is conducted at 240–300 °C. Released hydrogen is purified by adsorbent of activated carbon to remove impurities. However, 100–1400 ppm of methane is observed after the purification, and the PEMFC stack power is reduced from 39.4 W to 39.0 W during the operation by hydrogen dilution and physical adsorption of methane. Then, to evaluate the irreversible damage, pure hydrogen was supplied to the PEMFC stack. The stack power is recovered to 39.4 W. It is concluded that the connected operation of the LOHC dehydrogenation reactor and PEMFC stack is feasible, and the activated carbon adsorbent can be a cost-effective purification method for LOHC.     

35-We polymer electrolyte membrane fuel cell system for notebook computer using a compact fuel processor

A polymer electrolyte membrane fuel cell (PEMFC) system is developed to power a notebook computer. The system consists of a compact methanol-reforming system with a CO preferential oxidation unit, a 16-cell PEMFC stack, and a control unit for the management of the system with a d.c.–d.c. converter. The compact fuel-processor system (260 cm³) generates about 1.2 L min⁻¹ of reformate, which corresponds to 35 We, with a low CO concentration (<30 ppm, typically 0 ppm), and is thus proven to be capable of being targetted at notebook computers.     

Polymer electrolyte fuel cell mini power unit for portable application

This paper describes the design, realisation and test of a power unit based on a polymer electrolyte fuel cell, operating at room temperature, for portable application. The device is composed of an home made air breathing fuel cell stack, a metal hydride tank for H₂ supply, a dc–dc converter for power output control and a fan for stack cooling. The stack is composed by 10 cells with an active surface of 25 cm² and produces a rated power of 15 W at 6 V and 2 A. The stack successfully runs with end-off fed hydrogen without appreciable performance degradation during the time. The final assembled system is able to generate 12 W at 9.5 V, and power a portable DVD player for 3 h in continuous. The power unit has collected about 100 h of operation without maintenance.     

Operating characteristics of an air-cooling PEMFC for portable applications

Optimal design and proper operation is important to get designed output power of a polymer electrolyte membrane fuel cell (PEMFC) stack. The air-cooling fuel cell stack is widely used in sub kW PEMFC systems. The purpose of this study is to analyze the operating conditions affecting the performance of an air-cooling PEMFC which is designed for portable applications. It is difficult to maintain well balanced operating conditions. These parameters are the relative humidity, the temperature of the stack, the utility ratio of the reactant gas and so on. In this study a 500 W rate air-cooling PEMFC was fabricated and tested to evaluate the design performance and to determine optimal operating conditions. Moreover, basic modeling also is carried out. These results can be used as design criteria and optimal operating conditions for portable PEMFCs.     

Portable PEMFC stack using sulfonated poly (fluorenyl ether ketone) ionomer as membrane

Portable polymer electrolyte membrane fuel cells (PEMFCs) stack was assembled with sulfonated poly(fluorenyl ether ketone) (SPFEK) ionomer membranes. The portable PEMFC stack was studied by means of cell performance tests at high temperatures under low relatively humidity (RH). The experimental results showed that the output power of the stack increased from 28.74 W to 37.11 W with increasing operating temperature from 30 to 90 °C under 100% RH. When the operating temperature was over 100 °C, the output power decreased with further increasing temperature from 27.68 W (100 °C, 85% RH) to 19.87 W (120 °C, 50% RH). The output at 120 °C and under 50% RH was 69% output power of the stack at 30 °C and under 100% RH. These results demonstrated that the self-prepared SPFEK ionomer membrane was a promising PEM for the application in high-temperature PEMFC.     

