Experimental study of metal hydride-based hydrogen storage tank at constant supply pressure

Metal hydride-based hydrogen storage tank is tested using 1 kg of AB₅ alloy, namely LaNi₅. The hydrogen tank is of annular cylindrical with inner and outer heat exchangers. The inner one is a finned spiral heat exchanger and the outer one is a conventional jacket. Performance (storage capacity and storage time) studies are carried out by varying the supply pressure and the cooling temperature of the hydride bed. At any given cooling temperature, hydrogen storage rate is found to increase with supply pressure. Cooling temperature is found to have a significant effect on hydrogen storage capacity at lower supply pressures.     

Energy management of a thermally coupled fuel cell system and metal hydride tank

Being produced from renewable energy, hydrogen is one of the most efficient energy carriers of the future. Using metal alloys, hydrogen can be stored and transported at a low cost, in a safe and effective manner. However, most metals react with hydrogen to form a compound called metal hydride (MH). This reaction is an exothermic process, and as a result releases heat. With sufficient heat supply, hydrogen can be released from the as-formed metal hydride. In this work, we propose an integrated power system of a proton exchange membrane fuel cell (PEMFC) together with a hydride tank designed for vehicle use. We investigate different aspects for developing metal hydride tanks and their integration in the PEMFC, using water as the thermal fluid and a FeTi intermetallic compound as the hydrogen storage material. Ground truth simulations show that the annular metal hydride tank meets the hydrogen requirements of the fuel cell, but to the detriment of the operating temperature of the fuel cell (FC).     

Enhancement of hydrogen storage performance in shell and tube metal hydride tank for fuel cell electric forklift

Novel metal hydride (MH) hydrogen storage tanks for fuel cell electric forklifts have been presented in this paper. The tanks comprise a shell side equipped with 6 baffles and a tube side filled with 120 kg AB₅ alloy and 10 copper fins. The alloy manufactured by vacuum induction melting has good hydrogen storage performance, with high storage capacity of 1.6 wt% and low equilibrium pressure of 4 MPa at ambient temperature. Two types of copper fins, including disk fins and corrugated fins, and three kinds of baffles, including segmental baffles, diagonal baffles and hole baffles, were applied to enhance the heat transfer in metal hydride tanks. We used the finite element method to simulate the hydrogen refueling process in MH tanks. It was found that the optimized tank with corrugated fins only took 630 s to reach 1.5 wt% saturation level. The intensification on the tube side of tanks is an effective method to improve hydrogen storage performance. Moreover, the shell side flow field and hydrogen refueling time in MH tanks with different baffles were compared, and the simulated refueling time is in good agreement with the experimental data. The metal hydride tank with diagonal baffles shows the shortest hydrogen refueling time because of the highest velocity of cooling water. Finally, correlations regarding the effect of cooling water flow rate on the refueling time in metal hydride tanks were proposed for future industrial design.     

Refuelling scenarios of a light urban fuel cell vehicle with metal hydride hydrogen storage. Comparison with compressed hydrogen storage counterpart

The high price of hydrogen fuel in the fuel cell vehicle refuelling market is highly dependent on the one hand from the production costs of hydrogen and on the other from the capital cost of a hydrogen refuelling station's components to support a safe and adequate refuelling process of contemporary fuel cell vehicles. The hydrogen storage technology dominated in the vehicle sector is currently based on high-pressure compressed hydrogen tanks to extend as much as possible the driving range of the vehicles. However, this technology mandates the use of large hydrogen compression and cooling systems as part of the refuelling infrastructure that consequently increase the final cost of the fuel. This study investigated the prospects of lowering the refuelling cost of small urban hydrogen vehicles through the utilisation of metal hydride hydrogen storage. The results showed that for low compression hydrogen storage, metal hydride storage is in favour in terms of the dispensed hydrogen fuel price, while its weight is highly comparable to the one of a compressed hydrogen tank. The final refuelling cost from the consumer's perspective however was found to be higher than the compressed gas due to the increased hydrogen quantity required to be stored in fully empty metal hydride tanks to meet the same demand.     

