A comparative study of “in-out” and “out-in” hydrogen reaction alternatives for metal hydride beds using RET 1 computer code

The paper presents the results of a comparative study of two alternatives for progress for hydrogen reaction in metal hydride hydrogen storage beds; namely “In-Out” and “Out-In” through the application of a space-time dependent computer code “RET 1” for the solution of the associated mass and heat transfer problem. The reference model for the metal hydride storage bed is considered of cylindrical shape and composed of a multiple of a cylindrical cell, that either consists of a coaxial fluid tube surrounded by the granular iron-titanium metal hydride; called “In-Out” cell; or consists of a coaxial rod of the granular iron-titanium metal hydride surrounded by an annular fluid tube; called “Out-In” cell. The results of the study lead to the conclusion that for the same operating and physical conditions, the rate of hydrogen reaction in the “Out-In” cell is many times higher than that in the “In-Out” one.     

On the optimization of hydrogen storage in metal hydride beds

This work presents a novel systematic approach for the optimal design and control of metal hydride beds used for hydrogen storage. A detailed 2-D mathematical model is developed and validated against experimental and theoretical literature results. Based on recent advances in dynamic optimization, the objective is then to find the optimal process design (e.g. cooling systems design) and operating strategy (e.g. cooling fluid profile over time, hydrogen charging profile, etc.) so as to minimize the storing time, while satisfying, a number of operating constraints. Such constraints account for pressure drop limitations, cooling fluid availability and maximum tank temperature. Optimization results indicate that almost 60% improvement of the storage time can be achieved, over the case where the system is not optimized, for a minimum storage capacity of 99% of the total bed capacity. Trade-offs between various objectives, alternative design options and optimal cooling control policies are systematically revealed illustrating the potential offered by modern optimization techniques.     

Three-dimensional modeling of hydrogen sorption in metal hydride hydrogen storage beds

This paper conducts a three-dimensional (3D) modeling study to investigate the hydrogen absorption process and associated mass and heat transport in a metal hydride (LaNi₅) hydrogen storage tank. The 3D model is further implemented numerically for validation purpose and the detailed investigation on absorption process. Results indicate that at the very initial absorption stage the bed temperature evolves almost uniformly, while it varies greatly spatially at the latter stage. At the initial seconds, most hydrogen is absorbed in the region near the cooling wall due to the better heat removal. The absorption in the core is slow at the beginning, but becomes important at the very end stage. It also shows that the initial hydrogen flow in the bed is several-fold larger than the latter stage and the flow may provide extra cooling to the hydriding process. By analyzing the Peclet number, we find that the heat convection by the hydrogen flow may play an important role in local heat transfer. This work provides an important platform beneficial to the fundamental understanding of multi-physics coupling phenomena during hydrogen absorption and the development of on-board hydrogen storage technology.     

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.     

Dynamic modelling and optimization of hydrogen storage in metal hydride beds

This work presents a systematic approach for modelling, optimization and control of metal hydride beds used for hydrogen storage. A detailed 2-D mathematical model is developed and validated against experimental and theoretical literature results. Based on recent advances in dynamic optimization, the objective is then to find the optimal process design (e.g. cooling systems design) and operating strategy (e.g. cooling fluid profile over time) so as to minimize the storing time, while satisfying a number of operating constraints. Such constraints account for pressure drop limitations, cooling fluid availability, maximum tank temperature, etc. Optimization results indicate that almost 60% improvement of the storage time can be achieved, over the case where the system is not optimized, for a minimum storage capacity of 99% of the total bed capacity. Trade-offs between various objectives, alternative design options and optimal cooling control policies are systematically revealed illustrating the potential offered by modern optimization techniques.     

Analysis of a metal hydride reactor for hydrogen storage

In this paper a two-dimensional model of an annular cylindrical reactor filled with metal hydride suitable for hydrogen storage is presented. Comparison of the computed bed temperatures with published experimental data shows a reasonably good agreement except for the initial period. Effects of hydrogen pressure and external fluid temperatures on heat transfer and entropy generation are obtained. Results show that the time required for hydrogen charging and discharging is higher when the thermal capacity of the reactor wall is considered. The time required for absorption and desorption can be reduced significantly by varying the hydrogen gas pressure and external fluid temperatures. However, along with reduction in time the entropy generated during hydrogen storage and discharge increases significantly. Results also show that for the given input conditions, heat transfer between the external fluid and hydride bed is the main source of entropy generation.     

