Development of a compact hydrogen generator from sodium borohydride

Chemical hydrides can be a simple and safe hydrogen vector for polymer fuel cells. In particular the catalytic hydrolysis of sodium borohydride (NaBH₄) is here envisaged to produce on-demand hydrogen to be supplied to a small solid polymer fuel cell in a portable energy generator.     

Hydrogen generation from hydrolysis of solid sodium borohydride promoted by a cobalt–molybdenum–boron catalyst and aluminum powder

Direct use of solid sodium borohydride (NaBH₄) to react with minimized amount of water provides a straightforward means for increasing the hydrogen density of the system. But meanwhile, the resulting solid–liquid reaction system always suffers from serious kinetic problem. Our study found that the cobalt–molybdenum–boron (Co–Mo–B) catalyst prepared using an ethylene glycol solution of cobalt chloride is highly effective for promoting the hydrolysis reaction of solid NaBH₄. Particularly, a combined usage of small amounts of Co–Mo–B catalyst, aluminum powder and sodium hydroxide enables a rapid and high-yield hydrogen generation from the hydrolysis reaction of solid NaBH₄. A systematic study has been conducted to investigate the property dependence of the system on the components. In addition, the by-products of reaction were analyzed using powder X-ray diffraction and thermogravimetry/differential scanning calorimetry/mass spectroscopy techniques. Our study demonstrates that the multi-component system with an optimized composition can fulfill over 95% fuel conversion, yielding 6.43 wt% hydrogen within 3 min. The favorable combination of high hydrogen density, fast hydrogen generation kinetics and high fuel conversion makes the newly developed solid NaBH₄-based system promising for portable hydrogen source applications.     

Design and development of a fuel cell-powered small unmanned aircraft

The design, construction, and flight test of a fuel cell-powered small unmanned aircraft are described. A fuel cell system featuring a polymer electrolyte membrane fuel cell combined with a hydrogen generator, which serves as a new power source alternative to the existing batteries, is proposed. The hydrogen generator uses a catalytic hydrolysis reaction to extract hydrogen from an alkaline solution of sodium borohydride, and constructed with a reactor, pump, separator, and fuel cartridge. Considering the performance characteristics of the fuel cell, the hybrid power management of a fuel cell and a battery was contrived. The fuel cell stack, hydrogen generator, and power management system were evaluated at the various load conditions. A high efficiency unmanned aircraft was designed and fabricated to validate the possibility of the proposed fuel cell system, and a small flight control system was developed for a high endurance test flight. Wind-tunnel tests were conducted before the flight tests under actual flight conditions. The possibility for the utilization of a fuel cell in a small aircraft was validated through the fuel cell powered flight test. The fuel cell aircraft flew for 2 h without incidents in the fuel cell system.     

Effect of anode conditions on the performance of direct borohydride–hydrogen peroxide fuel cell system

Direct borohydride–hydrogen peroxide fuel cells (DBHPFCs) are attractive power sources for space applications. Although the cathode conditions are known to affect the system performance, the effect of the anode conditions is rarely investigated. Thus, in this study, a DBHPFC system was tested under various anode conditions, such as electrocatalyst, fuel concentration, and stabilizer concentration, to investigate their effects on the system performance. A virtual DBHPFC system was analyzed based on the experimental data obtained from fuel cell tests. The anode electrocatalyst had a considerable effect on the mass and electrochemical reaction rate of the fuel cell system, but had minimal effect on the decomposition reaction rate. The NaBH₄ concentration greatly influenced the mass and decomposition reaction rate of the fuel cell system; however, it had minimal impact on the electrochemical reaction rate. The NaOH concentration affected the electrochemical reaction rate, decomposition reaction rate, and mass of the fuel cell system. Therefore, the significant effects of the anode conditions on the electrochemical reaction rate, decomposition reaction rate, and mass of the fuel cell system prompt the need for their careful selection through fuel cell tests and system analysis.     

Preparation of hollow poly(vinylidene fluoride) capsules containing nickel catalyst for hydrogen storage and production

Hollow polymer capsules offer an approach for storage of hydrogen. Thus, in this paper, hollow poly(vinylidene fluoride) capsules were prepared by phase inversion of a polyvinylidene fluoride solution containing sodium borohydride that reacts with water to produce hydrogen during the phase separation. The effects of additives on the structure of the capsules were observed by scanning electronic microscopy and on the adsorption property were investigated by adsorbing sodium borohydride. The effects of the amount of capsules, concentration of sodium borohydride, and temperature on hydrogen production were studied via catalytic hydrolysis of sodium borohydride in aqueous solution. It was noticed that the capsules have good catalytic activity for hydrolysis of sodium borohydride with an activation energy of 49.3 kJ mol^?1. And the capsules can be used for adsorption of sodium borohydride in tetrahydrofuran before catalytic hydrolysis of sodium borohydride in water. Copyright © 2014 John Wiley & Sons, Ltd.     