Accurate simplified dynamic model of a metal hydride tank

As proton exchange membrane fuel cell technology advances, the need for hydrogen storage intensifies. Metal hydride alloys offer one potential solution. However, for metal hydride tanks to become a viable hydrogen storage option, the dynamic performance of practical tank geometries and configurations must be understood and incorporated into fuel cell system analyses. A dynamic, axially-symmetric, multi-nodal metal hydride tank model has been created in Matlab–Simulink^® as an initial means of providing insight and analysis capabilities for the dynamic performance of commercially available metal hydride systems. Following the original work of Mayer et al. [Mayer U, Groll M, Supper W. Heat and mass transfer in metal hydride reaction beds: experimental and theoretical results. Journal of the Less-Common Metals 1987;131:235–44], this model employs first principles heat transfer and fluid flow mechanisms together with empirically derived reaction kinetics. Energy and mass balances are solved in cylindrical polar coordinates for a cylindrically shaped tank. The model tank temperature, heat release, and storage volume have been correlated to an actual metal hydride tank for static and transient absorption and desorption processes. A sensitivity analysis of the model was accomplished to identify governing physics and to identify techniques to lessen the computational burden for ease of use in a larger system model. The sensitivity analysis reveals the basis and justification for model simplifications that are selected. Results show that the detailed and simplified models both well predict observed stand-alone metal hydride tank dynamics, and an example of a reversible fuel cell system model incorporating each tank demonstrates the need for model simplification.     

Bounding material properties for automotive storage of hydrogen in metal hydrides for low-temperature fuel cells

Metal hydride material properties required for on-board hydrogen storage for use with automotive polymer electrolyte fuel cell systems are discussed. Thermodynamic relationships between enthalpy and entropy of sorption are determined such that the storage system can be thermally integrated with the fuel cell system and be refueled at reasonable H₂ supply pressures of 50–200 atm. Simple criteria are developed for specifying minimum discharge kinetic rates needed to satisfy hydrogen demand on automotive duty cycles. Simple criteria are also developed for specifying minimum charge kinetic rates needed to refuel metal hydride tanks in reasonable time. Accessible intrinsic capacity and bulk density of the metal hydride are determined for the storage system to achieve system level targets for gravimetric and volumetric capacities. Based on these analyses, it is recommended that the storage media properties be measured on samples prepared by mixing the metal hydride with a high thermal conductivity material, and compacted to 600 kg m⁻³ bulk density. The compact should have a minimum effective thermal conductivity of 8.5 W m⁻¹ K⁻¹.     

Hydrogen storage properties of TiMn1.5V0.2-based alloys for application to fuel cell system

To meet the requirements of fuel cell power system for electric bike, the influence of partial substitution of Zr and Cr on hydrogen storage performance of TiMn_1.5V_0.2-based alloys is investigated first, and a hydrogen storage tank is then built using the developed TiMn_1.5V_0.2-based alloy as metal hydride bed and its hydrogen supply ability is further evaluated. It is found that for TiMn_1.5V_0.2-based alloys, the Zr substitution for Ti effectively reduces the plateau pressure but increases the plateau slope, while the partial substitution of Mn by Cr decreases the absorption plateau pressure, leading to a smaller hysteresis factor. After the optimization of components, 6 kg of Ti_0.95Zr_0.05Mn_1.4Cr_0.1V_0.2 alloy powder with 5 wt.% aluminum foam is mixed uniformly to form a metal hydride bed inside the tank. The measurements show that the tank releases up to 82 g of hydrogen to produce a 200 W fuel cell output for 300 min and has a stable cyclic capacity, indicating that hydrogen storage system of TiMn_1.5V_0.2-based alloys for fuel cell power system of electric bike is applicable.     

