All-in-one portable electric power plant using proton exchange membrane fuel cells for mobile applications

A portable electric power plant is developed using a NaBH₄ (sodium borohydride)-based proton exchange membrane fuel cell stack. The power plant consists of a NaBH₄-based hydrogen generator, a fuel cell stack, a DC-DC converter, a micro-processed controller and a data monitoring device. The hydrogen generator can produce 5.9 L/min pure hydrogen gas using catalytic hydrolysis of 20 wt% NaBH₄ to feed a 500-W scale fuel cell stack. Thus, the Co/γ-Al₂O₃ and Co-P/Ni foam catalysts in the hydrogen generator play significant roles in promoting hydrogen production rates that are as fast as necessary by enhancing the slow response that is intrinsic to using only Co-P/Ni foam catalysts. Moreover, different hydrogen production rates can easily be achieved during the operation by controlling NaBH₄ solution rates using a fuel pump so that the hydrogen storage efficiency can be improved by supplying required hydrogen gas in accordance with load demands. The specific energy density of the electric power plant was measured 211 Wh/kg. Therefore, the power plant described here can be a power source for mobile applications, such as cars and UAVs, as well as a stationary power supplier when electric energy is required.     

Hydrogen generation from solid NaBH4 with catalytic solution for planar air-breathing proton exchange membrane fuel cells

In the pursuit of the development of alternative mobile power sources with high energy densities, this study elucidated a new hydrogen generation approach from solid NaBH₄ using a new catalyst, sodium hydrogen carbonate (NaHCO₃), which was placed in a small and compact cartridge. A planar air-breathing PEMFC system fitted with the cartridge has been investigated for testing hydrogen generation from NaBH₄ and NaHCO₃. NaHCO₃ allowed the hydrogen cartridge to control hydrogen generation and to improve the power density, fuel efficiency, energy efficiency, and cell response. The cell performance of solid NaBH₄ air-breathing PEMFC system strongly depended on the operating conditions: the feeding rates and concentrations of catalytic solutions for NaBH₄ hydrolysis. In various concentrations (5 - 12 wt %) of NaHCO₃ aqueous solutions, 10 wt % NaHCO₃ aqueous solution exhibited the highest maximum power density of 128 mW cm⁻² at 0.7 V, which was estimated to be a Faradic efficiency of 78.4% and an energy efficiency of 46.3%. The data illustrated that NaHCO₃ was an effective catalyst for hydrogen generation with the solid NaBH₄, which is considered as a hydrogen carrier for air-breathing micro PEMFCs operated without auxiliary hydrogen controller or devices.     

Hydrogen generation from hydrolysis of concentrated NaBH4 solutions under adiabatic conditions

In this study, catalytic hydrolysis of aqueous solutions of NaBH₄ under isothermal and adiabatic conditions was investigated. A finely dispersed cobalt powder based on titanium oxide was used as a model catalyst. It was determined that catalytic activity of this catalyst practically did not change after 20 cycles. It was shown that the activation energy, determined by the rate of hydrogen generation, depends on NaBH₄ concentrations. We believe that this effect is associated with sorption/desorption processes. If to conduct hydrolysis under conditions close to adiabatic, the time of hydrolysis is significantly reduced. As united solution of equations of kinetics and energy conversation shows, the data of experiments in a thermally insulated reactor can be reasonably predicted.     

Enhanced hydrogen generation by hydrolysis of LiBH4 doped with multiwalled carbon nanotubes for micro proton exchange membrane fuel cell application

