Performance analysis of LaNi5 added with expanded natural graphite for hydrogen storage system

This paper presents a comparative study of two cases of metal hydride hydrogen storage units working on (i) LaNi₅ (ii) Compacts of LaNi₅ incorporated with expanded natural graphite (ENG). It has been observed from the previous studies that the hydriding/dehydriding reactions eventually causes large strain changes, due to which the hydride forming metal alloys disintegrate and form a powder bed. Such reactor beds usually have a low thermal conductivity which minimizes the heat transfer phenomenon occurring during the absorption of hydrogen gas. Therefore, there is a need to implement heat augmentation methods to significantly enhance the thermal conductivity. The objective of this research is to present a 2-D numerical model using Finite Volume Method (FVM) and estimate the hydrogen storage performance of a cylindrical metal hydride bed for both the cases, i.e. powdered metal hydride bed and ENG compacts-based reactor bed at different values of inlet pressure and heat transfer fluid temperature. In this study, a detailed investigation on the absorption process reveals that reactor beds with compacted disks of LaNi₅ and ENG demonstrate an enhanced effective thermal conductivity and efficient mass transfer. The simulation results show that a remarkable improvement in the heat transfer and hydrogen storage capacity with reduced absorption time can be achieved by using LaNi₅ and ENG compacts. It was observed that the average reactor bed temperature dropped from 345.13 K to 337.37 K when the ENG based compacted disks was introduced into the reactor bed. Moreover, for supply pressure of 24 bar and fluid temperature of 293 K, the time taken to absorb hydrogen into the rector to achieve stabilized hydrogen storage capacity was estimated to be 446s and 232 s for the case of metal hydride and ENG compacts-based bed, respectively.     

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.     

Metal hydride hydrogen storage and compression systems for energy storage technologies

Along with a brief overview of literature data on energy storage technologies utilising hydrogen and metal hydrides, this article presents results of the related R&D activities carried out by the authors. The focus is put on proper selection of metal hydride materials on the basis of AB₅- and AB₂-type intermetallic compounds for hydrogen storage and compression applications, based on the analysis of PCT properties of the materials in systems with H₂ gas. The article also presents features of integrated energy storage systems utilising metal hydride hydrogen storage and compression, as well as their metal hydride based components developed at IPCP and HySA Systems.     

Thermal management of metal hydride hydrogen storage reservoir using phase change materials

Metal hydride hydrogen storage reservoir should be carefully designed to achieve acceptable performance due to significant thermal effect on the system during hydriding/dehydriding. Phase change materials can be applied to metal hydride hydrogen storage system in order to improve the system performance. A transient two-dimensional axisymmetric numerical model for the metal hydride reservoir packed with LaNi₅ has been developed on Comsol platform, which was validated by comparing the simulation results with the experiment data from other work. Then, the performances of metal hydride hydrogen storage reservoir using phase change materials were predicted. The effects of some parameters, such as the thermal conductivity, the mass and the latent heat of fusion of the phase change materials, on the metal hydride hydrogen storage reservoir were discussed. The results shown that it was good way to improve the efficiency of the system by increasing the thermal conductivity of phase change materials and selecting a relatively larger latent heat of fusion. Due to the relatively lower thermal conductivity of phase change materials, different metal foams were composited with the phase change materials in order to improve the heat transfer from the metal hydride bed to the phase change materials and the hydrogen storage efficiency. The effect of aluminium foam on the metal hydride reservoir was studied and validated. The phase change materials composited with copper foam shown better performance than that composited with aluminium foam.     

Selection of metal hydrides for a thermal energy storage device to support low-temperature concentrating solar power plants

Metal hydrides have become more and more significant both as hydrogen storage devices and as basic elements in energy conversion systems. Besides the well-known rare earth hydrides, magnesium alloys are very promising in the field of thermal energy storage for concentrating solar power plants. There is interest in analysing the performances of such materials in this context; for this purpose, a numerical model to describe hydrogen absorption and desorption processes of a metal hydride has been connected to a model elaborated with the help of Cycle-Tempo software to simulate a CSP plant operation. The integration of this plant with four metal hydride systems, based on the combination of two low-temperature hydrides (LaNi₅, LaNi_4.8Al_0.2) and two high-temperature hydrides (Mg, Mg₂Ni) has been studied. The investigation has taken into account CSP overall performances, transfer surfaces and storage efficiencies, to determine the feasibility of designed plants. Results show that the selection of the optimal hydrides must take into account hydride operation temperatures, reaction enthalpies, storage capacities and kinetic compatibility. In the light of the calculated parameters, a solar ORC plant using R134a as the working fluid is a valuable choice if matched to a storage system composed of LaNi₅ and Mg₂Ni hydrides.     

