Accurate measurement of pressure-composition isotherms and determination of thermodynamic and kinetic parameters of metal hydrides

This work presents an in-depth investigation of different techniques used to accurately determine pressure-composition isotherms (pcI) as well as thermodynamic and kinetic parameters of metal hydrides. A case study is presented for an alloy of the type LaNi₅. The results combine experimental measurements with theoretical modeling. Firstly, the numerical work presented discusses a numerical method for the evaluation of pcI raw data in order to minimize the experimental error. A simple, efficient iterative algorithm is presented to solve for the van der Waals equation of state in order to take into account the compressibility of hydrogen. Secondly, the measurements of dynamic (mass-flow) and quasi-static (Sievert's type) isotherms at different temperatures and different flow rates are presented. The dead volume of the apparatus as well as its experimental error, which is key parameter for the accurate calculation of hydrogen capacity, are also measured. Finally, important thermodynamic and kinetic parameters are deduced from the pcI curves. The kinetics of the absorption and desorption reactions are modelled and the reaction rate constants are found using both dynamic and quasi-static methods. The presented work goes beyond the calculation of the entropy and enthalpy of reaction, as the lattice gas model is also used to determine the critical temperature as well as the interaction energy between hydrogen-metal atoms and hydrogen-hydrogen atoms.     

Phase field modeling of hydrogen transport and reaction in metal hydrides

The reaction of hydrogen with metals to form metal hydrides has numerous potential energy storage and management applications. The metal hydrogen system has a high volumetric energy density and is often reversible with a high cycle life. However, improving the often poor gravimetric performance of such systems through the use of lightweight metals usually comes at the cost of reduced reaction rates or the requirement of pressure and temperature conditions far from the desired operating conditions. Most studies of reaction kinetics of such systems focus on fitting low-dimensional kinetic models to measured rates and inferring the rate-limiting process based on the quality of the fit.     

Effect of cycling on hydrogen storage properties of Ti2CrV alloy

In the present work, we have studied the hydrogen absorption–desorption properties of the Ti₂CrV alloy, and effect of cycling on the hydrogen storage capacity. The material has been characterized for the structure, morphology, pressure composition isotherms, hydrogen storage capacity, hydrogen absorption kinetics and the desorption profile at different temperatures in detail. The Ti₂CrV crystallizes in body centered cubic (bcc) structure like TiCrV. The pressure composition isotherm of the alloy has been measured at room temperature and at 373K. The Ti₂CrV alloy shows maximum hydrogen storage capacity of 4.37 wt.% at room temperature. The cyclic hydrogen absorption capacity of Ti₂CrV alloy has been investigated at room temperature upto 10th cycle. The hydrogen storage capacity decreased progressively with cycling initially, but the alloy can maintain steady cyclic hydrogen absorption capacity 3.5 wt.% after 5th cycle. To get insight about the desorption behavior of the hydride in-situ desorption has been done at different temperatures and the amount of hydrogen desorbed has been calculated. The TG (Thermo gravimetric) and DTA analysis has been done on uncycled hydride shows that the surface poisoned sample gives a desorption onset temperature of 675K. The DSC measurement of uncycle and multi-cycled saturated hydrides shows that the hydrogen desorption temperature decreasing with cycling.     

Impact of nanostructuring on the enthalpy of formation of metal hydrides

High-energy ball milling has been shown to decrease the release temperature, increase the reaction kinetics, and lower the enthalpy of formation of metal hydrides in certain cases. This paper discusses several potential mechanisms for the reduction of the enthalpy of formation. Although the increased surface and grain boundary energy could play a role in reducing the enthalpy of formation, the predicted magnitude is too small to account for experimental observations. Structural deformation and the associated volume change provide another mechanism for the change in this thermodynamic property. We employed three equations of state models to characterize the excess energy present in the deformed regions and found that the excess volume provides a plausible explanation for the experimentally observed change in thermodynamic properties.     

Performance simulation and experimental confirmation of a mini-channel metal hydrides reactor

A theoretical and experimental study about a proposed mini-channel reactor was carried out to enhance heat transfer performance for metal hydrides applications, such as hydrogen storage, hydrogen compression and chemical heat pumps. The configuration of the reactor and working principles are described in detail. The predicted hydride bed temperature profiles in the reactor are compared with the experimental data from the performance test system, and a reasonable agreement is observed. The simulation of the hydrogen adsorption and desorption processes in a mini-channel reactor packed with LaNi₅ is conducted, and the influences of some important parameters, e.g. the bed thickness, the number of the mini-channels, hydrogen supply and discharge pressure are analyzed. Comparing with the traditional reactors, such as tubular reactor and disc reactor, the mini-channel reactor has some obvious advantages, therefore can be recommended for applications.     

