Tests on a metal hydride based thermal energy storage system

In this paper, the performance tests on Mg + 30% MmNi₄ based thermal energy storage device is presented. Experiments were carried out at different supply pressures (10–30 bar) and absorption temperatures (120–150 °C). The effects of hydrogen supply pressure and absorption temperature on the amount of hydrogen/heat stored and thermal energy storage coefficient are presented. The maximum hydrogen storage capacity of 2.5wt% is reported at the operating conditions of 20 bar supply pressure and 150 °C absorption temperature. For a given absorption temperature of 150 °C, the thermal energy storage coefficient is found to increase from 0.5 at 10 bar to 0.74 at 30 bar supply pressure. For the given operating conditions of 20 bar supply pressure and 150 °C absorption temperature, the maximum amount of heat stored is about 0.714 MJ/kg and the corresponding thermal energy storage coefficient is 0.74.     

Selection of metal hydrides-based thermal energy storage: Energy storage efficiency and density targets

Thermo-chemical energy storage based on metal hydrides has gained tremendous interest in solar heat storage applications such as concentrated solar power systems (CSP) and parabolic troughs. In such systems, two metal hydride beds are connected and operating in an alternative way as energy storage or hydrogen storage. However, the selection of metal hydrides is essential for a smooth operation of these CSP systems in terms of energy storage efficiency and density. In this study, thermal energy storage systems using metal hydrides are modeled and analyzed in detail using first law of thermodynamics. For these purpose, four conventional metal hydrides are selected namely LaNi₅, Mg, Mg₂Ni and Mg₂FeH₆. The comparison of performance is made in terms of volumetric energy storage and energy storage efficiency. The effects of operating conditions (temperature, hydrogen pressure and heat transfer fluid mass flow rates) and reactor design on the aforementioned performance metrics are studied and discussed in detail. The preliminary results showed that Mg-based hydrides store energy ranging from 1.3 to 2.4 GJ m^?3 while the energy storage can be as low as 30% due to their slow intrinsic kinetics. On the other hand, coupling Mg-based hydrides with LaNi₅ allow us to recover heat at a useful temperature above 330 K with low energy density ca.500 MJ m^?3 provided suitable operating conditions are selected. The results of this study will be helpful to screen out all potentially viable hydrides materials for heat storage applications.     

An operational high temperature thermal energy storage system using magnesium iron hydride

Metal hydrides have been demonstrated as energy storage materials for thermal battery applications. This is due to the high energy density associated with the reversible thermochemical reaction between metals and hydrogen. Magnesium iron hydride (Mg₂FeH₆) is one such material that has been identified as a thermal energy storage material due to its reversible hydrogenation reaction at temperatures between 400 and 600 °C. This study demonstates an automated thermal battery prototype containing 900 g of Mg₂FeH₆ as the thermal energy storage material with pressurised water acting as the heat transfer fluid to charge and discharge the battery. The operating conditions of the system were optimised by assessing the ideal operating temperature, flow rate of the heat transfer fluid, and hydrogen pressures. Overall, excellent cyclic energy storage reversibility was demonstrated between 410 and 450 °C with a maximum energy capacity of 1650 kJ which is 87% of the theoretical value (1890 kJ).     

Study of a metal hydride based thermal energy storage system using multi-phase heat exchange for the application of concentrated solar power system

Thermal energy storage system is of great significance for the concentrated solar power system to keep the balance between power generation and demand. Metal hydride based thermal energy storage system is regarded as a promising method due to its good reversibility, low cost, and no by-product. Multi-phase heat exchange has much higher heat transfer coefficient than single-phase fluid heat exchange, thus facilitating the steam generation. In this study, a two-dimensional model of the metal hydride reactor using multi-phase heat exchange is proposed to estimate the performance and its feasibility of application in the concentrated solar power system. The results show that the velocity of the heat transfer fluid should match well with the thermal conductivity of the metal hydride bed to maintain the heat flux at a relatively constant value. The match of thermal conductivity of 3 or 5 W/(m·K) and fluid velocity of 0.0050 m/s results in the heat flux up to about 19 kW/m², which is increased by 3 orders of magnitude than single-phase heat exchange. In the thermal energy storage system, the reheating cycle is recommended to improve the utilization of the thermal energy. The efficiency of the system could be improved from 18.4% to 30.8% using the reheating cycle. The increased efficiency is comparable to the previously reported efficiency of 39.2%. Besides, the operation strategy of raising the steam temperature by increasing the hydrogen pressure or the superheater temperature is suggested for the system to obtain higher efficiency.     

