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- Simulation of a stand-alone residential PEMFC power system with sodium borohydride as hydrogen sourcePublication . Pinto, P.J.R.; Sousa, T.; Fernandes, Vitor; Pinto, A. M. F. R.; Rangel, C. M.Catalytic hydrolysis of sodium borohydride (NaBH4) has been investigated as a method to generate hydrogen for fuel cell applications. The high purity of the generated hydrogen makes this process a potential source of hydrogen for polymer electrolyte membrane fuel cells (PEMFCs). In this paper, a PEMFC power system employing a NaBH4 hydrogen generator is designed to supply continuous power to residential power applications as stand-alone loads and simulated using Matlab/Simulink software package. The overall system is sized to meet a real end-use load, representative of standard European domestic medium electric energy consumption, over a 1-week period. Supervisory control strategies are proposed to manage the hydrogen generation and storage, and the power flow. Simulation results show that the proposed supervisory control strategies are effective and the NaBH4–PEMFC power system is a technologically feasible solution for stand-alone residential applications.
- Integrating hydrogen generation and storage in a novel compact electrochemical system based on metal hydridesPublication . Rangel, C. M.; Fernandes, Vitor; Slavkov, Y.; Bozukov, Latchezar N.A novel electrochemical system has been developed which integrates hydrogen production, storage and compression in only one device, at relatively low cost and high efficiency. The development of efficient and reliable energy storage systems based on hydrogen technology represents a challenge to seasonal storage based on renewable hydrogen. State of the art renewable energy generation systems include separate units such as electrolyser, hydrogen storage vessel and a fuel cell system for the conversion of H2 back into electricity, when required. In this work, a compact unit integrating production and storage is proposed. The developed prototype comprises a six electrode cell assembly using an AB5 type metal hydride and Ni plates as counterelectrodes, in a 35 wt% KOH solution. During charging, hydrogen is absorbed in the metal hydride and corresponding oxygen is conveyed out of the system. Conversely, in the case of discharging hydrogen stored in the metal hydride is released to an external H2 storage. In the present prototype, released hydrogen was delivered into the hydrogen storage up to a pressure of 15 Bar. Metal hydride electrodes with chemical composition LaNi4.3Co0.4Al0.3 were prepared by high frequency vacuum melting followed by high temperature annealing at 1000O C during 8 hours. X-Ray phase analysis showed typical hexagonal structure and no traces of other intermetallic compounds belonging to the La-Ni phase diagram. Thermodynamic study has been performed in a Sieverts type of apparatus produced by Labtech. Int. During cycling, charging was run at 40 A at cell voltages of 1.7 V for two hours which corresponds to C/2 charging time. Hydrogen was released by applying a constant current of 40A for two hours until cell voltage rise from 0.5 to 1.7V, at the end of the processes. The process was studied in-situ using a gas chromatograph from Agilent. It is anticipated that the device will be integrated as a combined hydrogen generator and storage unit in a stand alone system associated to a 1 kW fuel cell.
- Fuel Starvation: irreversible degradation mechanisms in PEM Fuel CellsPublication . Rangel, C. M.; Travassos, Maria Antónia; Fernandes, Vitor; Silva, R. A.; Paiva Luís, TeresaPEM fuel cell operates under very aggressive conditions in both anode and cathode. Failure modes and mechanism in PEM fuel cells include those related to thermal, chemical or mechanical issues that may constrain stability, power and lifetime. In this work, the case of fuel starvation is examined. The anode potential may rise to levels compatible with the oxidization of water. If water is not available, oxidation of the carbon support will accelerate catalyst sintering. Diagnostics methods used for in-situ and ex-situ analysis of PEM fuel cells are selected in order to better categorize irreversible changes of the cell. Electrochemical Impedance Spectroscopy (EIS) is found instrumental in the identification of fuel cell flooding conditions and membrane dehydration associated to mass transport limitations / reactant starvation and protonic conductivity decrease, respectively. Furthermore, it indicates that water electrolysis might happen at the anode. Cross sections of the membrane catalyst and gas diffusion layers examined by scanning electron microscopy indicate electrode thickness reduction as a result of reactions taking place during hydrogen starvation. Catalyst particles are found to migrate outwards and located on carbon backings. Membrane degradation in fuel cell environment is analyzed in terms of the mechanism for fluoride release which is considered an early predictor of membrane degradation.
- Can small additions of an organic polymer or surfactant to sodium borohydride show the way to high hydrogen storage systems for portable applications?Publication . Ferreira, M. J. F.; Gales, L.; Fernandes, Vitor; Rangel, C. M.; Pinto, A. M. F. R.
- H2MS_Hydrogen production management system for prototype reactor [Resumo]Publication . Gano, António; Fernandes, Vitor; Rangel, C. M.