Heat and mass transfer studies on metal-hydrogen reactor filled with MmNi4.6Fe0.4

A transient, three-dimensional computational investigation of coupled heat and mass transfer in an annular cylindrical hydrogen storage tank, equipped with fins and filled with MmNi_4.6Fe_0.4, is presented. The effects of different parameters such as length, thickness and thermal conductivity of fins and overall heat transfer coefficient on the hydrogen storage performance of the tank are studied. The predicted hydrogen storage capacity at different supply pressures showed good agreement with the experimental data reported in the literature. In addition, it is observed that the use of fins enhances heat transfer within the hydride bed and consequently 40% improvement of the time required for 90% storage can be achieved over the case without fins.     

Dynamic modeling and simulation of hydrogen supply capacity from a metal hydride tank

The current study presents a modeling of a LaNi₅ metal hydride-based hydrogen storage tank to simulate and control the dynamic processes of hydrogen discharge from a metal hydride tank in various operating conditions. The metal hydride takes a partial volume in the tank and, therefore, hydrogen discharge through the exit of the tank was driven by two factors; one factor is compressibility of pressurized gaseous hydrogen in the tank, i.e. the pressure difference between the interior and the exit of the tank makes hydrogen released. The other factor is desorption of hydrogen from the metal hydride, which is subsequently released through the tank exit. The duration of a supposed full load supply is evaluated, which depends on the initial tank pressure, the circulation water temperature, and the metal hydride volume fraction in the tank. In the high pressure regime, the duration of full load supply is increased with increasing circulation water temperature while, in the low pressure regime where the initial amount of hydrogen absorbed in the metal hydride varies sensitively with the metal hydride temperature, the duration of full load supply is increased and then decreased with increasing circulation water temperature. PID control logic was implemented in the hydrogen supply system to simulate a representative scenario of hydrogen consumption demand for a fuel cell system. The demanded hydrogen consumption rate was controlled adequately by manipulating the discharge valve of the tank at a circulation water temperature not less than a certain limit, which is increased with an increase in the tank exit pressure.     

Numerical simulation of the hydrogen storage with reaction heat recovery using metal hydride in the totalized hydrogen energy utilization system

Numerical simulation of a hydrogen storage tank of a Totalized Hydrogen Energy Utilization System (THEUS) for application to commercial buildings was done to verify the practicality of THEUS. THEUS consists of a fuel cell, water electrolyzer, hydrogen storage tank and their auxiliary machinery. The hydrogen storage tanks with metal hydrides for load leveling have been previously experimentally investigated as an important element of THEUS. A hydrogen storage tank with 50 kg AB5 type metal hydride was assembled to investigate the hydrogen-absorbing/desorbing process, which is exothermic/endothermic process. The goal of this tank is to recover the cold heat of the endothermic process for air conditioning, and thus improve the efficiency of THEUS. To verify the practical effectiveness of this improved system, we developed a numerical simulation code of hydrogen storage tank with metal hydride. The code was validated by comparing its results with experimental results. In this code the specific heat value of the upper and lower flanges of the hydrogen storage tank was adjusted to be equal to the thermal capacity of the entire tank. The simulation results reproduce well the experimental results.     

Modeling and optimization of multi-tubular metal hydride beds for efficient hydrogen storage

This work presents a novel systematic approach for the optimal design of a multi-tubular metal hydride tank, containing up to nine tubular metal hydride reactors, used for hydrogen storage. The tank is designed to store enough amount of hydrogen for 25 km range¹, for a fuel cell vehicle. A detailed 3D Cartesian, mathematical model is developed and validated against a 2D cylindrical developed by Kikkinides et al. [1]. The objective is to find the optimal process design so as to increase the overall thermal efficiency, and thus minimize the storage time. Optimization results indicate that almost 90% improvement of the storage time can be achieved, over the case where the tank is not optimized and for a minimum storage capacity of 99% of the maximum value.     