Electrooxidation of hydrogen peroxide and sodium borohydride on Ni deposited carbon fiber electrode for alkaline fuel cells

In this study, Ni deposited carbon fiber electrode (Ni/CF) prepared by electroless deposition method was examined for their redox process and electrocatalytic activities during the oxidation of hydrogen peroxide and sodium borohydride in alkaline solutions. The Ni/CF catalyst was characterized by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), scanning electron microscopy (SEM) and electrochemical voltammetry analysis. The electrocatalytic activity of the Ni/CF for oxidation of hydrogen peroxide and sodium borohydride in alkaline solutions was investigated by cyclic voltammetry. The anodic peak current density is found to be three times higher on Ni/CF catalyst for sodium borohydride compared to that for hydrogen peroxide. Preliminary tests on a single cell of a direct borohydride/peroxide fuel cell (DBPFC) and direct peroxide/peroxide fuel cell (DPPFC) indicate that DBPFC with the power density of 5.9 mW cm⁻² provides higher performance than DPPFC (3.8 mWcm⁻²).     

Optimized hydrogen generation in a semicontinuous sodium borohydride hydrolysis reactor for a 60 W-scale fuel cell stack

Catalyzed hydrolysis of sodium borohydride (SBH) is a promising method for the hydrogen supply of fuel cells. In this study a system for controlled production of hydrogen from aqueous sodium borohydride (SBH) solutions has been designed and built. This simple and low cost system operates under controlled addition of stabilized SBH solutions (fuel solutions) to a supported CoB catalyst. The system works at constant temperature delivering hydrogen at 1 L min⁻¹ constant rate to match a 60-W polymer electrolyte membrane fuel cell (PEMFC). For optimization of the system, several experimental conditions were changed and their effect was investigated. A simple model based only on thermodynamic considerations was proposed to optimize system parameters at constant temperature and hydrogen evolution rate. It was found that, for a given SBH concentration, the use of the adequate fuel addition rate can maximize the total conversion and therefore the gravimetric storage capacity. The hydrogen storage capacity was as high as 3.5 wt% for 19 wt% SBH solution at 90% fuel conversion and an operation temperature of 60 °C. It has been demonstrated that these optimized values can also be achieved for a wide range of hydrogen generation rates. Studies on the durability of the catalyst showed that a regeneration step is needed to restore the catalytic activity before reusing.     

Highly efficient and reactivated electrocatalyst of ruthenium electrodeposited on nickel foam for hydrogen evolution from NaBH4 alkaline solution

Cyclic life of catalyst for hydrolysis of sodium borohydride is one of the key issues, which hinder commercialization of hydrogen generation from sodium borohydride (NaBH₄) solution. This paper is aimed at promoting the cyclic life of Ru/Ni foam catalysts by employing an electro-deposition method. The effect of hydrolysis parameters on hydrolysis of sodium borohydride was studied for improving the catalytic performance. It is found that the hydrogen generation rate (HGR) of the hydrolysis reaction catalyzed by Ru/Ni foam catalyst can reach as high as 23.03 L min^?1 g^?1 (Ru). The Ru/Ni foam catalyst shows good catalytic activity after a cycleability test of 100 cycles by rinsing with HCl, which is considered as more effective method than rinsing with water for recovering the performance of Ru/Ni foam catalyst.     

Advanced mathematical model for the passive direct borohydride/peroxide fuel cell

In the literature a mathematical model has been developed for the direct borohydride fuel cells by Verma et al. [1]. This model simply simulates the fuel cell system via kinetic mechanisms of the borohydride and oxygen. Their mathematical expression contains the activation losses caused by the oxidation of the borohydride and the concentration overpotential increased by the reduction of oxygen. In this study a direct borohydride/peroxide fuel cell has been constructed using hydrogen peroxide (H₂O₂) as oxidant instead of the oxygen. Therefore we created an advanced model for peroxide fuel cells, including the activation overpotential of the peroxide. The goal of our model is to provide the information about the peroxide reduction effect on the cell performance. Our comprehensive mathematical model has been developed by taking Verma’s model into account. KH₂O₂ used in the advanced model was calculated as 6.72 × 10⁻⁴ mol cm⁻² s⁻¹ by the cyclic voltammogram of Pt electrode in the acidic peroxide solution.     