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.     

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.     

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.     

Simulation of high temperature thermal energy storage system based on coupled metal hydrides for solar driven steam power plants

Concentrating solar power plants can achieve low cost and efficient renewable electricity production if equipped with adequate thermal energy storage systems. Metal hydride based thermal energy storage systems are appealing candidates due to their demonstrated potential for very high volumetric energy densities, high exergetic efficiencies, and low costs. The feasibility and performance of a thermal energy storage system based on NaMgH₂F hydride paired with TiCr_1.6Mn_0.2 is examined, discussing its integration with a solar-driven ultra-supercritical steam power plant. The simulated storage system is based on a laboratory-scale experimental apparatus. It is analyzed using a detailed transport model accounting for the thermochemical hydrogen absorption and desorption reactions, including kinetics expressions adequate for the current metal hydride system. The results show that the proposed metal hydride pair can suitably be integrated with a high temperature steam power plant. The thermal energy storage system achieves output energy densities of 226 kWh/m³, 9 times the DOE SunShot target, with moderate temperature and pressure swings. In addition, simulations indicate that there is significant scope for performance improvement via heat-transfer enhancement strategies.     

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.     

Investigation of coupled AB5 type high-power metal hydride reactors

The objective of this study is to investigate the coupled AB₅ type high-power metal hydride reactors in thermal energy applications. A system to test the reactors was set up coupling two reactors containing either LaNi_xAl_5−x or Ca_yMm_1−yNi₅ alloys, used as low and high pressure metal hydrides, respectively. In order to develop the high-power reactor, the metal hydrides were thinly coated (about 1–2 μm thickness) with copper and compressed to form the Porous Metal Hydrides (PMH) compacts. During the experiments, the dynamic behaviors of the reactive kinetics of the system were monitored. Among the tested systems, the coupling of Ca_0.6Mm_0.4Ni₅ and LaNi_4.75Al_0.25 was the most effective for thermal energy applications. It took the least time to reach the equilibrium state in both hydriding and dehydriding processes (approximately 250 s) and had the highest amount of heat generation/absorption. The smaller the value of y in Ca_1−yMm_yNi₅ alloys, causing the alloy to contain more calcium, the faster the reaction kinetics. In the case of the LaNi_xAl_5−x reactor, the addition of aluminum enhanced the reaction kinetics. Moreover, the reactor with the low pressure metal hydride, LaNi_xAl_5−x, took a longer period of time to reach the equilibrium state than when the high pressure metal hydride, Ca_1−yMm_yNi₅, was employed.     

Thermal management and power saving operations for improved energy efficiency within a renewable hydrogen energy system utilizing metal hydride hydrogen storage

To ensure the energy efficiency of renewable hydrogen energy systems, power conservation and thermal management are necessary. This study applies these principals to the operation of metal hydride tanks (MHTs) in a bench-scale hydrogen system, named Hydro Q-BiC?, comprising photovoltaic panels (20 kW), an electrolyzer (5 Nm³/h), MHTs containing a TiFe-based MH (40 Nm³), fuel cells (FC; 3.5 kW(power)/2.5 kW(heat)), and Li-ion batteries (20 kW/20 kWh). Here, we show that in a modified hydrogen production operation, with limited use of auxiliaries for cooling the MHTs, the power consumption of the MHTs was reduced by more than 99% compared to a typical operation. The thermal requirements for the MHTs were reduced by ceasing production in a pressurized state. During the hydrogen use operation, the power consumption was reduced to 1/4 and the FC heat output could be fully used; hence, the overall energy efficiency (power-to-hydrogen-to-power/heat) was as high as ~ 60% (43% for the typical operation).     

