Study on a compact methanol reformer for a miniature fuel cell

A compact methanol reformer for hydrogen production has been successfully fabricated, which integrated one reforming chamber, one water gas shift reaction chamber, two preheating chambers and two combustion chambers. It can be started-up at room temperature by the combustion of liquid methanol in the combustion chamber within 7 min without any external heating. The cold start response of the methanol reformer has been investigated using different parameters including methanol and air supply rate, and the experiments revealed that the optimum methanol and air flow rate were 0.55 mL/min and 3 L/min respectively. The results indicated that this methanol reformer can provide a high concentration of hydrogen (more than 73%) and the system efficiency is always maintained above 74%. It is further demonstrated in more than 1600 h continuous performance that the reformer could be operated autothermally and exhibited good test stability.     

Modelling and evaluation of heating strategies for high temperature polymer electrolyte membrane fuel cell stacks

Experiments were conducted on two different cathode air cooled high temperature PEM (HTPEM) fuel cell stacks; a 30 cell 400 W prototype stack using two bipolar plates per cell, and a 65 cell 1 kW commercial stack using one bipolar plate per cell. The work seeks to examine the use of different heating strategies and find a strategy suited for fast start-up of the HTPEM fuel cell stacks. Fast start-up of these high temperature systems enables use in a wide range of applications, such as automotive and auxiliary power units, where immediate system response is needed. The development of a dynamic model to simulate the temperature development of a fuel cell stack during heating can be used for assistance in system and control design. The heating strategies analyzed and tested reduced the start-up time of one of the fuel cell stacks from 1 h to about 6 min.     

Impedance characterization of high temperature proton exchange membrane fuel cell stack under the influence of carbon monoxide and methanol vapor

This work presents a comprehensive mapping of electrochemical impedance measurements under the influence of CO and methanol vapor contamination of the anode gas in a high temperature proton exchange membrane fuel cell, at varying load current. Electrical equivalent circuit model parameters based on experimental evaluation of electrochemical impedance spectroscopy measurements were used to quantify the changes caused by different contamination levels. The changes are generally in good agreement with what is found in the literature. It is shown that an increased level of CO contamination resulted in an increase in the high frequency and intermediate frequency impedances. When adding CO and methanol to the anode gas, the low frequency part of the impedance spectrum is especially affected at high load currents, which is clearly seen as a result of the high load current resolution used in this work. The negative effects of methanol vapor are found to be more pronounced on the series resistance. When CO and methanol vapor are both present in anode gas, the entire frequency spectrum and thereby all the equivalent circuit model parameters are affected. It is also shown that the trends of contamination effects are similar for all the test cases, namely, CO alone, methanol alone and a mix of the two, suggesting that effects of methanol may include oxidation into CO on the catalyst layer.     

Water transport study in a high temperature proton exchange membrane fuel cell stack

A study of water transport in a high temperature phosphoric acid doped polybenzimidazole (PBI) membrane fuel cell stack is reported. Tests with different stoichiometries of dry cathode and different humidity levels of anode are performed. It is found that water transport across the membrane electrode assembly (MEA) is noteworthy and that water vapor partial pressure on the anode outlet is almost always higher than on the cathode outlet, even when using dry hydrogen. The water transport is a strong function of current density but it also depends on stoichiometry and humidity level. In a series of tests with dry nitrogen on one side and humid nitrogen on the other side, the membrane's water permeability coefficient is determined to be 2.4 × 10⁻¹³ mol s⁻¹ cm⁻¹ Pa⁻¹ at 160 °C which is more than an order of magnitude higher than the values previously reported in the literature. Also, the results indicate that the permeability coefficient might be relative humidity dependent and could even be somewhat higher than the value reported here, but further investigation is needed. The experimental findings are reproduced and explained with a 2D steady state computational fluid dynamics (CFD) model. Internal water transport profiles across the membrane and along the gas flow channels are presented and discussed.     

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.     

Micro methanol reformer combined with a catalytic combustor for a PEM fuel cell

This paper presents the development of a micro methanol reformer for portable fuel cell applications. The micro reformer consists of a methanol steam reforming reactor, catalytic combustor, and heat exchanger in-between. Cu/ZnO was selected as a catalyst for a methanol steam reforming and Pt for a catalytic combustion of hydrogen with air. Porous ceramic material was used as a catalyst support due to the large surface area and thermal stability. Photosensitive glass wafer was selected as a structural material because of its thermal and chemical stabilities. Performance of the reformer was measured at various test conditions and the results showed a good agreement with the three-dimensional analysis of the reacting flow. Considering the energy balance of the reformer/combustor model, the off-gas of fuel cell can be recycled as a feed of the combustor. The catalytic combustor generated the sufficient amount of heat to sustain the steam reforming of methanol. The conversion of methanol was 95.7% and the hydrogen flow of 53.7 ml/min was produced including 1.24% carbon monoxide. The generated hydrogen was the sufficient amount to operate 4.5 W polymer electrolyte membrane fuel cells.     