Controlled hydrogen generation by reaction of aluminum/sodium hydroxide/sodium stannate solid mixture with water

Aluminum/water reaction system has gained considerable attention for potential hydrogen storage applications. In this paper, we report a new aluminum-based hydrogen generation system that is composed of aluminum/sodium hydroxide/sodium stannate solid mixture and water. This new system is characterized by the features as follows: the combined usage of sodium hydroxide and sodium stannate promoters, the use of solid fuel in a tablet form and the direct use of water as a reaction controlling agent. The factors that influence the hydrogen generation performance of the system were investigated. The optimized system exhibits a favorable combination of high hydrogen generation rate, high fuel conversion, rapid dynamic response, which makes it promising for portable hydrogen source applications.     

Ceria supported manganese(0) nanoparticle catalysts for hydrogen generation from the hydrolysis of sodium borohydride

Herein we report for the first time the preparation and catalytic use of the ceria supported manganese(0) nanoparticles in hydrogen generation from the hydrolysis of sodium borohydride. They are in situ formed from the reduction of manganese(II) ions on the surface of ceria nanopowders during the catalytic hydrolysis of sodium borohydride in aqueous solution at room temperature. Manganese(0) nanoparticles are isolated from the reaction solution by centrifugation and characterized by a combination of analytical techniques. Nanoceria supported manganese(0) nanoparticles are highly active and long-lived catalysts providing a turnover frequency of 417 h^?1 and 45,000 turnovers in hydrogen generation from the hydrolysis of sodium borohydride at 25.0 ± 0.1 °C. They also have high durability as they retain 55% of their initial catalytic activity after the fifth cycle of hydrolysis providing a release of 4 equivalent H₂ gas per mol of sodium borohydride. The noticeable activity loss in successive runs of hydrolysis is attributed to the deactivation due to agglomeration. High activity and stability of ceria supported manganese(0) nanoparticles are ascribed to the unique nature of reducible cerium oxide. The formation of cerium(III) defects under catalytic conditions provides strong binding for the manganese(0) nanoparticles to oxide surface which makes the catalytic activity and stability favorable. Our report also includes the results of kinetic study of catalytic hydrolysis of sodium borohydride depending on the temperature, catalyst and substrate concentration.     

Hydrolysis of sodium borohydride in concentrated aqueous solution

Sodium borohydride is being commercialized to provide hydrogen storage for portable fuel cells. Prior kinetic studies have focused on catalytic hydrolysis of dilute aqueous solutions at room temperature. This work reports on a new NMR method for studying the kinetics of non-catalyzed sodium borohydride hydrolysis in highly concentrated solutions. The effects of initial NaBH₄ concentration, temperature and pH on conversion are studied. It is found that higher initial NaBH₄ concentration and higher temperature both improve the reaction rate. The reaction rate is slowed down with increasing pH of basic solutions and is accelerated with decreasing pH of acidic solutions. In addition, temperature effect seems to be more important than that of the acidic pH on the reaction rate.     

A 28-W portable direct borohydride–hydrogen peroxide fuel-cell stack

A 28-W direct borohydride–hydrogen peroxide fuel-cell stack operating at 25 °C is reported for contemporary portable applications. The fuel cell operates with the peak power-density of ca. 50 mW cm⁻² at 1 V. This performance is superior to the anticipated power-density of 9 mW cm⁻² for a methanol–hydrogen peroxide fuel cell. Taking the fuel efficiency of the sodium borohydride–hydrogen peroxide fuel cell as 24.5%, its specific energy is ca. 2 kWh kg⁻¹. High power-densities can be achieved in the sodium borohydride system because of its ability to provide a high concentration of reactants to the fuel cell.     

Ragone Plot Comparison of Radioisotope Cells and the Direct Sodium Borohydride/Hydrogen Peroxide Fuel Cell With Chemical Batteries

Radioisotope cells (RCs) and a direct sodium borohydride/hydrogen peroxide fuel cell ( FC) are compared to conventional chemical batteries through Ragone plots of theoretical (RCs) and experimental (chemical batteries and FC) data. It is found that the RCs are projected to have superior specific energy but inferior specific power, while the borohydride/peroxide FC shows an impressive range for both parameters. Thus, RCs may be especially useful in battery charging, communications, or other applications that require a long-lived, low-power source or periodic pulses of energy. While the borohydride/peroxide FC can be scaled to a variety of high-power applications, it is especially well suited for space and undersea use where air independence is essential.     