Active cooling of a metal hydride system for hydrogen storage

Reversible high-pressure metal hydrides offer excellent cold start capability and potentially increased hydrogen storage capacity. However, efficient thermal management is a critical issue in this kind of systems. In the present work, hydriding and dehydriding tests have been conducted with 100 g of Ti_1.1MnCr metal hydride at pressures up to 330 bar. Thermal characteristics of the Ti_1.1MnCr system have been quantified from the experimental data and simulated using a basic numerical model. By varying the coolant flow rates, a hydrogen filling time of 12 min has been achieved.     

Optimum output temperature setting and an improved bed structure of metal hydride hydrogen storage reactor for thermal energy storage

As the well-known solid hydrogen storage materials, metal hydrides (MHs) have been developed systematically for decades. During recent years, due to the development of thermal energy storage (TES) market, they have also received much attention gradually as the excellent TES materials because of the high energy density, low cost, and good reversibility. In this study, the stabilized discharging performance of an MH reactor for TES was investigated by numerical simulation. A mathematical model combining multi-physics and proportional-integral controller was established. Based on finite-time thermodynamics, gravimetric exergy-output rate (GEOR) considering the control requirement, finite-material, and finite-time constraints was defined. For a given reactor, the output temperature setting could be optimized based on GEOR. Besides, the effects of the reactor parameters on the optimum output temperature setting were systematically studied. The heat transfer analysis indicated the occurrence of the axial non-uniform reaction in the bed due to the inherent increase in the temperature of heat transfer fluid, resulting in the decrease of both GEOR and material availability. Accordingly, a new tapered bed structure (L/D_o = 600/50 mm) was proposed to effectively improve the discharging efficiency from 76 to 90% and GEOR from 65 to 120 W kg⁻¹, which provides a helpful guidance for the advanced designing and construction of MH reactor for the practical TES applications.     

Development of a hydrogen catalytic heater for heating metal hydride hydrogen storage systems

This paper describes the design, fabrication and performance evaluation of a high efficiency, compact heater that uses the catalytic oxidation of hydrogen to provide heat to a hydrogen storage system. The heater was designed to transfer up to 30 kW of heat from the catalytic reaction to the hydrogen storage system via a recirculating heat transfer fluid.     

Three-dimensional modeling and simulation of hydrogen absorption in metal hydride hydrogen storage vessels

In this paper, a three-dimensional hydrogen absorption model is developed to precisely study the hydrogen absorption reaction and resultant heat and mass transport phenomena in metal hydride hydrogen storage vessels. The 3D model is first experimentally validated against the temperature evolution data available in the literature. In addition to model validation, the detailed 3D simulation results show that at the initial absorption stage, the vessel temperature and H/M ratio distributions are uniform throughout the entire vessel, indicating that hydrogen absorption is very efficient early during the hydriding process; thus, the local cooling effect is not influential. On the other hand, non-uniform distributions are predicted at the subsequent absorption stage, which is mainly due to differential degrees of cooling between the vessel wall and core regions. In addition, a parametric study is carried out for various designs and hydrogen feed pressures. This numerical study provides a fundamental understanding of the detailed heat and mass transfer phenomena during the hydrogen absorption process and further indicates that efficient design of the storage vessel and cooling system is critical to achieve rapid hydrogen charging performance.     

Excellent catalytic effect of LaNi5 on hydrogen storage properties for aluminium hydride at mild temperature

The catalytic effect of rare-earth hydrogen storage alloy is investigated for dehydrogenation of alane, which shows a significantly reduced onset dehydrogenation temperature (86 °C) with a high-purity hydrogen storage capacity of 8.6 wt% and an improved dehydrogenation kinetics property (6.3 wt% of dehydrogenation at 100 °C within 60 min). The related mechanism is that the catalytic sites on the surface of the hydrogen storage alloy and the hydrogen storage sites of the entire bulk phase of the hydrogen storage reduce the dehydrogenation temperature of AlH₃ and improve the dehydrogenation kinetic performance of AlH₃. This facile and effective method significantly improves the dehydrogenation of AlH₃ and provides a promising strategy for metal hydride modification.     