Experiments on solid state hydrogen storage device with a finned tube heat exchanger

The absorption and desorption performances of a solid state (metal hydride) hydrogen storage device with a finned tube heat exchanger are experimentally investigated. The heat exchanger design consists of two “U” shaped cooling tubes and perforated annular copper fins. Copper flakes are also inserted in between the fins to increase the overall effective thermal conductivity of the metal hydride bed. Experiments are performed on the storage device containing 1 kg of hydriding alloy LaNi₅, at various hydrogen supply pressures. Water is used as the heat transfer fluid. The performance of the storage device is investigated for different operating parameters such as hydrogen supply pressure, cooling fluid temperature and heating fluid temperature. The shortest charging time found is 490 s for the absorption capacity of 1.2 wt% at a supply pressure of 15 bar and cooling fluid temperature and velocity of 288 K and 1 m/s respectively. The effect of copper flakes on absorption performance is also investigated and compared with a similar storage device without copper flakes.     

Enhancement of hydrogen charging in metal hydride-based storage systems using heat pipe

Heat transfer in metal hydride bed significantly affects the performance of metal hydride reactors (MHRs). Enhancing heat transfer within the reaction bed improves the hydriding rate. This study presents performance analysis in terms of storage capacity and time of three different cylindrical MHR configurations using storage media LaNi₅: a) reactor cooled with natural convection, b) reactor with a heat pipe on the central axis, c) reactor with finned heat pipe. This study shows the impact of using heat pipes and fins for enhancing heat transfer in MHRs at varying hydrogen supply pressures (2–15 bar). At any absorption temperature, hydrogen absorption rate and hydrogen storage capacity increase with the supply pressure. Results show that using a heat pipe improves hydrogen absorption rate. It was found that finned heat pipe has a significant effect on the hydrogen charge time, which reduced by approximately 75% at 10 bar hydrogen supply pressure.     

Study on absorption/desorption characteristics of a metal hydride tank for boil-off gas from liquid hydrogen

We have been performing research on the Totalized Hydrogen Energy Utilization System (THEUS) which has applications to commercial buildings and a planned added function of supplying energy to stations for hydrogen and electric vehicles. In that case we will utilize liquid hydrogen transported from a hydrogen station and all Boil-Off Gas (BOG) will be recovered in THEUS’s metal hydride tanks. It is known that BOG is chiefly composed of para-hydrogen, which has different thermo-physical properties from normal hydrogen. It has been reported that some metal hydride alloys work as a catalyst to accelerate the para-ortho conversion and the conversion proceeds relatively fast in the case of La–Ni₅. The conversion is considered to be an endothermic reaction. A misch metal (Mm)-Ni₅ metal hydride alloy, which contained La and Ni, was used in our THEUS metal hydride tank. To examine the effect of the para-ortho conversion on the THEUS operation, we investigated the absorption/desorption characteristics of the metal hydride tank with BOG. We confirmed that the effect of the heat of conversion was very small and BOG could be treated as normal hydrogen for practical application.     

Using metal hydride H2 storage in mobile fuel cell equipment: Design and predicted performance of a metal hydride fuel cell mobile light

This study examines the practical prospects and benefits for using interstitial metal hydride hydrogen storage in “unsupported” fuel cell mobile construction equipment and aviation GSE applications. An engineering design and performance study is reported of a fuel cell mobile light tower that incorporates a 5 kW Altergy Systems fuel cell, Grote Trilliant LED lighting and storage of hydrogen in the Ovonic interstitial metal hydride alloy OV679. The metal hydride hydrogen light tower (mhH₂LT) system is compared directly to its analog employing high-pressure hydrogen storage (H₂LT) and to a comparable diesel-fueled light tower with regard to size, performance, delivered energy density and emissions. Our analysis indicates that the 5 kW proton-exchange-membrane (PEM) fuel cell provides sufficient waste heat to supply the desorption enthalpy needed for the hydride material to release the required hydrogen. Hydrogen refueling of the mhH₂LT is possible even without external sources of cooling water by making use of thermal management hardware already installed on the PEM fuel cell. In such “unsupported” cases, refueling times of ∼3–8 h can be achieved, depending on the temperature of the ambient air. Shorter refueling times (∼20 min) are possible if an external source of chilled water is available for metal hydride bed cooling during rapid hydrogen refueling. Overall, the analysis shows that it is technically feasible and in some aspects beneficial to use metal hydride hydrogen storage in portable fuel cell mobile lighting equipment deployed in remote areas. The cost of the metal hydride storage technology needs to be reduced if it is to be commercially viable in the replacement of common construction equipment or mobile generators with fuel cells.     