Hydrogen storage systems for fuel cells: Comparison between high and low-temperature metal hydrides

The need for the enhancement of alternative energy sources is increasingly recognised and, in this perspective, the achievement of hydrogen economy seems to be fundamental. In this regard, fuel cells represent an interesting option for small and medium scale distributed renewable generation; however, these systems are inextricably linked with the concept of hydrogen storage. Research on metal hydrides revealed the opportunity to use these materials as basic elements in hydrogen storage devices, called MH systems. This means that interest exists in investigating the behaviour of metal hydrides: in fact, MH system operation is based on the hydriding/dehydriding reactions hydrides undergo, and, with the aim of evaluating the performance of such devices, these processes must be discussed and modelled.In the light of this, a simple numerical model to study hydride-based storage systems and their integration with fuel cells was developed: two low-temperature hydrides (LaNi₅, LaNi_4·8Al_0.2) and two high-temperature hydrides (Mg, Mg₂Ni) were selected and their behaviours in a MH system were simulated and compared with the help of such a model. This is an essential step in identifying the hydrides more suited to the application in question. Results showed that the choice is the trade off between encumbrance and reaction times; this implies that low-temperature hydrides are preferable because their encumbrance is limited and their reaction temperature range grants a greater versatility in small scale generation.     

Machine learning analysis of alloying element effects on hydrogen storage properties of AB2 metal hydrides

Zirconium-titanium-based AB₂ is a potential candidate for hydrogen storage alloys and NiMH battery electrodes. Machine learning (ML) has been used to discover and optimize the properties of energy-related materials, including hydrogen storage alloys. This study used ML approaches to analyze the AB₂ metal hydrides dataset. The AB₂ alloy is considered promising owing to its slightly high hydrogen density and commerciality. This study investigates the effect of the alloying elements on the hydrogen storage properties of the AB₂ alloys, i.e., the heat of formation (ΔH), phase abundance, and hydrogen capacity. ML analysis was performed on the 314 pairs collected and data curated from the literature published during 1998–2019, comprising the chemical compositions of alloys and their hydrogen storage properties. The random forest model excellently predicts all hydrogen storage properties for the dataset. Ni provided the most contribution to the change in the enthalpy of the hydride formation but reduced the hydrogen content. Other elements, such as Cr, contribute strongly to the formation of the C14-type Laves phase. Mn significantly affects the hydrogen storage capacity. This study is expected to guide further experimental work to optimize the phase structure of AB₂ and its hydrogen sorption properties.     

Effects of NH4+ doping on the hydrogen storage properties of metal hydrides

Doping can modify the properties of metal hydrogen storage materials significantly. Currently, the metal doping is a frequent strategy, while the non-metal cation doping has not been examined extensively so far. In this study, the effects of NH₄⁺ doping on the hydrogen storage properties of different metal hydrides, including TiH₂, Ti_0·25V_0·25Nb_0·25Zr_0·25H₂, Ti_0·5V_0·5H₂ and VH₂, are investigated by first-principles calculations. It is found that the NH₄⁺ presents a good affinity for metal hydrides and the NH₄⁺ incorporation leads to charge redistribution and formation of dihydrogen bond. Furthermore, the NH₄⁺ doping in metal hydrides is favorable for enhancing the hydrogen storage capacity and decreasing the thermal stability simultaneously. The possible reason for the NH₄⁺ doping induced destabilization in metal hydrides is the relatively weak interaction between NH₄⁺ and hydrogen atoms.     

Effect of design parameters on enhancement of hydrogen charging in metal hydride reactors

The effects of heat transfer mechanisms on the charging process in metal hydride reactors are studied under various charging pressures. Three different cylindrical reactors with the same base dimensions are designed and manufactured. The first one is a closed cylinder cooled with natural convection, the fins are manufactured around the second reactor and the third reactor is cooled with water circulating around the reactor. The temperatures of the reactor at several locations are measured during charging with a range of pressure of 1–10 bar. The third reactor shows the lowest temperature increase with the fastest charging time under all charging pressures investigated. The effective heat transfer coefficients of the reactors are also calculated according to the experimental results and they are found to be 5.5 ± 1 W m⁻² K⁻¹, 35 ± 2 W m⁻² K⁻¹ and 113 ± 1 W m⁻² K⁻¹, respectively. The experimental results showed that the charging of hydride reactors is mainly heat transfer dependent and the reactor with better cooling exhibits the fastest charging characteristics.     