Recyclable hydrogen storage system composed of ammonia and alkali metal hydride

Ammonia (NH₃) reacts with alkali metal hydrides MH (M = Li, Na, and K) in an exothermic reaction to release hydrogen (H₂) at room temperature, resulting that alkali metal amides (MNH₂) which are formed as by-products. In this work, hydrogen desorption properties of these systems and the condition for the recycle from MNH₂ back to MH were investigated systematically. For the hydrogen desorption reaction, the reactivities of MH with NH₃ were better following the atomic number of M on the periodic table, Li < Na < K. It was confirmed that the hydrogen absorption reaction of all the systems proceeded under 0.5 MPa of H₂ flow condition below 300 °C.     

Experimental and numerical analysis of dynamic metal hydride hydrogen storage systems

This paper examines the dynamics of metal hydride storage systems by experimentation and numerical modelling. A specially designed and instrumented metal hydride tank is used to gather data for a cyclic external hydrogen load. Thermocouples provide temperature measurements at various radial and axial locations in the metal hydride bed. This data is used to validate a two-dimensional mathematical model previously developed by the authors. The model is then used to perform a parametric study on some of the key variables describing metal hydride systems. These variables are the equilibrium pressure, where the tails and concentration dependence are investigated, and the effective thermal conductivity of the metal hydride bed, where the pressure and concentration dependence are analyzed. Including tails on the equilibrium pressure curves was found to be important particularly for the accuracy of the initial cycles. Introducing a concentration dependence for the plateau region of the equilibrium pressure curve was found to be important for both pressure and temperature results. Effective thermal conductivity was found to be important, and the inclusion of pressure and concentration dependence produced more precise modelling results.     

Enhanced hydrogen storage properties and mechanisms of magnesium hydride modified by transition metal dissolved magnesium oxides

Magnesium hydride (MgH₂) is a promising on-board hydrogen storage material due to its high capacity, low cost and abundant Mg resources. Nevertheless, the practical application of MgH₂ is hindered by its poor dehydrogenation ability and cycling stability. Herein, the influences and mechanisms of thin pristine magnesium oxide (MgO) and transition metals (TM) dissolved Mg(TM)O layers (TM = Ti, V, Nb, Fe, Co, Ni) on hydrogen desorption and reversible cycling properties of MgH₂ were investigated using first-principles calculations method. The results demonstrate that either thin pristine MgO or Mg(TM)O layer weakens the MgH bond strength, leading to the decreased structural stability and hydrogen desorption energy of MgH₂. Among them, the Mg(Nb)O layer exhibits the most pronounced destabilization effect on MgH₂. Moreover, the Mg(Nb)O layer presents a long-acting confinement effect on MgH₂ due to the stronger interfacial bonding strength of Mg(Nb)O/MgH₂ and the lower brittleness of Mg(Nb)O itself. Further analyses of electronic structures indicate that these thin oxide layers coating on MgH₂ surface reduce the bonding electron number of MgH₂, which essentially accounts for the weakened MgH bond strength and enhanced hydrogen desorption properties of modified MgH₂ systems. These findings provide a new avenue for enhancing the hydrogen desorption and reversible cycling properties of MgH₂ by designing and adding suitable MgO based oxides with high catalytic activity and low brittleness.     

Charging dynamics of metal hydride hydrogen storage bed for small wind hybrid systems

Small hybrid wind systems are capable of storing and supplying power for residential applications. In this paper, the excess wind energy is converted into hydrogen by electrolysis and is stored in a metal hydride. Metal hydride beds are known for their high volumetric capacity compared to the compressed hydrogen storage, and offers hydrogen storage at a reasonable operating temperature and pressure. A system simulation model is developed in Matlab/Simulink platform for the dynamics of the metal hydride hydrogen storage system, which is charged by the wind energy. The thermal loads of the metal hydride storage system is met by passing water at ambient temperature for cooling the bed while hydrogen is being absorbed. The effect of the transient turbulent wind velocity profile on the storage system is analyzed. The thermal management of the storage system plays an important role in the overall design, and hence it is discussed in detail.     