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.     

System simulation model for high-pressure metal hydride hydrogen storage systems

On-board hydrogen storage systems employing high-pressure metal hydrides promise advantages including high volumetric capacities and cold start capability. In this paper, we discuss the development of a system simulation model in Matlab/Simulink platform. Transient equations for mass balance and energy balance are presented. Appropriate kinetic expressions are used for the absorption/desorption reactions for the Ti_1.1CrMn metal hydride. During refueling, the bed is cooled by passing a coolant through tubes embedded within the bed while during driving, the bed is heated by pumping the radiator fluid through same set of tubes. The feasibility of using a high-pressure metal hydride storage system for automotive applications is discussed. Drive cycle simulations for a fuel cell vehicle are performed and detailed results are presented.     

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.     

Design of a AB5-metal hydride cylindrical tank for hydrogen storage

Hydrogen storage in metal hydrides presents distinct challenges which encourage the study of effective heat management strategies. Hydrogen absorption in metal hydrides is an exothermic reaction, consequently the generated heat must be removed effectively to achieve the desired performance. This work presents a mathematical model describing the adsorption of hydrogen in La Ni_4.7Co_0.3 metal hydride as a storage material. Heat and mass transfer effects are modeled in detail. The effect of heat transfer coefficient is also estimated. Besides, a heat transfer fluid for cooling is incorporated to the model. The problem is mathematically formulated presenting a numerical simulation of a design of a cylindrical tank for hydrogen storage. The alloy is studied by using pressure-composition-temperature curves which are carried out at different temperatures. Thermodynamic parameters and hydrogen storage capacity are determined. For isotherm's kinetics, the Jonhson-Mehl-Avrami-Kolomogorov model is used, from which the kinetic constant of the hydriding process is determined.     

Performance prediction of a coupled metal hydride based thermal energy storage system

The present study discusses the thermodynamic compatibility criteria for the selection of metal hydride pairs for the application in coupled metal hydride based thermal energy storage systems. These are closed systems comprising of two metal hydride beds – a primary bed for energy storage and a secondary bed for hydrogen storage. The performance of a coupled system is analyzed considering Mg₂Ni material for energy storage and LaNi₅ material for hydrogen storage. A 3-D model is developed and simulated using COMSOL Multiphysics® at charging and discharging temperatures of 300 °C and 230 °C, respectively. The LaNi₅ bed used for hydrogen storage is operated close to ambient temperature of 25 °C. The results of the first three consecutive cycles are presented. The thermal storage system achieved a volumetric energy storage density of 156 kWh m⁻³ at energy storage efficiency of 89.4% during third cycle.     

Heat transfer characteristics of the metal hydride vessel based on the plate-fin type heat exchanger

Heat transfer characteristics of the metal hydride vessel based on the plate-fin type heat exchanger were investigated. Metal hydride beds were filled with AB₂ type hydrogen-storage alloy’s particles, Ti_0.42Zr_0.58Cr_0.78Fe_0.57Ni_0.2Mn_0.39Cu_0.03, with a storage capacity of 0.92 wt.%. Heat transfer model in the metal hydride bed based on the heat transfer mechanism for packed bed proposed by Kunii and co-workers is presented. The time-dependent hydrogen absorption/desorption rate and pressure in the metal hydride vessel calculated by the model were compared with the experimental results. During the hydriding, calculated hydrogen absorption rates agreed with measured ones. Calculated thermal equilibrium hydrogen pressures were slightly lower than the measured hydrogen pressures at the inlet of metal hydride vessel. Taking account of the pressure gradient between the inlet of metal hydride vessel and the metal hydride bed, it is considered that this discrepancy is reasonable. During the dehydriding, there were big differences between the calculated hydrogen desorption rates and measured ones. As calculated hydrogen desorption rates were lower than measured ones, there were big differences between the calculated thermal equilibrium hydrogen pressures and the measured hydrogen pressures at the inlet of metal hydride vessel. It is considered that those differences are due to the differences of the heat transfer characteristics such as thermal conductivity of metal hydride particles and porosity between the assumed and actual ones. It is important to obtain the heat transfer characteristics such as thermal conductivity of metal hydride particles and porosity both during the hydriding and dehydriding to design a metal hydride vessel.     