LiBH₄ has a high hydrogen storage capacity and could potentially serve as a superior hydrogen storage material. However, during the hydrolysis process for hydrogen generation, the agglomeration of the hydrolysis product of LiBH₄ limits its full utilization. In order to completely release the stoichiometric amount of H₂ from LiBH₄ hydrolysis, multiwalled carbon nanotubes (MWCNTs) were doped with LiBH₄ by mechanical milling. The results show that MWCNT carried LiBH₄ can slowly react with water vapor at room temperature which is 25 °C lower than the reaction temperature of neat LiBH₄. Agglomeration can be avoided when the addition of MWCNTs exceeds 7 wt.%, which results in a complete hydrolysis process. The total hydrogen capacity is 7.5 wt.%. The enhanced hydrolysis of LiBH₄ can be attributed to the MWCNTs which increased the contact areas between LiBH₄ and water and created gas channels for hydrogen diffusion. The performance of a micro proton exchange membrane fuel cell connected to MWCNT-doped LiBH₄ powder packed-bed reactor was examined. The result demonstrates that doping with MWCNTs enhanced the hydrogen generation of LiBH₄ hydrolysis. MWCNT-doped LiBH₄ can be applied as hydrogen source of fuel cells.     

Decentralized generation of electricity from biomass with proton exchange membrane fuel cell

Biomass can be applied as the primary source for the production of hydrogen in the future. The biomass is converted in an atmospheric fluidized bed gasification process using steam as the gasifying agent. The producer gas needs further cleaning and processing before the hydrogen can be converted in a fuel cell; it is assumed that the gas cleaning processes are able to meet the requirements for a PEM-FC. The compressed hydrogen is supplied to a hydrogen grid and can be used in small-scale decentralized CHP units. In this study it is assumed that the CHP units are based on low temperature PEM fuel cells. For the evaluation of alternative technologies the whole chain of centralized hydrogen production from biomass up to and including decentralized electricity production in PEM fuel cells is considered.Two models for the production of hydrogen from biomass and three models for the combined production of electricity and heat with PEM fuel cells are built using the computer program Cycle-Tempo. Two different levels of hydrogen purity are considered in this evaluation: 60% and 99.99% pure hydrogen. The purity of the hydrogen affects both the efficiencies of the hydrogen production as well as the PEM-FC systems. The electrical exergy efficiency of the PEM-FC system without additional heat production is calculated to be 27.66% in the case of 60% hydrogen and 29.06% in the case of 99.99% pure hydrogen. The electrical exergy efficiencies of the whole conversion chain appear to be 21.68% and 18.74%, respectively. The high losses during purification of the hydrogen gas result in a higher efficiency for the case with low purity hydrogen. The removal of the last impurities strongly increases the overall exergy losses of the conversion chain.     

Hydrogen generation from noncatalytic hydrolysis of LiBH4/NH3BH3 mixture for fuel cell applications

Ammonia borane (NH₃BH₃) and lithium borohydride (LiBH₄) are promising hydrides as they contain 19.6 wt.% and 18.5 wt.% hydrogen respectively. However, hydrolysis of NH₃BH₃ needs catalysts or high temperature to initiate the release of hydrogen. On the other hand, hydrolysis of LiBH₄ is incomplete, because the agglomeration of LiBH₄ and its products limits its full utilization. In the present work, hydrolysis performance of LiBH₄/NH₃BH₃ mixture was investigated. The results show that LiBH₄/NH₃BH₃ mixture can fully release its theoretical amount of hydrogen at room temperature without catalysts. In the presence of LiBH₄, NH₃BH₃ can be fully hydrolyzed at room temperature. In return, in the presence of NH₃BH₃, the agglomeration can be avoided resulting in a complete hydrolysis process. Our results indicate that the improvements are attributed to the intermolecular electron migration between LiBH₄ and NH₃BH₃, which changes the reactivity of these compounds. Hydrolytic heat of LiBH₄ also contributes to the promoted hydrolysis of NH₃BH₃. Our results present a novel strategy for noncatalytic hydrolysis of NH₃BH₃ and LiBH₄ for proton exchange membrane fuel cell 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.     