Refueling-station costs for metal hydride storage tanks on board hydrogen fuel cell vehicles

Refueling costs account for much of the fuel cost for light-duty hydrogen fuel-cell electric vehicles. We estimate cost savings for hydrogen dispensing if metal hydride (MH) storage tanks are used on board instead of 700-bar tanks. We consider a low-temperature, low-enthalpy scenario and a high-temperature, high-enthalpy scenario to bracket the design space. The refueling costs are insensitive to most uncertainties. Uncertainties associated with the cooling duty, coolant pump pressure, heat exchanger (HX) fan, and HX operating time have little effect on cost. The largest sensitivities are to tank pressure and station labor. The cost of a full-service attendant, if the refueling interconnect were to prevent self-service, is the single largest cost uncertainty. MH scenarios achieve $0.71–$0.75/kg-H₂ savings by reducing compressor costs without incurring the cryogenics costs associated with cold-storage alternatives. Practical refueling station considerations are likely to affect the choice of the MH and tank design.     

New dynamic modeling of a real embedded metal hydride hydrogen storage system

In this work, the dynamic responses of the on board hydrogen storage system with commercially available metal hydride tanks are investigated based on the database collected from fuel cell electric vehicles operation experiments. A mathematical model considering the heat transfer measured by the temperature control system is developed to analyze the absorption and desorption reaction during operation. As a seal container filled with unknown metal hydride, the practical used hydrogen storage tank is a gray box in the embedded storage system. Without the information about characteristics of material, current operation state and degradation degree, the parameters of the model are uncertain. Particle swarm optimization (PSO) algorithm is applied to search for the optimal parameter set. The simulation results of the hydrogen storage system model using these parameters show great agreements with the real operating data under different temperature conditions; the maximal error is lower than 9%.     

Numerical simulation of heat and mass transfer in metal hydride hydrogen storage tanks for fuel cell vehicles

This paper presents a two-dimensional mathematical model to optimized heat and mass transfer in metal hydride storage tanks (hereinafter MHSTs) for fuel cell vehicles, equipped with finned spiral tube heat exchangers. This model which considers complex heat and mass transfer was numerically solved and validated by comparison with experimental data and a good agreement is obtained.     

Structural analysis of metal hydride-based hybrid hydrogen storage systems

Hybrid hydrogen storage systems, which see the adoption of metal hydride materials charged at high pressure, can be a viable method to reach good gravimetric and volumetric capacities under selected conditions, since hydrogen is stored both as element bound to the hydride and as high pressure gas. A general structural model, which can simulate high pressure hybrid storage tanks, has been developed, with the aim of describing the performance of the system under various operating conditions. A baseline case has been simulated, comparing tanks composed of SS316 and IM6 graphite fiber reinforced epoxy composite that contain metal hydride materials that can store weight fractions of bound hydrogen ranging from 2% to 8%. Sensitivity analyses were performed for the baseline studies with the aim of determining the operating conditions that maximize gravimetric and volumetric capacities. Results show that high pressure systems are optimal (in terms of gravimetric and volumetric capacity) for tank materials having low density and a high allowable stress, while a low operating pressure is preferable for high density tank materials, especially when coupled with metal hydrides capable of storing a high weight fraction of bound hydrogen.     

Novel hydrogen generator/storage based on metal hydrides

A novel electrochemical system has been developed which integrates hydrogen production, storage and compression in only one device, at relatively low cost and higher efficiency than a classical electrolyser. 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 LaNi₄.₃Co_0.4Al₀.₃ have 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 Sievert-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. 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.