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.     

The potential of metal hydrides paired with compressed hydrogen as thermal energy storage for concentrating solar power plants

Concentrating solar power (CSP) plants require thermal energy storage (TES) systems to produce electricity during the night and periods of cloud cover. The high energy density of high-temperature metal hydrides (HTMHs) compared to state-of-the-art two-tank molten salt systems has recently promoted their investigation as TES systems. A common challenge associated with high-temperature metal hydride thermal energy storage systems (HTMH TES systems) is storing the hydrogen gas until it is required by the HTMH to generate heat. Low-temperature metal hydrides can be used to store the hydrogen but can comprise a significant proportion of the overall system cost and they also require thermal management, which increases the engineering complexity. In this work, the potential of using a hydrogen compressor and large-scale underground hydrogen gas storage using either salt caverns or lined rock caverns has been assessed for a number of magnesium- and sodium-based hydrides: MgH₂, Mg₂FeH₆, NaMgH₃, NaMgH₂F and NaH. Previous work has assumed that the sensible heat of the hydrogen released from the HTMH would be stored in a small, inexpensive regenerative material system. However, we show that storing the sensible heat of the hydrogen released would add between US$3.6 and US$7.5/kWh_th to the total system cost for HTMHs operating at 565 °C. If the sensible heat of released hydrogen is instead exploited to perform work then there is a flow-on cost reduction for each component of the system. The HTMHs combined with underground hydrogen storage all have specific installed costs that range between US$13.7 and US$26.7/kWh_th which is less than that for current state-of-the-art molten salt heat storage. Systems based on the HTMHs Mg₂FeH₆ or NaH have the most near term and long term potential to meet SunShot cost targets for CSP thermal energy storage. Increasing the operating temperature and hydrogen equilibrium pressure of the HTMH is the most effective means to reduce costs further.     

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.     

Modeling of a thermal energy storage system based on coupled metal hydrides (magnesium iron – sodium alanate) for concentrating solar power plants

Concentrating solar power plants represent low cost and efficient solutions for renewable electricity production only if adequate thermal energy storage systems are included. Metal hydride thermal energy storage systems have demonstrated the potential to achieve very high volumetric energy densities, high exergetic efficiencies, and low costs. The current work analyzes the technical feasibility and the performance of a storage system based on the high temperature Mg₂FeH₆ hydride coupled with the low temperature Na₃AlH₆ hydride. To accomplish this, a detailed transport model has been set up and the coupled metal hydride system has been simulated based on a laboratory scale experimental configuration. Proper kinetics expressions have been developed and included in the model to replicate the absorption and desorption process in the high temperature and low temperature hydride materials. The system showed adequate hydrogen transfer between the two metal hydrides, with almost complete charging and discharging, during both thermal energy storage and thermal energy release. The system operating temperatures varied from 450 °C to 500 °C, with hydrogen pressures between 30 bar and 70 bar. This makes the thermal energy storage system a suitable candidate for pairing with a solar driven steam power plant. The model results, obtained for the selected experimental configuration, showed an actual thermal energy storage system volumetric energy density of about 132 kWh/m³, which is more than 5 times the U.S. Department of Energy SunShot target (25 kWh/m³).     

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.     

Thermal conductivity measurements of magnesium hydride powder beds under operating conditions for heat storage applications

One of the major issues of the change in energy politics is the storage of renewable energy in order to facilitate a continuous energy supply to the grid. An efficient way to store energy (heat) is provided by the usage of Thermochemical Energy Storage (TES) in metal hydrides. Energy is stored in dehydrogenated metal hydrides and can be released by hydrogenation for consumption. One prominent candidate for high temperature (400 °C) heat storage is magnesium hydride. It is a well-known and investigated material which shows high cycling stability over hundreds of cycles. It is an abundant material, non-toxic and easy to prepare in bigger scales. One of the major drawbacks for heat storage applications is the low heat transfer capability of packed beds of magnesium hydrides. In this work we present results of effective thermal conductivity (ETC) which were measured under hydrogen pressure up to 25 bar and temperatures up to 410 °C in order to meet the operating conditions of magnesium hydride as a thermochemical heat storage material. We could show that the effective thermal conductivity of a magnesium hydride – hydrogen system at 410 °C and 25 bar hydrogen increases by 10% from 1.0 W m⁻¹ K⁻¹ to 1.1 W m⁻¹ K⁻¹ after 18 discharging and charging cycles. In dehydrogenated magnesium hydride this increase of the thermal conductivity was found to be at 50% from 1.20 W m⁻¹ K⁻¹ to 1.80 W m⁻¹ K⁻¹ at 21 bar hydrogen. These data are very important for the design and construction of heat storage tanks based on high temperature metal hydrides in the future.     

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.     