- PEM Fuel Cell performance at sub-zero temperaturesPublication . Rangel, C. M.; Paiva Luís, Teresa; Fernandes, VitorIn this work a study of the performance of a low power fuel cell at sub-freezing temperatures has been undertaken. Knowledge in this area is still scarce. After global characterization of the stack on a wide range of temperatures and relative humidity’s the behaviour at negative temperatures (-5ºC -10ºC, -15ºC) has been established. Furthermore, performance was evaluated after the cell was submitted to cycles from -25ºC to + 25ºC. At the end of 10 cycles only marginal loss in performance was registered, when testing at + 2.5ºC and + 25ºC. On the basis of the obtained results a strategy for start-up and shut-down has been designed in order to be implemented for operation at low temperatures. A failure analysis of the membrane and catalyst layers and GDLs is under way in order to evaluate material degradation
- Novel hydrogen generator: storage based on metal hydridesPublication . Rangel, C. M.; Fernandes, Vitor; Slavkov, Y.; Bozukov, Latchezar N.A novel electrochemical system has been developed which integrates hydrogen production, storage and compression in only one device, at relatively low cost and high efficiency. The prototype comprises a six electrode cell assembly using an AB5 type metal hydride and Ni plates as counter electrodes, in a KOH solution. Metal hydride electrodes with chemical composition LaNi4.3Co0.4Al0.3 has been prepared by high frequency vacuum melting followed by high temperature annealing. X-Ray phase analysis showed typical hexagonal structure and no traces of other intermetallic compounds belonging to the La-Ni phase diagram. Thermodynamic study of the alloy has been performed in a Sieverts type apparatus produced by Labtech. Ltd. In the present prototype during charging, hydrogen is absorbed in the metal hydride and corresponding oxygen is conveyed out of the system. Conversely, in the case of discharging the hydrogen stored in the metal hydride it is released to an external H2 storage. Released hydrogen is delivered into the hydrogen storage up to a pressure of 15 bar. In this work, a compact unit integrating production, storage and compressing hydrogen is proposed as one device at relatively low cost and higher efficiency than a classical electrolyser. It is anticipated that the device will be integrated as a combined hydrogen generator in a stand alone system associated to a 1 kW fuel cell.
- Hydrogen generation by borohydrides: critical issues for portable applicationsPublication . Fernandes, Vitor; Ferreira, M. J. F.; Pinto, A. M. F. R.; Rangel, C. M.High volumetric and gravimetric efficiency are key to potential hydrogen energy carriers. Sodium borohydride emerges as such potentiality and a storage capacity well within DOE targets for 2015. Limitations exist due to the fact that hydrolysis is restricted by available water and due to the lack of low cost re-usable catalysts. An extensive amount of work has been done in our laboratories on Ni and Ru based catalysts, including synthesis and characterization and solutions have been found for durability, stability and reutilization under operating conditions in small volume batch reactors. Results showed that the Langmuir-Hinshelwood model described fairly well the reaction kinetics for all tested temperatures up to 60ºC and up to reactant exhaustion. In this work, issues such as self-hydrolysis, stability of solutions for storage, water management, some aspects of the catalyzed hydrolysis as well as gas conditioning are studied in order to associate a storage solution with sodium borohydride to a low power air breathing cathode PEM fuel cell.
- Hydrogen production from sodium borohydride on a Ni-Ru catalyst : an electrochemical studyPublication . Rangel, C. M.; Fernandes, Vitor; Ferreira, M. J. F.; Pinto, A. M. F. R.; Hashimoto, T.; Thompson, G. E.Previous work by the authors has demonstrated a high rate and high yield hydrolysis of sodium borohydride, in the presence of a Ni-Ru catalyst synthesized by wet chemistry. The catalyst has been fully characterized and utilized more than 300 times exhibiting high stability and durability. In this work, results of an electrochemical study are reported using the powder catalyst supported on a Ni foam in order to measure the open circuit potential during hydrogen production and to study the reaction using voltammetry and ac impedance. Production rates were as high as 10 Lmin-1gcat -1 at 65ºC. Electrochemical studies indicated that the hydrogen evolution mechanism corresponds to a Volmer- Heyrovsky type, suggested by a Tafel slope of 117 mVdec-1. Tafel region potentials are in agreement with values found for hydrolysis at the open circuit. The Langmuir-Hinshelwood mechanism explains the hydrolysis of sodium borohydride using a Ni-Ru catalyst. The role of Ni and Ru is briefly discussed.
- Deactivation and regeneration of Pt-Titania-reduced graphene oxide nanocomposites as catalysts in the photochemical generation of hydrogen [Resumo]Publication . Esteves, M. Alexandra; Fernandes, Vitor; Rangel, C. M.