Synergetic integration of a methanol steam reforming cell with a high temperature polymer electrolyte fuel cell

In this work an integrated unit, combining a methanol steam-reforming cell (MSR-C) and a high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) was operated at the same temperature (453 K, 463 K and 473 K) allowing thermal integration and increasing the system efficiency of the combined system. A novel bipolar plate made of aluminium gold plated was built, featuring the fuel cell anode flow field in one side and the reformer flow field on the other. The combined unit (MSR-C/HT-PEMFC) was assembled using Celtec^® P2200N MEAs and commercial reforming catalyst CuO/ZnO/Al₂O₃ (BASF RP60). The water/methanol vaporisation originates oscillations in the vapour flowrate; reducing these oscillations increase the methanol conversion from 93% to 96%. The MSR-C/HT-PEMFC showed a remarkable high performance at 453 K. The integrated unit was operated during ca. 700 h at constant at 0.2 A cm^?2, fed alternately with hydrogen and reformate at 453 K and 463 K. Despite the high operating temperature, the HT-PEMFC showed a good stability, with an electric potential difference decreasing rate at 453 K of ca. 100 μV h^?1. Electrochemical impedance spectroscopy (EIS) analysis revealed an overall increase of the ohmic resistances and charge transfer resistances of the electrodes; this fact was assigned to phosphoric acid losses from the electrodes and membrane and catalyst particle size growth.     

The effects of excess phosphoric acid in a Polybenzimidazole-based high temperature proton exchange membrane fuel cell

A series of experiments are conducted in order to investigate the performance of a proton exchange membrane (PEM) fuel cell using a commercially available polybenzimidazole (PBI)-based high temperature membrane. During the study a drastic degradation in performance is observed over time and a significant amount of solid material built-up is found in the flow field plate and the membrane-electrode assembly (MEA). The built-up material is examined by the use of a Scanning Electron Microscope (SEM). Further elemental analysis using Energy Dispersive X-ray Spectroscopy (EDS) finds that the built-up material contains large amount of phosphorus, thus relating it with the excess phosphoric acid found in the MEA. Additional experimental studies show that the built-up material is caused by the excess acid solution in the MEA, and when the excess phosphoric acid is removed from the MEA the fuel cell performance improves significantly and becomes very stable.     

Design of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system

The method of Computational Fluid Dynamics is used to predict the process parameters and select the optimum operating regime of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system. The analysis uses a three reactions kinetics model for methanol steam reforming, water gas shift and methanol decomposition reactions on Cu/ZnO/Al₂O₃ catalyst. Numerical simulations are performed at single channel level for a range of reformer operating temperatures and values of the molar flow rate of methanol per weight of catalyst at the reformer inlet. Two operating regimes of the fuel processor are selected which offer high methanol conversion rate and high hydrogen production while simultaneously result in a small reformer size and a reformate gas composition that can be tolerated by phosphoric acid-doped high temperature membrane electrode assemblies for proton exchange membrane fuel cells. Based on the results of the numerical simulations, the reactor is sized, and its design is optimized.     

Performance and endurance of a high temperature PEM fuel cell operated on methanol reformate

This paper analyzes the effects of methanol and water vapor on the performance of a high temperature proton exchange membrane fuel cell (HT-PEMFC) at varying temperatures, ranging from 140 °C to 180 °C. For the study, a H₃PO₄ – doped polybenzimidazole (PBI) – based membrane electrode assembly (MEA) of 45 cm² active surface area from BASF was employed. The study showed overall negligible effects of methanol-water vapor mixture slips on performance, even at relatively low simulated steam methanol reforming conversion of 90%, which corresponds to 3% methanol vapor by volume in the anode gas feed. Temperature on the other hand has significant impact on the performance of an HT-PEMFC. To assess the effects of methanol-water vapor mixture alone, CO₂ and CO are not considered in these tests. The analysis is based on polarization curves and impedance spectra registered for all the test points. After the performance tests, endurance test was performed for 100 h at 90% methanol conversion and an overall degradation rate of −55 μV/h was recorded.     

Part two: Control of a novel HTPEM-based micro combined heat and power fuel cell system

A novel micro combined heat and power system and a dynamic model thereof were presented in part one of the publication. In the following, the control system and dynamic performance of the system are presented. The model is subjected to a measured consumption pattern of 25 Danish single family houses with measurements of heat, power and hot water consumption every 15th minute during one year.     

Analysis and control of a hybrid fuel delivery system for a polymer electrolyte membrane fuel cell

A polymer electrolyte membrane fuel cell (PEM FC) system as a power source used in mobile applications should be able to produce electric power continuously and dynamically to meet the demand of the driver by consuming the fuel, hydrogen. The hydrogen stored in the tank is supplied to the anode of the stack by a fuel delivery system (FDS) that is comprised of supply and recirculation lines controlled by different actuators. Design of such a system and its operation should take into account several aspects, particularly efficient fuel usage and safe operation of the stack.     