Performance enhancement of air-breathing proton exchange membrane fuel cell through utilization of an effective self-humidifying platinum-carbon catalyst

One issue with air-breathing proton exchange membrane fuel cells (AB-PEMFCs) is that the reactants are not externally humidified, and thus the membrane or the catalyst layers might dry out due to electro-osmotic drag, diffusion and evaporation at the opening cathode. This results in a drop in internal ionic conductivity and thus in cell performance. Here, the preparation and characterization of self-humidifying carbon-supported Pt catalyst using citric acid modified carbon black (CA-CB) as the catalyst support are reported. Pt/CA-CB is highly hydrophilic due to the functional groups attached on the carbon support, which endows the ability to retain water in the membrane electrolyte assembly (MEA) and thereby help to improve the performance of AB-PEMFCs. A maximum power density of 204 mW cm⁻² can be achieved in an air-breathing PEMFC stack using Pt/CA-CB, a thick polymer membrane (NRE212) and a circular opening cathode. A 23.4% enhancement in the output power density is obtained by using Pt/CA-CB in place of a commercial catalyst when oblique slit cathodes are employed. This self-humidifying catalyst is particularly suitable for portable PEMFC applications.     

Scale-up of a high temperature polymer electrolyte membrane fuel cell based on polybenzimidazole

A high temperature PEM fuel cell stack with a total active area 150 cm² has been studied. The PEM technology is based on a polybenzimidazole (PBI) membrane. Cast from a PBI polymer synthesised in our lab, the performance of a three-cell stack was analysed in static and dynamic modes. In static mode, operating at high constant oxygen flow rate (QO₂>1105 ml O₂/min) produces a small decrease on the stack performance. High constant oxygen stoichiometry (λO₂>3) does not produce a decrease on the performance of the stack. There are not differences between operating at constant flow rate of oxygen and constant stoichiometry of oxygen in the stack performance. The effect of operating at high temperature with a pressurization system and operating at higher temperatures are beneficial since the performance of the fuel cell is enhanced. A large shut-down stage produces important performance losses due to the loss of catalyst activity and the loss of membrane conductivity. After 150 h of operation at 0.2 A cm⁻², it is observed a very high voltage drop. The phosphoric acid leached from the stack was also evaluated and did not exceed 2% (w/w). This fact suggests that the main degradation mechanism of a fuel cell stack based on polybenzimidazole is not the electrolyte loss. In dynamic test mode, it was observed a rapid response of power and current output even at the lower step-time (10 s). In the static mode at 125 °C and 1 atm, the stack reached a power density peak of 0.29 W cm⁻² (43.5 W) at 1 V.     

Analysis of a PEMFC durability test under low humidity conditions and stack behaviour modelling using experimental design techniques

A polymer electrolyte membrane fuel cell (PEMFC) stack has been operated under low humidity conditions during 1000 h. The fuel cell characterisation is based both on polarisation curves and electrochemical impedance spectra recorded for various stoichiometry rates, performed regularly throughout the ageing process. Some design of experiment (DoE) techniques, and in particular the response surface methodology (RSM), are employed to analyse the results of the ageing test and to propose some numerical/statistical laws for the modelling of the stack performance degradation. These mathematical relations are used to optimise the fuel cell operating conditions versus ageing time and to get a deeper understanding of the ageing mechanisms. The test results are compared with those obtained from another stack operated in stationary regime at roughly nominal conditions during 1000 h (reference test). The final objective is to ensure for the next fuel cell systems proper operating conditions leading to extended lifetimes.     

Stand-alone PEM water electrolysis system for fail safe operation with a renewable energy source

A complete stand-alone electrolyser system has been constructed as a transportable unit for demonstration of a sustainable energy facility based on hydrogen and a renewable energy source. The stand-alone unit is designed to support a polymer electrolyte membrane (PEM) stack operating at up to ∼4 kW input power with a stack efficiency of about 80% based on HHV of hydrogen. It is self-pressurizing and intended for operation initially at a differential pressure of less than 6 bar across the membrane electrode assembly with the hydrogen generation side being at a higher pressure. With a slightly smaller stack, the system has been operated at an off-site facility where it was directly coupled to a 2.4 kW photovoltaic (PV) solar array. Because of its potential use in remote areas, the balance-of-plant operates entirely on 12 V DC power for all monitoring, control and safety requirements. It utilises a separate high-current supply as the main electrolyser input, typically 30–40 V at 100 A from a renewable source such as solar PV or wind. The system has multiple levels of built-in operator and stack safety redundancy. Control and safety systems monitor all flows, levels and temperatures of significance. All fault conditions are failsafe and are duplicated, triggering latching relays which shut the system down. Process indicators monitor several key variables and allow operating limits to be easily adjusted in response to experience of system performance gained in the field.     