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.     

Thermal modeling and performance analysis of industrial-scale metal hydride based hydrogen storage container

In this paper, a performance analysis of a metal hydride based hydrogen storage container with embedded cooling tubes during absorption of hydrogen is presented. A 2-D mathematical model in cylindrical coordinates is developed using the commercial software COMSOL Multiphysics 4.2. Numerical results obtained are found in good agreement with experimental data available in the literature. Different container geometries, depending upon the number and arrangement of cooling tubes inside the hydride bed, are considered to obtain an optimum geometry. For this optimum geometry, the effects of various operating parameters viz. supply pressure, cooling fluid temperature and overall heat transfer coefficient on the hydriding characteristics of MmNi_4.6Al_0.4 are presented. Industrial-scale hydrogen storage container with the capacity of about 150 kg of alloy mass is also modeled. In summary, this paper demonstrates the modeling and the selection of optimum geometry of a metal hydride based hydrogen storage container (MHHSC) based on minimum absorption time and easy manufacturing aspects.     

Hydrogen storage systems based on hydride materials with enhanced thermal conductivity

The reaction of hydrogen gas with a metal to form a metal hydride is exothermic. If the heat released is not removed from the system, the resulting temperature rise of the hydride will reduce the hydrogen absorption rate. Hence, hydrogen storage systems based on hydride materials must include a way to remove the heat generated during the absorption process. The heat removal rate can be increased by (i) increasing the effective thermal conductivity of the metal hydride by mixing it with high-conductivity materials such as aluminum foam or graphite, (ii) optimizing the shape of the tank, and (iii) introducing an active cooling environment instead of relying on natural convection. This paper presents a parametric study of hydrogen storage efficiency that explores quantitatively the influence of these parameters. An axisymmetric mathematical model was formulated in Ansys Fluent 12.1 to evaluate the transient heat and mass transfer in a cylindrical metal hydride tank, and to predict the transient temperatures and mass of hydrogen stored as a function of the thermal conductivity of the enhanced hydride material, aspect ratio of the cylindrical tank, and thermal boundary conditions. The model was validated by comparing the transient temperature at selected locations within the storage tank with concurrent experiments conducted with LaNi₅ material. The parametric study revealed that the aspect ratio of the tank has a stronger influence when the effective thermal conductivity of the metal hydride bed is low or when the heat removal rate from the tank surface is high (active cooling). It was also found that for a hydrogen filling time of 3 min, adding 30% aluminum foam to the metal hydride maximizes hydrogen absorption under natural convection, whereas the addition of only 10% aluminum foam maximizes the hydrogen content under active cooling. For filling times beyond 3 min, the amount of aluminum foam required to maximize hydrogen content can be reduced for both natural convection and active cooling. This study should prove useful in the design of practical metal hydride-based hydrogen storage systems.     

A thermally coupled metal hydride hydrogen storage and fuel cell system

This paper examines the ability of metal hydride storage systems to supply hydrogen to a fuel cell with a time varying demand, when the metal hydride tanks are thermally coupled to the fuel cell. A two-dimensional mathematical model is utilized to compare different heat transfer enhancements and storage tank configurations. The scenario investigated involves two metal hydride tanks containing the alloy Ti_0.98Zr_0.02V_0.43Fe_0.09Cr_0.05Mn_1.5, located in the air exhaust stream of a fuel cell. Three cases are simulated: a base case with no heat transfer enhancements, a case with external fins attached to the outside of the tank, and a case where an annular tank design is used. For the imposed duty cycle, the base case is insufficient to provide the hydrogen demands of the system, while both the finned and annular cases are able to meet the demands. The finned case yields higher pressures and occupies more space, while the annular case yields acceptable pressures and requires less space. Furthermore, the annular metal hydride tank meets the requirements of the fuel cell while providing a more robust and compact hydrogen storage system.     