Thermal conductivity of metal hydride materials for storage of hydrogen: Experimental investigation

The effective thermal conductivity of a powdery material, comprising heat conduction in the solid particles and in gas and temperature radiation across the pores, was determined by the transient hot wire method. The materials investigated were LaNi_4.7Al_0.3H_x, which is practically applied at medium temperature, and HWT 5800, applied at low temperatures. The temperature range investigated was −80 to +140 °C, the pressure range 10⁻⁶ to 60 bar. The porosity of the powder material in the state of delivery was 0.045 and 0.531. Concentration/pressure isotherms (CPI) and the effective thermal conductivity k_eff were measured. Various filling gases (H₂, He, N₂, Ar) were used. There is a clear effect of the gas in the state of delivery of the powder. An effect of particle decay can be observed. The effective thermal conductivity depends primarily on the hydrogen pressure, while the temperature has only an indirect influence.     

Study of hydrogen storage properties of oxygen modified Ti- based AB2 type metal hydride alloy

A multi component AB₂ type hydrogen storage intermetallic alloy (A = Ti_0.85Zr_0.15, B₂ = Mn_1.22Ni_0.22Cr_0.2V_0.3Fe_0.06; was investigated in this work. The intermetallic specified above was modified by oxygen to yield the composition AB₂O_0.05. The oxygen was introduced by adding TiO₂ to the charge, with corresponding decrease of the Ti amount, followed by arc melting and annealing at the same conditions as for the oxygen free AB₂-type alloy. The addition of oxygen to the alloy did not change much the PCT properties; the only difference was that the plateau pressure for the oxygen-modified alloy increased slightly. Both alloys have shown to be excellent candidates for H₂ storage, particularly for utility vehicles, due to their relatively high reversible H₂ storage capacity (1.6 wt%) and low plateau pressure at room temperature (<5 bar). The addition of oxygen improved hydrogen absorption kinetics in the AB₂ alloy allowing it to immediately absorb H₂ without activation while for the non-modified sample an incubation period (30 min) was observed at the same conditions.     

A critical review on improving hydrogen storage properties of metal hydride via nanostructuring and integrating carbonaceous materials

Hydrogen-based economy has a great potential for addressing the world's environmental concerns by using hydrogen as its future energy carrier. Hydrogen can be stored in gaseous, liquid and solid-state form, but among all solid-state hydrogen storage materials (metal hydrides) have the highest energy density. However, hydrogen accessibility is a challenging step in metal hydride-based materials. To improve the hydrogen storage kinetics, effects of functionalized catalysts/dopants on metal atoms have been extensively studied. The nanostructuring of metal hydrides is a new focus and has enhanced hydrogen storage properties by allowing higher surface area and thus reversibility, hydrogen storage density, faster and tunable kinetics, lower absorption and desorption temperatures, and durability. The effect of incorporating nanoparticles of carbon-based materials (graphene, C60, carbon nanotubes (CNTs), carbon black, and carbon aerogel) showed improved hydrogen storage characteristics of metal hydrides. In this critical review, the effects of various carbon-based materials, catalysts, and dopants are summarized in terms of hydrogen-storage capacity and kinetics. This review also highlights the effects of carbon nanomaterials on metal hydrides along with advanced synthesis routes, and analysis techniques to explore the effects of encapsulated metal hydrides and carbon particles. In addition, effects of carbon composites in polymeric composites for improved hydrogen storage properties in solid-state forms, and new characterization techniques are also discussed. As is known, the nanomaterials have extremely higher surface area (100–1000 time more surface area in m²/g) when compared to the bulk scale materials; thus, hydrogen absorption and desorption can be tuned in nanoscale structures for various industrial applications. The nanoscale tailoring of metal hydrides with carbon materials is a promising strategy for the next generation of solid-state hydrogen storage systems for different industries.