A critical review on design aspects and developmental status of metal hydride based thermal machines

Over two decades, research in the field of metal hydride based thermal machines has gained immense attention by the researchers of different fields. Because of its capability to store large volume of hydrogen per unit mass at near ambient condition, its utilization has been spread in numerous applications such as energy storage and other biological, chemical, aerospace and nuclear applications. Though there have been several review reports published on metal hydride based hydrogen storage, but the present work is focused on the thermal management issues and worldwide developmental status of various metal hydride based thermal machines such as thermal energy storage, heat upgradation, heat pump, cooling system, and hydrogen purification and compression. With a brief discussion about the basic understanding of metal hydride alloy formation, this paper also covers screening of metal hydride alloys, design considerations and evolution of different reactor geometries for various metal hydride based thermal management systems. The review also addresses the benefit of coupling of a metal hydride based hydrogen energy system with a conventional thermal system in order to a produce hybrid system with much higher performance and almost zero environmental pollution.     

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.     

Experimental studies on LaNi4.25Al0.75 alloy for hydrogen and thermal energy storage applications

Reversible exothermic and endothermic reactions between metals/alloys and hydrogen gas provide great opportunity to utilize various thermal energy sources such as waste heat, industrial exhaust, and solar thermal energy. Metal hydrides with favourable properties to operate at medium temperature heat (about 150 °C) are limited, and studies on hydrides in this temperature range are scarce. Hence, the present study aims at experimental investigations on LaNi_4.25Al_0.75 alloy in the temperature range of 150 °C–200 °C. A novel cartridge type of reactor is employed to investigate the hydrogen storage characteristics and thermal storage performance of this alloy. LaNi_4.25Al_0.75 is found to have a hydrogen storage capacity of about 1.20 wt% at 10 bar and 25 °C. In addition, it can store a total thermal energy of 285.7 ${\mathrm{k}\mathrm{J}.\mathrm{k}\mathrm{g}}_{\mathrm{M}\mathrm{H}}^{-1}$ and can deliver heat at an average rate of 287.5 ${\mathrm{W}.\mathrm{k}\mathrm{g}}_{\mathrm{M}\mathrm{H}}^{-1}$ at an efficiency of 64.1%.     

Thermodynamic simulation of hydrogen based thermochemical energy storage system

The increasing energy demand needs the attention for energy conservation as well as requires the utilisation of renewable sources. In this perspective, hydrogen provides an eco-friendly and regenerative solution toward this matter of concern. Thermochemical energy storage system working on gas-solid interaction is a useful technology for energy storage during the availability of renewable energy sources. It provides the same during unavailability of energy sources. This work presents a performance analysis of metal hydride based thermal energy storage system (MH-TES), which can transform the waste heat into useful high-grade heat output. This system opens new doors to look at renewable energy through better waste heat recovery systems. Experimentally measured PCIs of chosen metal hydride pairs, i.e. LaNi_4.6Al_0.4/La_0.9Ce_0.1Ni₅ (A-1/A-3; pair 1) and LaNi_4.7Al_0.3/La_0.9Ce_0.1Ni₅ (A-2/A-3; pair 2) are employed to estimate the thermodynamic performance of MH-TES at operating temperatures of 298 K, 373 K, 403 K and 423 K as atmospheric temperature (T_atm), waste heat input temperature (T_m), storage temperature (T_s) and upgraded/enhanced heat output temperature (T_h) respectively. It is observed that the system with alloy pair A-1/A-3 shows higher energy storage density of 121.83 kJ/kg with a higher COP of 0.48 as compared to A-2/A-3 pair. This is due to the favourable thermodynamic properties, and the pressure differential between coupled MH beds, which results in higher transferrable hydrogen. Besides, the effect of operating temperatures on COP is studied, which can help to select an optimum temperature range for a particular application.     