Numerical simulation and experimental validation of Ti0.95Zr0.05Mn0.9Cr0.9V0.2 alloy in a metal hydride tank for high-density hydrogen storage

In order to achieve rapid hydrogen charging and discharging of high-density hydrogen storage alloys in metal hydride (MH) tank, it is key to optimize the design of MH tank by simulation based on a credible numerical model. Herein, a multi-physical field mathematical model coupled with kinetic equations and heat & mass transfer equations for the de-/hydrogenation of Ti_0.95Zr_0.05Mn_0.9Cr_0.9V_0.2 alloy in MH tank is proposed. According to experimental kinetic curves, appropriate kinetic equations dominated by different rate control steps are chosen for simulating gas-solid reactions. With excellent match between experimental and simulated kinetic results under different pressure and temperature operating conditions, a novel numerical model is established to predict the local temperature variation during the de-/hydrogenation of Ti_0.95Zr_0.05Mn_0.9Cr_0.9V_0.2 alloy in a self-designed hydrogen storage tank with high-density hydrogen storage of 55.1 g H₂/L. Interestingly, further calculated results reveal that the temperature evolution can be accurately matched, which proves the reliability of the designed numerical model and favors to predict the de-/hydriding behaviors. This investigation provides an effective means for subsequent structure optimization and energy & mass transfer performance optimization of high-density hydrogen storage devices, and sheds light on the numerical simulation of heat & mass transfer for advanced energy storage applications.     

Thermal Modeling of Mg2Ni-Based Solid-State Hydrogen Storage Reactor

In this paper, a numerical study of coupled heat and hydrogen transfer characteristics in an annular cylindrical hydrogen storage reactor filled with Mg₂Ni is presented. An unsteady, two-dimensional (2-D) mathematical model of a metal hydride reaction bed of cylindrical configuration is developed for predicting the hydrogen storage capacity. The effect of volumetric radiation is accounted in the thermal model. Effects of hydride bed thickness, initial absorption temperature, hydride bed thermal conductivity, and hydrogen supply pressure on the hydrogen storage capacity are studied. A thinner hydride bed is found to enhance the hydriding rate, accomplishing a rapid reaction. At an operating condition of 20 bar supply pressure and 573 K initial absorption temperature, Mg₂Ni stores about 36.7 g hydrogen per kg alloy. For a given bed thickness and an overall heat transfer coefficient, there exists an optimum value of hydride bed thermal conductivity. The present numerical results are compared with the experimental data reported in the literature, and good agreement was observed.     

Predicting hydrogen adsorption and desorption rates in cylindrical metal hydride beds: Empirical correlations and machine learning

A major limitation in chemisorptive hydrogen storage in metal hydrides is the long time required for the adsorption reaction during charging. This study investigates how the shape and material of the reaction chamber influences the adsorption and desorption rates. Numerical simulations of hydrogen storage in a cylindrical reaction chamber filled with LaNi₅ hydride are conducted for a range of chamber thermal conductivities and aspect ratios. The results show that adsorption and desorption processes are limited by thermal diffusion in the hydride bed and storage chamber. A storage efficiency is proposed based on an ideal isothermal process and used to evaluate the impact of chamber thermal conductivity and aspect ratio on the adsorption and desorption rates. Empirical correlations are proposed for predicting the adsorption and desorption efficiency of cylindrical LaNi₅ hydride beds. Finally, a machine-learning based data model for predicting storage efficiency in metal hydride chambers is presented. Comparison against the empirical correlations highlights that the machine learning-based data model can predict the storage efficiency more accurately.     

Aluminum hydride coated single-walled carbon nanotube as a hydrogen storage medium

We report a first principle study on the hydrogen storage in Aluminum hydride (AlH₃) coated (5, 5) single-walled carbon nanotube (SWCNT). Our study indicates that a SWCNT coated with Aluminum hydride (Alane – AlH₃) can bind up to four hydrogen molecules. At half coverage of AlH₃, the hydrogen storage capacity of the SWCNT is 8.3 wt%. The system with full coverage is also studied and it is found that, even though the hydrogen storage capacity increases, the binding of H₂ is weak. All the H₂ adsorption is molecular with H–H bond length of 0.756 Å. Our result on a full molecular adsorption of hydrogen via light metal hydride is new and it leads to a practically viable storage process.     

Integrating hydrogen generation and storage in a novel compact electrochemical system based on metal hydrides

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 electrolyzer, hydrogen storage vessel and a fuel cell system for the conversion of H₂ back into electricity, when required. In this work, 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 developed prototype comprises a six-electrode cell assembly using an AB₅-type metal hydride and Ni plates as counter electrodes, in a 35-wt% KOH solution. Metal hydride electrodes with chemical composition LaNi_4.3Co_0.4Al_0.3 were 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 has been performed in a Sieverts type of apparatus produced by Labtech Int. During cycling, the charging/discharging 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.