Future perspectives of thermal energy storage with metal hydrides

Thermochemical energy storage materials have advantage of much higher energy densities compared to latent or sensible heat storage materials. Metal hydrides show good reversibility and cycling stability combined with high enthalpies. They can be used for short and long-term heat storage applications and can increase the overall flexibility and efficiency of solar thermal energy production. Metal hydrides with working temperatures less than 500 °C were in the focus of research and development over the last years. For the new generation of solar thermal energy plants new hydrides materials with working temperatures above 600 °C must be developed and characterized. In addition to thorough research on new metal hydrides, the construction and engineering of heat storage systems at these high temperatures are challenging. Corrosion problems, hydrogen embrittlement and selection of heat transfer fluids are significant topics for future research activities.     

Hydrogen storage by Mg-based nanocomposites

Hydrogen storage materials research is entered to a new and exciting period with the advance of the nanocrystalline alloys, which show substantially enhanced absorption/desorption kinetics, even at room temperatures. In this work, hydrogen storage capacities and the electrochemical discharge capacities of the Mg₂(Ni, Cu)-, LaNi₅-, ZrV₂-type nanocrystalline alloys and Mg₂Ni/LaNi₅-, Mg₂Ni/ZrV₂-type nanocomposites have been measured. The electronic properties of the Mg₂Ni_1-xCu_x, LaNi₅ and ZrV₂ alloys were calculated. The nanocomposite structure reduced hydriding temperature and enhanced hydrogen storage capacity of Mg-based materials. The nanocomposites (Mg,Mn)₂Ni (50 wt%)-La(Ni,Mn,Al,Co)₅ (50 wt%) and (Mg,Mn)₂Ni (75 wt%)-(Zr,Ti)(V,Cr,Ni)_2.4 (25 wt%) materials releases 1.65 wt% and 1.38 wt% hydrogen at 25 °C, respectively. The strong modifications of the electronic structure of the nanocrystalline alloys could significantly influence hydrogenation properties of Mg-based nanocomposities.     

Boosting the hydrogenation activity of dibenzyltoluene catalyzed by Mg-based metal hydrides

Hydrogenation of dibenzyltoluene (DBT) is of great significance for the application in liquid organic hydrogen carriers (LOHCs). We successfully develop Mg-based metal hydrides (Mg₂NiH₄, MgH₂, and LaH₃) reactive ball-milling for the hydrogenation of DBT. Mg-based metal hydrides milled with 500 min exhibit the best catalytic activity, the hydrogen uptake of DBT can reach 4.63 wt% at the first 4 h and finally achieve 5.70 wt% through 20 h, which is the first time to use hydrogen storage material as a catalyst for the hydrogenation of DBT. The excellent catalytic hydrogenation performance of Mg-based metal hydrides mostly originates from numerous catalytic activity centers formed at the surfaces of Mg₂NiH₄ nanoparticles in the MgH₂ matrix. Inspired by this mechanism, more general metal hydrides can be explored for catalyzing the hydrogenation of LOHCs. The new application of Mg-based metal hydrides is beneficial to developing efficient LOHC based hydrogen storage systems and offers novel insights to hydride-based catalysts.     

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).     

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.     

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.     

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

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

Efficient and highly rapid hydrogen release from ball-milled 3NH3BH3/MMgH3 (M = Na,K, Rb) mixtures at low temperatures

The stoichiometric reactions of ammonia borane (NH₃BH₃, AB) and selected alkali or alkaline-earth metal hydrides produce metal amidoboranes, which possess dehydrogenation property advantages over their parent AB. However, the losses of hydrogen capacity and chemical energy in the preparation process make metal amidoboranes less energy-effective for hydrogen storage application. In the present study, by combining the M⁺–Mg²⁺ double cations remarkably lowers the reactivity of the alkali metal hydrides toward AB. As a result, the starting Mg-based ternary hydrides MMgH₃ (M = Na, K, Rb) and AB phases are largely stable in the mechanical milling process, but transform to the corresponding mixed-cation amidoboranes in the subsequent heating process. Importantly, when the post-milled 3AB/MMgH₃ mixtures are isothermally heated at above 60 °C using water bath, the formation and decomposition processes of the mixed-cation amidoboranes can be favorably combined, giving rise to rapid and efficient dehydrogenation performances at the mild temperatures (60–80 °C). The results acquired may provide a generalized reactions coupling strategy for designing and synthesis other potentially efficient hydrogen storage system.     

Preparation and hydrogen storage property of Mg-based hydrogen storage composite embedded by polymethyl methacrylate

A novel embedded Mg-based hydrogen storage nanocomposite was prepared by mechanical milling of hydriding combustion synthesized (HCS) Mg-based hydride and hydrogen permissive/oxygen prohibitive polymer. The Mg-based hydride was mechanically milled with tetrahydrofuran solution of polymethyl methacrylate (PMMA) under argon atmosphere. It is determined by X-ray diffraction (XRD) analysis that the average grain size of all the milled nanocomposites become smaller and the nanocomposites exhibit a good air-stable property. The microstructures of the nanocomposites obtained by Field emission scanning electron microscopy (FESEM) and High-resolution transmission electron microscopy (HRTEM) analyses show that Mg₉₅Ni₅ particles embedded by PMMA have a diameter of smaller than 100 nm, approximately. The nanocomposites show the optimal hydriding/dehydriding properties, requiring 60 min to absorb 3.37 wt.% hydrogen at low temperature of 473 K, and desorbing as high as 1.02 wt.% hydrogen within 120 min at the same temperature. The onset dehydriding temperature of the composites is about 373 K, which is 150 K lower than that of HCS products Mg₉₅Ni₅.     