CeO2 supported multimetallic nano materials as an efficient catalyst for hydrogen generation from the hydrolysis of NaBH4

Nowadays, there is still no suitable method to store large amounts of energy. Hydrogen can be stored physically in carbon nanotubes or chemically in the form of hydride. In this study, sodium borohydride (NaBH₄) was used as the source of hydrogen. However, an inexpensive and useful catalyst (Co–Cr–B/CeO₂) was synthesized using the NaBH₄ reduction method and its property was characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), x-ray photoelectron spectroscopy (XPS) and Brunauer–Emmett–Teller (BET) measurements. The optimized Co–Cr–B/CeO₂ catalyst exhibited an excellent hydrogen generation rate (9182 mLg_metal⁻¹min⁻¹) and low activation energy (35.52 kJ mol⁻¹). The strong catalytic performance of the Co–Cr–B/CeO₂ catalyst is thought to be based on the synergistic effect between multimetallic nanoparticles and the effective charge transfer interactions between the metal and the support material.     

Simulation studies of the membrane exchange assembly of an all-liquid,proton exchange membrane fuel cell

A model has been designed and constructed for the all-liquid, sodium borohydride/hydrogen peroxide fuel cell under development at the University of Illinois at Urbana-Champaign. The electrochemical behavior, momentum balance, and mass balance effects within the fuel cell are modeled using the Butler–Volmer equations, Darcy's law, and Fick's law, respectively, within a finite element modeling platform. The simulations performed with the model indicate that an optimal physical design of the fuel cell's flow channel land area or current collector exists when considering the pressure differential between channels, and the diffusion layer permeability and conductivity. If properties of the diffusion layer are known, the model is an effective method of improving the fuel cell design in order to achieve higher power density.     

Kinetics of hydrolysis of sodium borohydride for hydrogen production in fuel cell applications: A review

Hydrogen generation from the hydrolysis of sodium borohydride (NaBH₄) solution has drawn much attention since early 2000s, due to its high theoretical hydrogen storage capacity (10.8 wt%) and potentially safe operation. However, hydrolysis of NaBH₄ for hydrogen generation is a complex process, which is influenced by factors such as catalyst performance, NaBH₄ concentration, stabilizer concentration, reaction temperature, complex kinetics and excess water requirement. All of these limit the hydrogen storage capacities of NaBH₄, whose practical application, however, has not yet reached a scientific and technical maturity. Despite extensive efforts, the kinetics of NaBH₄ hydrolysis reaction is not fully understood. Therefore, better understanding of the kinetics of hydrolysis reaction and development of a reliable kinetic model is a field of great importance in the study of NaBH₄ based hydrogen generation system. This review summarizes in detail the extensive literature on kinetics of hydrolysis of aqueous NaBH₄ solution.     

A mini-type hydrogen generator from aluminum for proton exchange membrane fuel cells

A safe and simple hydrogen generator, which produced hydrogen by chemical reaction of aluminum and sodium hydroxide solution, was proposed for proton exchange membrane fuel cells. The effects of concentration, dropping rate and initial temperature of sodium hydroxide solution on hydrogen generation rate were investigated. The results showed that about 38 ml min⁻¹ of hydrogen generation rate was obtained with 25 wt.% concentration and 0.01 ml s⁻¹ dropping rate of sodium hydroxide solution. The cell fueled by hydrogen from the generator exhibited performance improvement at low current densities, which was mainly due to the humidified hydrogen reduced the protonic resistivity of the proton exchange membrane. The hydrogen generator could stably operate a single cell under 500 mA for nearly 5 h with about 77% hydrogen utilization ratio.     

Transient model of oxygen-starved proton exchange membrane fuel cell for predicting voltages and hydrogen emissions