Experimental analysis of dynamic characteristics on the PEM fuel cell stack by using Taguchi approach with neural networks

This study determines the optimum operating parameters for a proton exchange membrane fuel cell (PEMFC) stack to obtain small variation and maximum electric power output using a robust parameter design (RPD). The operating parameters examined experimentally are operating temperatures, operating pressures, anode/cathode humidification temperatures, and reactant flow rates. First, the dynamic Taguchi method is used to obtain the maximum and stable power density against the different current densities, which are regarded as the systemic inputs considered a signal factor. The relationship between control factors and responses in the PEMFC stack is determined using a neural network. The discrete parameter levels in the dynamic Taguchi method can be divided into desired levels to acquire real optimum operating parameters. Based on these investigations, the PEMFC stack is operated at the current densities of 0.4–0.8 A/cm². Since the voltage shift is quite small (roughly 0.73–0.83 V for each single cell), the efficiency would be higher. In the range of operation, the operating pressure, the cathode humidification temperature and the interactions between operating temperature and operating pressure significantly impact PEMFC stack performance. As the operating pressure increasing, the increments of the electric power decrease, and power stability is enhanced because the variation in responses is reduced.     

Computationally efficient modeling of the dynamic behavior of a portable PEM fuel cell stack

A numerically efficient mathematical model of a proton exchange membrane fuel cell (PEMFC) stack is presented. The aim of this model is to study the dynamic response of a PEMFC stack subjected to load changes under the restriction of short computing time. This restriction was imposed in order for the model to be applicable for nonlinear model predictive control (NMPC). The dynamic, non-isothermal model is based on mass and energy balance equations, which are reduced to ordinary differential equations in time. The reduced equations are solved for a single cell and the results are upscaled to describe the fuel cell stack. This approach makes our calculations computationally efficient. We study the feasibility of capturing water balance effects with such a reduced model. Mass balance equations for water vapor and liquid water including the phase change as well as a steady-state membrane model accounting for the electro-osmotic drag and diffusion of water through the membrane are included. Based on this approach the model is successfully used to predict critical operating conditions by monitoring the amount of liquid water in the stack and the stack impedance. The model and the overall calculation method are validated using two different load profiles on realistic time scales of up to 30 min. The simulation results are used to clarify the measured characteristics of the stack temperature and the stack voltage, which has rarely been done on such long time scales. In addition, a discussion of the influence of flooding and dry-out on the stack voltage is included. The modeling approach proves to be computationally efficient: an operating time of 0.5 h is simulated in less than 1 s, while still showing sufficient accuracy.     

Characterization and single cell testing of Pt/C electrodes prepared by electrodeposition

Electrodes for proton exchange membrane fuel cells (PEMFC) have been prepared by the electrodeposition method. For this task, the electrodeposition of platinum is carried out on a carbon black substrate impregnated with an ionomer, proton conducting, medium. Before electrodeposition, the substrate is submitted to an activation process to increase the hydrophilic character of the surface to a few microns depth.Electrodeposition of platinum takes place inside the generated surface hydrophilic layer, resulting in a continuous phase covering totally or partially carbon substrate grains. Cross sectional images show a decay profile of platinum towards the interior of the substrate, reflecting a deposition process limited by diffusion of PtCl₆²⁻ through the porous substrate. Electrodes with different platinum loads have been prepared, and membrane electrode assemblies (MEA) have been mounted with the electrodeposited electrodes as cathode and other standard components (commercial anode and Nafion^R 117 membrane). The electrochemically active surface area determined from hydrogen underpotential deposition charge, is lower on the electrodeposited electrodes than on standard electrodes. However, single cell testing shows higher mass specific activity on electrodeposited cathodes with low and intermediate Pt load (below 0.05 mg Pt cm⁻²).     