Response to Disselkamp: Direct peroxide/peroxide fuel cell as a novel type fuel cell

Besides hydrogen peroxide is known as conventionally oxidizer, it is both a fuel and a source of ignition. Platinum is not suitable catalyst for oxidation and reduction of hydrogen peroxide, because it directly converts the hydrogen peroxide to oxygen gas. In this study, the oxidation mechanism of peroxide is investigated and a fuel cell operating with acidic peroxide as oxidant and basic peroxide as fuel is constructed. The peroxide oxidation reaction in novel alkaline direct peroxide/peroxide fuel cell (DPPFC), shown feasible here using less expensive carbon supported Nickel catalyst, makes the alkaline direct peroxide/peroxide fuel cell a potentially low cost technology compared to PEM fuel cell technology, which employs platinum catalysts. The power density of 3.75 mW cm⁻² at a cell voltage of 0.55 V and a current density of 14 mA cm⁻² was achieved in our fuel cell.     

A composite of borohydride and super absorbent polymer for hydrogen generation

To develop a hydrogen source for underwater applications, a composite of sodium borohydride and super absorbent polymer (SAP) is prepared by ball milling sodium borohydride powder with SAP powder, and by dehydrating an alkaline borohydride gel. When sodium polyacrylate (NaPAA) is used as the SAP, the resulting composite exhibits a high rate of borohydride hydrolysis for hydrogen generation. A mechanism of hydrogen evolution from the NaBH₄-NaPAA composite is suggested based on structure analysis by X-ray diffraction and scanning electron microscopy. The effects of water and NiCl₂ content in the precursor solution on the hydrogen evolution behavior are investigated and discussed.     

A review: Hydrogen generation from borohydride hydrolysis reaction

In this review, a convenient hydrogen generation technology based on sodium borohydride and water as hydrogen carriers has been summarized. The recent progresses in the development of the hydrogen generation from sodium borohydride hydrolysis are reviewed. The NaBH₄ hydrolysis behavior is discussed in detail. From reported results, it is considered that hydrogen generation from sodium borohydride hydrolysis is a feasible technology to supply hydrogen for the PEMFC. It has been found that the reported results are encouraging although there are some engineering problems that lie ahead. The critical issues of this hydrogen generation technology have been highlighted and discussed.     

Indirect hydrolysis of sodium borohydride: Isolation and crystallographic characterization of methanolysis and hydrolysis by-products

The use of sodium borohydride as a means for hydrogen generation has focused on the base-stabilized hydrolysis reaction, while literature for the methanolysis of sodium borohydride remains scarce. Sodium borohydride methanolysis is an alternative for hydrogen production from sodium borohydride and has a number of advantages over hydrolysis reactions in terms of by-product handling. Previous studies have shown that the presence of water in methanol significantly retards the rate of hydrogen evolution from NaBH₄. This article reports the production of hydrogen from NaBH₄ using rigorously dried methanol. In addition, the solid-state structure of the methanolysis by-product is reported, which lends pertinent information for its hydrolysis for methanol recovery. Also reported is the solid-state structure of the hydrolysis by-product.     

Highly active porous Co–B nanoalloy synthesized on liquid-gas interface for hydrolysis of sodium borohydride

Porous Co–B nanoalloy is a low-cost and highly active catalyst towards the hydrolysis of sodium borohydride (NaBH₄). In this study, a facile and room-temperature hydrogen bubble-assisted method was developed to prepare porous Co–B nanoalloy (Co-B_bubble) materials exhibiting high catalytic activity. The obtained materials are characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma-optical emission spectrometer, transmission electron microscopy and surface area experiments. It is found that the hydrogen bubbles generated in-situ in the reaction system can act as template, which played an important role in determining the porous architecture of the final Co–B product. In the hydrolysis of sodium borohydride for hydrogen generation, the porous Co-B_bubble nanoalloy materials exhibit high catalytic activity with mass normalized rate constant of 5.31 L_hydrogen min^?1 g_catalyst^?1; a value which is much higher than those obtained for many other Co–B catalysts recently reported in the literature. The apparent activation energy (Ea) of the catalytic process is found to be ca. 30 kJ mol^?1. It is proposed that the high catalytic performance and low cost of Co-B_bubble nanoalloy catalyst can be a promising material candidate in the hydrolysis of sodium borohydride for hydrogen production for commercial applications.     

Hydrogen generation from sodium borohydride using microreactor for micro fuel cells

A microreactor for hydrogen generation from sodium borohydride was designed and fabricated in the present study. The microreactor has three photosensitive glasses, including the cover, the reactor layer and the base. A nickel form was inserted in the reactor layer as a catalyst support. A Co-P-B catalyst for sodium borohydride hydrolysis was coated on the nickel form by electroless plating. The characteristics of the catalyst were studied using SEM and EDS analysis. The hydrogen generation rate of the microreactor was measured under a variety of conditions and made up 15.6 ml/min at a temperature of 40 °C. The generated hydrogen was supplied to a micro fuel cell with a maximum power output of 157 mW at a current of 0.5 A.