Transfer (crossover) leaks initiated by the chemical deterioration of the PEM and the resulting performance degradation has been previously identified as one the primary life-limiting factors in fuel cells. The leaks result in reduced oxygen levels in affected cells, where a secondary factor intimately related to this is high hydrogen emissions in the cathode exhaust when some cells operate in fully-oxygen-starved conditions. This paper builds on previous work that developed a unified fuel cell model that predicts cell voltage behavior under driving (normal) and driven (oxygen-starved) conditions, where this latest analysis now explicitly includes hydrogen pumping and emissions release when operating under oxygen-depleted conditions. In addition to considering diffusion effects and electrochemical effects, the model tracks the evolution of hydrogen in the cell cathode when no oxygen remains to generate water. The voltage response of the model under normal (non-starved) conditions is first validated for steady-state and transient (current step-change) conditions against previously published experiments, and then the model is used to simulate the cell voltage and stack hydrogen emissions behavior measured from three different commercially available fuel cell stacks. In the first fuel cell stack, a 9-cell commercial short stack, only one cell was fully oxygen-starved. Excellent agreement is seen between the measured and simulated hydrogen release concentrations (where air injection was used downstream of the stack to ensure adequate oxygen levels for measurement with a catalytic hydrogen sensor and to condense water vapor in the exhaust), where the role of hydrogen pumping is seen to contribute significantly to the release behavior. The first fuel cell stack is then used transiently in comparison with testing performed where the hydrogen injection level in the cell is changed quickly, where the model gives good agreement with the measured emission response and cell voltage behavior. Further comparisons with test data from a second and third 10-cell commercial short stack models operated with stack inlet hydrogen injection show good agreement with measured emissions onset versus current, where the observed threshold of starvation and emissions occurs a few percent sooner in the third model than the simulation, but the overall behavior is well predicted.     

Hydrogen generation system using sodium borohydride for operation of a 400 W-scale polymer electrolyte fuel cell stack

Sodium borohydride (NaBH₄) in the presence of sodium hydroxide as a stabilizer is a hydrogen generation source with high hydrogen storage efficiency and stability. It generates hydrogen by self-hydrolysis in aqueous solution. In this work, a Co–B catalyst is prepared on a porous nickel foam support and a system is assembled that can uniformly supply hydrogen at >6.5 L min⁻¹ for 120 min for driving 400-W polymer electrolyte membrane fuel cells (PEMFCs). For optimization of the system, several experimental conditions were changed and their effect investigated. If the concentration of NaBH₄ in aqueous solution is increased, the hydrogen generation rate increases, but a high concentration of NaBH₄ causes the hydrogen generation rate to decrease because of increased solution viscosity. The hydrogen generation rate is also enhanced when the flow rate of the solution is increased. An integrated system is used to supply hydrogen to a PEMFCs stack, and about 465 W power is produced at a constant loading of 30 A.     

Enhancement of efficiency and power output of hydrogen fuelled proton exchange membrane (PEM) fuel cell using oxygen enriched air

This paper deals with the effects of the oxygen-enriched air (up to 50% oxygen by mass) along with other operating parameters (hydrogen flow rate, temperature, and relative humidity) on the performance of hydrogen-fuelled proton exchange membrane (PEM) fuel cell. The active area of a fuel cell considered was 50 cm² with three cells in series connections. The air was supplied with O₂ enriched from 23% to 50% at the cathode. The voltage obtained with the respective enriched air was 2.52 and 2.80 V respectively. The optimum oxygen enrichment was found as 45%. The stack temperature plays a significant role on performance improvement and the optimum temperature was found as 50 °C. The voltage efficiency and power output were improved by 9% and 33% with 45% oxygen-enriched air. Electrochemical impedance spectroscopy was used to analyze the impedance behavior of the fuel cell with the variable current demand. The bode plot indicates current dominates voltage at low oxygen-enriched air (25%) and vice-versa at high-enriched air. The inductive effect was dominating at the low frequency and overtaken by the capacitive effects at the higher frequency. These results would be useful to develop a dedicated fuel cell with the oxygen-enriched air.     

Performance prediction of proton exchange membrane fuel cells using a three-dimensional model

In this study a steady-state three-dimensional computational fluid dynamics (CFD) model of a proton exchange membrane fuel cell is developed and presented for a single cell. A complete set of conservation equations of mass, momentum, species, energy transport, and charge is considered with proper account of electrochemical kinetics based on Butler–Volmer equation. The catalyst layer structure is considered to be agglomerate. This model enables us to investigate the flow field, current distribution, and cell voltage over the fuel cell which includes the anode and cathode collector plates, gas channels, catalyst layers, gas diffusion layers, and the membrane. The numerical solution is based on a finite-volume method in a single solution domain. In this investigation a CFD code was used as the core solver for the transport equations, while mathematical models for the main physical and electrochemical phenomena were devised into the solver using user-developed subroutines. Three-dimensional results of the flow structure, species concentrations and current distribution are presented for bipolar plates with square cross section of straight flow channels. A polarization curve is obtained for the fuel cell under consideration. A comparison between the polarization curves obtained from the current study and the corresponding available experimental data is presented and a reasonable agreement is obtained. Such CFD model can be used as a tool in the development and optimization of PEM fuel cells.     