The effect of storage time on the thermal behavior of nanocrystalline magnesium hydride with metal halide additives

This work presents results concerning the thermal stability of nanocrystalline magnesium hydride milled with 7 wt% of metal halide additives such as ZrF₄, NbF₅, TaF₅, FeF₂, FeF₃, TiCl₃ and VCl₃ after one year of storage in a glovebox under a continuously purified argon atmosphere. The amounts of oxygen and water in the glovebox were below 0.1 ppm. The gases released from the materials during the thermal decomposition of all samples were analyzed using a quadrupole mass spectrometer. The oxidation of MgH₂ at low oxygen and water vapor pressures leads to an increase in the hydride decomposition temperatures of the samples compared to their initial (as-prepared) counterparts, which are shown in Ref. [1]. The differences in the decomposition temperatures between the powders stored for one year in a glovebox and the initial as-prepared powders were greater than 60 °C for MgH₂ with NbF₅, ZrF_4, TaF₅, TiCl₃ and VCl₃. The release of water from all long-term-stored materials and the emission of hydrogen fluoride (HF) from MgH₂ with metal fluorides were observed during heating. The observed results demonstrate that even a protective argon atmosphere did not prevent the degradation of the nanocrystalline MgH₂ powders with various metal halide additives during their long-term storage in a professional glovebox, which is an important practical concern.     

Parametric studies on a metal hydride based hydrogen storage device

In this paper, a two-dimensional computational investigation of coupled heat and mass transfer process in an annular cylindrical hydrogen storage device filled with _MmNi4.6Al0.4${\mathrm{MmNi}}_{4.6}{\mathrm{Al}}_{0.4}$ is presented using a commercial software FLUENT 6.1.22. Hydrogen storage performance of the device is studied by varying the operating parameters such as hydrogen supply pressure and absorption temperature. Further, the effects of various bed parameters such as hydride bed thickness and overall heat transfer coefficient on the storage performance of the device are also studied. The average temperature of the hydriding bed and hydrogen storage capacity at different supply pressures showed good agreement with the experimental data reported in the literature. It is observed that as the hydriding process is initiated, the absorption of hydrogen increases rapidly and then it slows down after the temperature of the hydride bed increases due to the heat of the reaction. At any given absorption temperature, the hydrogen absorption rate and hydrogen storage capacity are found to increase with the supply pressure. The variation in the hydrogen absorption capacity, rate of reaction and temperature profiles at different supply pressures from 5 to 35 bar in steps of 5 bar are presented. Further, the effects of overall heat transfer coefficients from 750 to 1250 W/m² K and cooling fluid temperatures from 288 to 298 K on hydrogen storage capacity are also investigated. It is shown that the heat transfer rate enhances the hydriding rate by accomplishing a rapid reaction. At the supply condition of 35 bar and 298 K, _MmNi4.6Al0.4${\mathrm{MmNi}}_{4.6}{\mathrm{Al}}_{0.4}$ stores about 13.1 g of hydrogen per kg of alloy.     

Development of large MH tank system for renewable energy storage

Metal Hydrides (MH) can absorb large quantities of hydrogen at room temperature and ordinary pressure. Because MH can store hydrogen at a pressure less than 0.1 MPa safely and compactly, it is looked to as a method of storing hydrogen produced by electricity derived from renewable energy sources. To study this method of storing renewable energy, we made a MH tank system which could store hydrogen in the range of 1000 Nm³. A Mm-NiMnCo alloy was used for this MH tank system. MH becomes pulverized with absorbing and desorbing hydrogen, and this causes the problem of MH tank transformation owing to the partial distribution of the pulverized MH powders. Our MH material, named “Hydrage?,” was made using a technique to compose the MH powders with polymer materials without decreasing the hydrogen absorption and desorption rate. With this technique, the MH powders were immobilized, and strain on the MH tank was reduced. Furthermore, this technique enabled uniform dispersion of the MH powders, and high-density filling in MH tank was achieved relative to that attainable in a conventional MH tank. An MH tank system with a capacity of 1000 Nm³ is 1,800 mm in width, 3,150 mm in length, and 2,145 mm in height. The system for renewable energy storage consists of 9 tanks. About 7.2 tons of MH were used in this system. This system could work at temperatures from 25 to 35° C, and its maximum hydrogen absorption and desorption rate is 70 Nm³/h with a medium flow rate of 30 NL/min. This type of MH tank system, which can store a large amount of hydrogen safely and compactly, has the potential to become popular with various applications in the future.