Demonstration of a 20 W class high-temperature polymer electrolyte fuel cell stack with novel fabrication of a membrane electrode assembly

Acid-doped polybenzimidazole (PBI) membrane and polytetrafluoroethylene (PTFE)-based electrodes are used for the membrane electrode assembly (MEA) in high-temperature polymer electrolyte fuel cells (HTPEFCs). To find the optimum PTFE content for the catalyst layer, the PTFE ratio in the electrodes is varied from 25 to 50 wt%. To improve the performance of the electrodes, PBI is added to the catalyst layer. With a weight ratio of PTFE to Pt/C of 45:55 (45 wt% PTFE in the catalyst layer), the fuel cell shows good performance at 150 °C under non-humidified conditions. When 5 wt% PBI is added to the electrodes, performance is further improved (250 mA cm⁻² at 0.6 V). Our 20 W class HTPEFC stack is fabricated with a novel MEA. This MEA consists of 8 layers (1 phosphoric acid-doped PBI membrane, 2 electrodes, 1 sub-gasket, 2 gas-diffusion media, 2 gas-sealing gaskets). The sub-gasket mitigates the destruction of a highly acid-doped PBI membrane and provides long-term durability to the fuel cell stack. The stack operates for 1200 h without noticeable cell degradation.     

Modelling and experimental studies on a direct methanol fuel cell working under low methanol crossover and high methanol concentrations

A number of issues need to be resolved before DMFC can be commercially viable such as the methanol crossover and water crossover which must be minimised in portable DMFCs.     

Externally cooled high temperature polymer electrolyte membrane fuel cell stack

One key issue in high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) stack development is heat removal at the operating temperature of 140–180 °C. Conventionally, this process is done using coolants such as thermooil, steam or pressurized water. In this contribution, external liquid cooling designs are described, which are avoiding two constraints. First, in the cell active area, no liquid coolant is present avoiding any sealing problems with respect to the electrode. Secondly, the external positioning allows high temperature gradients between the heat removal zone and the active area resulting in a good adjustability of appropriate reformate conversion temperatures (e.g. 160 °C) and a more compact cell design. Different design concepts were investigated using modeling techniques and a selection of them has also been investigated experimentally. The experiments proved the feasibility of the external cooling design and showed that the temperature gradients within the active area are below 15 K under typical operating conditions.     

Controller design for polymer electrolyte membrane fuel cell systems for automotive applications

Continuous developments in Proton Exchange Membrane Fuel Cells (PEMFC) make them a promising technology to achieve zero emissions in multiple applications including mobility. Incremental advancements in fuel cells materials and manufacture processes make them now suitable for commercialization. However, the complex operation of fuel cell systems in automotive applications has some open issues yet. This work develops and compares three different controllers for PEMFC systems in automotive applications. All the controllers have a cascade control structure, where a generator of setpoints sends references to the subsystems controllers with the objective to maximize operational efficiency. To develop the setpoints generators, two techniques are evaluated: off-line optimization and Model Predictive Control (MPC). With the first technique, the optimal setpoints are given by a map, obtained off-line, of the optimal steady state conditions and corresponding setpoints. With the second technique, the setpoints time profiles that maximize the efficiency in an incoming time horizon are continuously computed. The proposed MPC architecture divides the fast and slow dynamics in order to reduce the computational cost. Two different MPC solutions have been implemented to deal with this fast/slow dynamics separation. After the integration of the setpoints generators with the subsystems controllers, the different control systems are tested and compared using a dynamic detailed model of the automotive system in the INN-BALANCE project running under the New European Driving Cycle.     

Hydrogen production of two-stage temperature steam reformer integrated with PBI membrane fuel cells to optimize thermal management

An endothermic methanol steam reformer achieves optimal performance at a temperature of about 240 °C. A polybenzimidazole (PBI) membrane fuel cell was operated exothermically at 160 °C–200 °C. To better couple the lower temperature fuel cell to the higher temperature steam reformer, a two-stage temperature steam reformer to integrate into the PBI membrane fuel cell system is proposed. The reformer optimizes thermal management and increases the system efficiency.     

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.     

Study of flow channel geometry using current distribution measurement in a high temperature polymer electrolyte membrane fuel cell

To improve fuel cell design and performance, research studies supported by a wide variety of physical and electrochemical methods have to be carried out. Among the different techniques, current distribution measurement owns the desired feature that can be performed during operation, revealing information about internal phenomena when the fuel cell is working. Moreover, short durability is one of the main problems that is hindering fuel cell wide implementation and it is known to be related to current density heterogeneities over the electrode surface. A good flow channel geometry design can favor a uniform current density profile, hence hypothetically extending fuel cell life. With this, it was thought that a study on the influence of flow channel geometry on the performance of a high temperature polymer electrolyte membrane (PEM) fuel cell using current distribution measurement should be a very solid work to optimize flow field design. Results demonstrate that the 4 step serpentine and pin-type geometries distribute the reactants more effectively, obtaining a relatively flat current density map at higher current densities than parallel or interdigitated ones and yielding maximum powers up to 25% higher when using oxygen as comburent. If air is the oxidant chosen, interdigitated flow channels perform almost as well as serpentine or pin-type due to that the flow conditions are very important for this geometry.