Hydrogen generation from sodium borohydride hydrolysis by multi-walled carbon nanotube supported platinum catalyst: A kinetic study

In this study, it is aimed to investigate hydrogen (H₂) generation from sodium borohydride (NaBH₄) hydrolysis by multi-walled carbon nanotube supported platinum catalyst (Pt/MWCNT) under various conditions (0–0.03 g Pt amount catalyst, 2.58–5.03 wt % NaBH₄, and 27–67 °C) in detail. For comparison, carbon supported platinum (Pt/C) commercial catalyst was used for H₂ generation experiments under the same conditions. The reaction rate of the experiments was described by a power law model which depends on the temperature of the reaction and concentrations of NaBH₄. Kinetic studies of both Pt/MWCNT and Pt/C catalysts were done and activation energies, which is the required minimum energy to overcome the energy barrier, were found as 27 kJ/mol and 36 kJ/mol, respectively. Pt/MWCNT catalyst is accelerated the reaction less than Pt/C catalyst while Pt/MWCNT is more efficient than Pt/C catalyst, they are approximately 98% and 95%, respectively. According to the results of experiments and the kinetic study, the reaction system based on NaBH₄ in the presence of Pt/MWCNT catalyst can be a potential hydrogen generation system for portable applications of proton exchange membrane fuel cell (PEMFC).     

Design of an optical thermal sensor for proton exchange membrane fuel cell temperature measurement using phosphor thermometry

Internal temperatures in a proton exchange membrane (PEM) fuel cell govern the ionic conductivities of the polymer electrolyte, influence the reaction rate at the electrodes, and control the water vapor pressure inside the cell. It is vital to fully understand thermal behavior in a PEM fuel cell if performance and durability are to be optimized. The objective of this research was to design, construct, and implement thermal sensors based on the principles of the lifetime-decay method of phosphor thermometry to measure temperatures inside a PEM fuel cell. Five sensors were designed and calibrated with a maximum uncertainty of ±0.6 °C. Using these sensors, surface temperatures were measured on the cathode gas diffusion layer of a 25 cm² PEM fuel cell. The test results demonstrate the utility of the optical temperature sensor design and provide insight into the thermal behavior found in a PEM fuel cell.     

Hydrogen utilization enhancement of proton exchange membrane fuel cell with anode recirculation system through a purge strategy

Proton exchange membrane (PEM) fuel cells are widely considered as potential alternative energy candidates for internal combustion engines because of their low-temperature start, high energy density, and ease of scale up. However, their low hydrogen utilization rate is one of the main reasons for the limited commercial development. This study focuses on improving the hydrogen utilization rate of PEM fuel cells and system efficiency using optimal active recirculation system (ARS). An anode ARS and purging strategy are introduced to enhance the hydrogen utilization rate of PEM fuel cells. An ARS simulation model with purge strategy model is developed in a MATLAB/Simulink environment. A control-oriented dynamic model is developed to study the hydrogen recirculation system characteristics. The dynamic model is used as basis to propose a proportional integration differentiation controller to maintain the anode hydrogen concentration and increase the hydrogen utilization rate. Several experiments are performed using different purging strategies in conjunction with ARS. The hydrogen utilization rate is the highest when the purge time is 0.3 s and the purge period is 10 s. Simulation results show that the PEM fuel cells with an anode recirculation configuration exhibit a better performance than other configurations in terms of hydrogen utilization. Experimental results also demonstrate the feasibility of the proposed system, the performance of which is also superior to that of other hydrogen supply system.