Design,fabrication and performance analysis of a 200 W PEM fuel cell short stack

A PEM fuel cell short stack of 200 W capacity, with an active area of 100 cm² has been designed and fabricated in-house. The status of unit cell performance was 0.55 W cm⁻². Based on the unit cell technology, a short stack has been developed. The proper design of uniform flow distribution, cooling plate and compressed end plate were important to achieve the best performance of the short stack. The performance of four cells stack was analyzed in static and dynamic modes. In the static mode of polarization curve, the stack has peak power density of 0.55 W cm⁻² (220 W) at 0.5 V per cell, when the voltage was scanning from low to high voltage (1.5–3.5 V), and resulted in minimum water flooding inside the stack. In this study a series of dynamic loadings were tested to simulate the vehicle acceleration. The fuel cell performances respond to dynamic loading influenced by the hydrogen/air stoichiometric, back pressure, and dynamic-loading time. It was needed high hydrogen stoichiometric and back pressure to maintain high dynamic performance. In the long-time stable power testing, the stack was difficult to maintain at high performance, due to the water flooding at high output power. An adjusting cathode back-pressure method for purging water was proposed to prevent the water flooding at flow channels and maintain the stable output power at 170 W (0.42 W cm⁻²).     

The use of on-line hydrogen sensor for studying inert gas effects and nitrogen crossover in PEMFC system

The design and construction of a polymer electrolyte membrane fuel cell (PEMFC) system test bench suitable for investigating the effects of inert gas build-up and hydrogen quality on the performance of PEMFC systems is reported. Moreover, a new methodology to measure the inert gas crossover rate using an on-line hydrogen concentration sensor is introduced, and preliminary results are presented for an aged 8 kW PEMFC stack. The system test bench was also characterized using the same stack, whereupon its performance was observed to be close to commercial systems. The effect of inert gas accumulation and hence the quality of hydrogen on the performance of the system was studied by diluting hydrogen gas in the anode supply pipeline with nitrogen. During these experiments, uneven performance between cells was observed for the aged stack.     

Dynamic fuel cell stack model for real-time simulation based on system identification

The authors have been developing an empirical mathematical model to predict the dynamic behaviour of a polymer electrolyte membrane fuel cell (PEMFC) stack. Today there is a great number of models, describing steady-state behaviour of fuel cells by estimating the equilibrium voltage for a certain set of operating parameters, but models capable of predicting the transient process between two steady-state points are rare. However, in automotive applications round about 80% of operating situations are dynamic. To improve the reliability of fuel cell systems by model-based control for real-time simulation dynamic fuel cell stack model is needed. Physical motivated models, described by differential equations, usually are complex and need a lot of computing time. To meet the real-time capability the focus is set on empirical models. Fuel cells are highly nonlinear systems, so often used auto-regressive (AR), output-error (OE) or Box-Jenkins (BJ) models do not accomplish satisfying accuracy. Best results are achieved by splitting the behaviour into a nonlinear static and a linear dynamic subsystem, a so-called Uryson-Model. For system identification and model validation load steps with different amplitudes are applied to the fuel cell stack at various operation points and the voltage response is recorded. The presented model is implemented in MATLAB environment and has a computing time of less than 1 ms per step on a standard desktop computer with a 2.8 MHz CPU and 504 MB RAM. Lab tests are carried out at DaimlerChrysler R&D Centre with DaimlerChrysler PEMFC hardware and a good agreement is found between model simulations and lab tests.     

Inductively coupled plasma nitriding of chromium electroplated AISI 316L stainless steel for PEMFC bipolar plate

Chromium electroplated AISI 316L stainless steel was nitrided using inductively coupled plasma (ICP) for application in the bipolar plate of a polymer electrolyte membrane fuel cell (PEMFC). A continuous and thin chromium nitride layer was formed at the surface of the samples after ICP nitriding for 2 h at 400 °C. The interfacial contact resistance (ICR) and corrosion resistance in simulated PEMFC operating conditions were higher than the required values, while they varied with the applied dc bias voltage during the nitriding process. The ICR value decreased with an increase in bias voltage. Potentiodynamic polarization measurements showed that all of the nitrided samples had excellent corrosion resistance with a current density of ∼10⁻⁷ A cm⁻² at the cathode. It was also found that the oxygen content at the surface was not increased after the corrosion test. X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), and Auger electron spectroscopy (AES) were used to analyze the effect of plasma nitriding.     