Mg-based composites for enhanced hydrogen storage performance

Hydrogen storage in solids of hydrides is advantageous in comparison to gaseous or liquid storage. Magnesium based materials are being studies for solid-state hydrogen storage due to their advantages of high volumetric and gravimetric hydrogen storage capacity. However, unfavorable thermodynamic and kinetic barriers hinder its practical application. In this work, we presented that kinetics of Mg-based composites were significantly improved during high energy ball milling in presence of various types of carbon, including plasma carbon produced by plasma-reforming of hydrocarbons, activated carbon, and carbon nanotubes. The improvement of the kinetics and de-/re-hydrogenation performance of MgH₂ and TiC-catalysed MgH₂ by introduction of carbon are strongly dependent on the milling time, amount of carbon and carbon structure. The lowest dehydrogenation temperature was observed at 180 °C by the plasma carbon–modified MgH₂/TiC. We found that nanoconfinement of carbon structures stabilised Mg-based nanocomposites and hinders the nanoparticles growth and agglomeration. Plasma carbon was found to show better effects than the other two carbon structures because the plasma carbon contained both few layer graphene sheets that served as an active dispersion matrix and amorphous activated carbons that promoted the spill-over effect of TiC catalysed MgH₂. The strategy in enhancing the kinetics and thermodynamics of Mg-based composites is leading to a better design of metal hydride composites for hydrogen storage.     

Optimization study on a solar-assisted air source heat pump system with energy storage based on the economics method

Currently, hybrid renewable energy systems with thermal energy storage have various advantages and are widely used. This paper investigated the performance of a solar-assisted air source heat pump system with energy storage (SASHPS-ES) in Beijing, China, and proposed an optimal operation mode based on economic evaluation. The results indicate that with the optimal heat storage ratio of 50%, the rated capacity of the air source heat pump (ASHP) of the SASHPS-ES system can be reduced by 16.7%, decreasing its annual total cost by 26.5% under a peak-valley electricity price policy. The price of 620¥/m² is critical for the solar collectors. The economics of SASHPS-ES is better than that of an air source heat pump system with energy storage (ASHPS-ES) when the price of the selected solar collector units is less than this critical price (without subsidies from the government). In the current local market, the promotion of SASHPS-ES systems and other solar energy applications requires government subsidies for a period of time. The results can guide the utilization and popularity of SASHPS-ES in China.     

Polyetherimide-LaNi5 composite films for hydrogen storage applications

This study investigates the preparation of polyetherimide (PEI) – LaNi₅ composites films for hydrogen storage. Prior to the polymer addition, LaNi₅ was ball-milled at different conditions (250, 350, and 450 RPM) and annealed at 500 °C for 1 h under vacuum. The composites were produced with BM-LaNi₅-350 (PEI/LaNi₅-350) and annealed BM-LaNi₅-350 (PEI/LaNi₅-350-TT). Membranes were successfully produced through solvent casting assisted by an ultrasonic bath. The particles dispersion and the film morphology did not change after hydrogenation cycles. In the H₂ sorption experiments at 43 °C and 20 bar, the films stored H₂ without incubation time; both samples reached a capacity of ~0.6 wt%. The H₂ sorption kinetics of PEI/LaNi₅-350 was comparable to that of BM-LaNi₅-350, whereas PEI/LaNi₅-350-TT presented significantly slower kinetics. LaNi₅ oxidation was hindered by PEI, showing that it can be explored to improve metal hydrides air resistance. The results demonstrated that PEI films filled with LaNi₅ are promising materials for hydrogen storage.     

Latent heat storage for solar energy systems: Transient simulation of refrigerant storage

This paper presents a brief review of the available latent heat storage systems for solar energy utilization. A new concept of latent heat storage of solar energy via the refrigerant-absorbent mass storage in absorption cycle heat pump systems used for solar space heating/cooling has been proposed and assessed thermodynamically. A computer modelling and numerical simulation study shows that the concept of refrigerant storage is fundamentally sound, technically feasible and yields the following advantages over other storage methods: (i) the storage capacity per unit volume is high as the latent heat of vaporization of the refrigerant is high; (ii) the heat loss from the storage to the surroundings is minimum as the storage temperature is near the ambient; (iii) prolonged energy storage is possible with no degradation in system performance and hence suitable for combined solar heating and airconditioning. The effects of operating parameters on the energy storage concentration and storage efficiency have been studied in detail.