Sorption kinetics in metal hydrides by leaky coating

The 3D geometry of a hydrogen absorbing metal grain (Pd) is mimicked by a membrane made of the metal with identical properties, which is sealed on one side with a hydrogen semi-impermeable surface (Cu). The hydrogen loss through the sealed membrane surface is negligible, i.e., the hydrogen uptake measurement is that of a bulk material (Sieverts measurement), but the surface desorbs sufficient hydrogen to be detected by a mass spectrometer. With this, two independent spatial and temporal kinetic properties are defined which allow the reconstruction of the time dependent hydrogen distribution inside the membrane. As proof of concept, the mechanism of hydride formation in Pd is analyzed, corroborating the formation and growth of incoherent interfaces during hydrogen sorption.     

Characterization of metal hydrides by in-situ XRD

In-situ synchrotron radiation powder X-ray diffraction (SR-PXD) technique is a powerful tool to gain a deeper understanding of reaction mechanisms in crystalline materials. In this paper, the implementation of a new in-situ SR-PXD cell for solid–gas reactions is described in detail. The cell allows performing measurements in a range of pressure which goes from light vacuum (10⁻² bar) up to 200 bar and temperatures from room temperature up to 550 °C. The high precision, with which pressure and temperature are measured, enables to estimate the thermodynamic properties of the observed changes in the crystal structure and phase transformations.     

Experimental investigations and a simple balance model of a metal hydride reactor

The metal hydride reactor filled with 5 kg of the AB₅-type (LaFe_0.5Mn_0.3Ni_4.8) alloy was investigated with respect to the hydrogen discharge rates classified using C-rate value, which is discharge of the maximum hydrogen capacity 750 st L within 1 h. The reactor cannot be fully discharged with a constant flow rate, for each temperature of hot water and flow rate there exists a moment of crisis at which the hydrogen flow drops under the constant value. The nominal capacity of the reactor reaches 80% of maximum capacity if sufficient heat transfer is provided. The simple balance model of a metal hydride reactor is developed based on the assumption of uniform temperature and pressure inside a metal hydride bed. The model permits to predict behavior of the metal hydride reactor in different operation regimes, quantitative agreement is obtained for low C-rates (less than 4) and sub-critical modes.     

The effect of copper coated metal hydride at different ratios on the reaction kinetics

In this study, the process parameters that affect the improvement of hydrogen storage material properties were investigated. In order to accelerate the hydrogen charge/discharge processes and to obtain the required hydrogen at the desired flow rates in a short time, the thermal conductivity of the storage materials has been improved, and density analyses have been made. The ideal grinding time has been determined for the LaNi₅ material. Within the scope of the experimental studies, the thermal conductivity coefficients of LaNi₅ coated with copper and LaNi₅ ground for 5 h and coated with copper were increased by 500–750%, and the copper plating ratios were optimized. The materials obtained were characterized by XRD, SEM, and their density was measured with the Helium Pyknometer device and their thermal conductivity coefficients with the Hot Disk Thermal Constants Analyzer. In addition, the hydrogen storage of materials with increased thermal conductivity was investigated experimentally in the metal hydride reactor at the determined pressure. In the study, it was seen that the storage material coated with copper increases the heat transfer, reduces the hydrogen charging time in the metal hydride reactor, and increases the stable discharge time.     

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.     

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.     

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.     

A metal hydride system for a forklift: Feasibility study on on-board chemical storage of hydrogen using numerical simulation

This paper describes a technical feasibility study of on-board metal hydride storage systems. The main advantages of these systems would be that of being able to replace counterweights with the weight of the storage system and using the heat emissions of fuel cells for energy, making forklifts a perfect use case. The main challenge is designing a system that supplies the required energy for a sufficiently long period. A first draft was set up and analyzed to provide a forklift based on a fuel cell with hydrogen from HydralloyC5 or FeTiMn. The primary design parameter was the required amount of stored hydrogen, which should provide energy equal to the energy capacity of a battery in an electric vehicle. To account for highly dynamic system requirements, the reactor design was optimized such that the storage was charged in a short time. Additionally, we investigated a system in which a fixed amount of hydrogen energy was required. For this purpose, we used a validated simulation model for the design concepts of metal hydride storage systems. The model includes all relevant terms and parameters to describe processes inside the system's particular reactions and the thermal conduction due to heat exchangers. We introduce an embedded fuel cell model to calculate the demand for hydrogen for a given power level. The resulting calculations provide the required time for charging or a full charge depending on the tank's diameter and, therefore, the necessary number of tanks. We conclude that the desired hydrogen supply times are given for some of the use cases. Accordingly, the simulated results suggest that using a metal hydride system could be highly practical in forklifts.