Development of porous carbon foam polymer electrolyte membrane fuel cell

In order to prove the feasibility of using porous carbon foam material in a polymer electrolyte membrane fuel cell (PEMFC), a single PEMFC is constructed with a piece of 80PPI (pores per linear inch) Reticulated Vitreous Carbon (RVC) foam at a thickness of 3.5 mm employed in the cathode flow-field. The cell performance of such design is compared with that of a conventional fuel cell with serpentine channel design in the cathode and anode flow-fields. Experimental results show that the RVC foam fuel cell not only produces comparative power density to, but also offers interesting benefits over the conventional fuel cell. A 250 h long term test conducted on a RVC foam fuel cell shows that the durability and performance stability of the material is deemed to be acceptable. Furthermore, a parametric study is conducted on single RVC foam fuel cells. Effect of geometrical and material parameters of the RVC foam such as PPI and thickness and operating conditions such as pressure, temperature, and stoichiometric ratio of the reactant gases on the cell performance is experimentally investigated in detail. The single cell with the 80PPI RVC foam exhibits the best performance, especially if the thinnest foam (3.5 mm) is used. The cell performance improves with increasing the operating gauge pressure from 0 kPa to 80 kPa and the operating temperature from 40 °C to 60 °C, but deteriorates as it further increases to 80 °C. The cell performance improves as the stoichiometric ratio of air increases from 1.5 to 4.5; however, the improvement becomes marginal when it is raised above 3.0. On the other hand, changing the stoichiometric ratio of hydrogen does not have a significant impact on the cell performance.     

Water management in a novel proton exchange membrane fuel cell stack with moisture coil cooling

Water flooding causes severe degradation of the performance and lifetime of proton exchange membrane fuel cell (PEMFC). In this study, a novel PEMFC stack with in-built moisture coil cooling was designed and the effects of moisture coil cooling on water management in the new PEMFC stack under various operating conditions were investigated. The result showed that the performance of the PEMFC stack was significantly improved due to the moisture condensation under high current density, high operating temperature, high relative humidity and high operating pressure. The output power was increases by 21.62% (525.71 W) at 1600·mA cm⁻² while the increased parasitic power was no more than 35W. Moreover, degradation of the cathode catalyst layer after 100 h operation was also reduced by using moisture coil cooling. Compared with the situation without moisture condensation, the maximum decay rate of the cathode catalyst layer thickness after 100 h operation was reduced by 13.01%. Accordingly, the novel design is valuable and can be widely used in the future design of PEMFC.     

Performance and degradation of high temperature polymer electrolyte fuel cell catalysts

An investigation of carbon-supported Pt/C and PtCo/C catalysts was carried out with the aim to evaluate their stability under high temperature polymer electrolyte membrane fuel cell (PEMFC) operation. Carbon-supported nanosized Pt and PtCo particles with a mean particle size between 1.5 nm and 3 nm were prepared by using a colloidal route. A suitable degree of alloying was obtained for the PtCo catalyst by using a carbothermal reduction. The catalyst stability was investigated to understand the influence of carbon black corrosion, platinum dissolution and sintering in gas-fed sulphuric acid electrolyte half-cell at 75 °C and in PEMFC at 130 °C. Electrochemical active surface area and catalyst performance were determined in PEMFC at 80 °C and 130 °C. A maximum power density of about 700 mW cm⁻² at 130 °C and 3 bar abs. O₂ pressure with 0.3 mg Pt cm⁻² loading was achieved. The PtCo alloy showed a better stability than Pt in sulphuric acid after cycling; yet, the PtCo/C catalyst showed a degradation after the carbon corrosion test. The PtCo/C catalyst showed smaller sintering effects than Pt/C after accelerated degradation tests in PEMFC at 130 °C.