Hydride Storage Research Articles

Metal Hydride Storage Systems: Approaches to Improve Their Performances

AbstractMetal hydrides provide a safe and efficient way to store hydrogen. However, current metal hydride storage systems, i.e., hydrides incorporated within a storage tank, are far from efficient. Depending on the design, (dis)charging rates may be very long. However, this can be significantly improved by implementing strategies tackling the issue of heat management at the level of: i) the metal hydride bed, and ii) the overall storage system design. This review summarises recent progress in tackling heat management of hydride systems. In this respect, modeling has emerged as a powerful tool. In particular, simulation results show that the compaction of hydride powders with binders and the use of metal foams are both effective in lifting the poor thermal conductivity of hydride beds. For tank designs, cylindrical shapes remain the preferred choice because of the flexibility and ease of supplementing heat management with fins and tubular heat exchangers. The addition of phase change materials to the hydride tank can lead to further heat storage, but any add‐on to simple hydride tanks can only lead to cumbersome systems. It is still a fine art to tune the thermal conductivity of hydride beds while selecting a suitable metal hydride alloy composition.

Towards standalone commercial buildings in the Mediterranean climate using a hybrid metal hydride and battery energy storage system

Given the critical role of hybrid energy storage systems in the building sector for enhancing renewable energy reliability and integration, this study examines the techno-economic feasibility of adopting a dual-level energy storage system for a PV-driven commercial building in the Mediterranean climate. The proposed system encompasses both hydrogen metal hydride and battery storage units. Aimed at off-grid electrification, the optimal component sizing of the hybrid system is identified by establishing a statistical optimization framework using the response surface methodology. Dynamic simulations of the hybrid system are performed through a TRNSYS model coupled with a numerical code that simulates the metal hydride system. Regarding optimal net-zero solutions, it is shown that the share of the direct PV electricity supply to end-use fluctuates within a limited range for all scenarios, namely between 57.7 and 60.5 %, while the share of each storage system varies distinctively in each solution. The results indicate a striking difference between scenarios in terms of economic aspects; differences of $ 19,791 and $ 32,621 are observed between the minimum and maximum values of the initial investment and life cycle cost, respectively. The levelized cost of electricity varies between 0.354 and 0.403 $/kWh, in which the case having the lowest payback period (10.8 years) demonstrates the lowest levelized cost of electricity too. Furthermore, an inverse relationship between the levelized cost of hydrogen and production rate is observed; the lowest levelized cost and the highest annual production are achieved in the scenario with the lowest BESS capacity and the highest electrolyzer power and hydrogen storage volume, which are equal to 5.77 $/kg and 304.7 kg H2/yr, respectively.

Exploring the hydrogen storage in novel perovskite hydrides: A DFT study

This work employs density functional theory calculations to investigate the structural, hydrogen storage, mechanical, electronic, optical, and bonding characteristics of perovskite hydrides KNaX2H6 (X = Mg, Ca) for potential hydrogen storage applications. Negative formation energies, positive phonon dispersions, and appropriate tolerance factor values confirm the thermodynamic, dynamic, and cubic structural stability of these compounds. KNaMg2H6 exhibits a promising gravimetric hydrogen storage capacity of 5.19%, while KNaCa2H6 shows 4.09%. Both compounds display semiconducting behavior with indirect energy band gaps of 3.31 eV and 3.17 eV, respectively. Key mechanical properties, including bulk modulus, shear modulus, and Poisson's ratio, were evaluated using computed elastic constants. The desorption temperature for KNaMg2H6, determined to be 470.4 K, renders it suitable for practical applications. Partial Bader charge analysis reveals both ionic and slightly covalent bonding interactions. Optical analysis demonstrates strong ultraviolet absorption capabilities with a redshift in the absorption spectrum. The computed properties indicate these materials hold promise for hydrogen storage applications.

Optimization of cold startup strategy with quasi 2-D model of metal hydride hydrogen storage with fuel cell

In this work, a novel cold startup strategy is presented for a large-scale metal hydride–fuel cell system. Due to the thermal requirement of the system, when the initial temperature of metal hydride and ambient air is low, the system cannot be started because the hydrogen pressure in the metal hydrides storage system is lower than the minimal pressure required by the fuel cell. The cold startup is achieved by maintaining a part of metal hydride storage at a target temperature and using coolant control to transfer heat to the remaining cold metal hydride storage upon operation of the fuel cells. The strategy is studied numerically and a novel Quasi-2-Dimensional approach is developed to describe heat transfer within metal hydrides and validated. By the proper selection of the value of the control variable, both fast startup and immediate uninterrupted fuel cell power supply are achieved. The effect of initial conditions on the startup process is studied and the strategy consumed 30 % less energy than the alternative without control. The proposed strategy is suitable and efficient for the cold startup of large-scale metal hydride-fuel cell systems.

Analysis of Power-to-gas-to-X systems with metal hydride storage based on coupled electrochemical and thermodynamic simulation

Power-to-gas-to-X systems consisting of photovoltaic cells, proton-exchange membrane electrolysis, hydrogen storage based on metal hydrides, proton-exchange membrane fuel cells and buffer batteries could be used to meet heat and electricity demands of homes, businesses, or small districts. The actual size of the individual components and their interplay have to be optimized for the technical and economic feasibility of the overall system. A simulation-based optimization workflow would be a suitable way to accomplish this task, but there are hardly any tools that can simultaneously simulate power, fluid and heat flows of such systems and efficiently perform their optimization. In this paper, a multiphysical energy system simulation and optimization tool is introduced which models electrochemical and thermodynamic processes simultaneously, including modern equations of state and an own numerical solver for the arising differential–algebraic system of equations, and provides new methods for the calibration of parameters of the metal hydride storage, proton-exchange membrane electrolyzer and fuel cell as well as a metamodel-based approach for sizing optimization. As a demonstrator for the novel tool, a simulation model of a hydrogen lab is successfully set up based on experimental results. The novel tool is able to extract polarization and jump curves of the fuel cell, determine a first temperature and pressure dependency of the efficiency of the electrolysis coupled with the metal hydride storage and speed up sizing optimization through metamodeling by a factor 262.1 at 4.9% and 32.7 at 3.3% accuracy.

Sensitivity analysis and calibration for a two-dimensional state-space model of metal hydride storage tanks based on experimental data

In this paper, a state-space model of a metal hydride tank is formulated and analyzed in detail. Firstly, a three-dimensional state-space model of the metal hydride tank is simplified by assuming that the tank temperature can be measured. Secondly, the model is completed with a pipe model, which allows to compute the input flow from the pipe pressure that can be easily measured. The proposed model solves the problem that the conventional metal hydride tank models usually take the mass flow rate as input and ignore the pressure as system input. Thirdly, the first-order trajectory sensitivity analysis method is adopted to determine the sensitivity of selected unknown parameters. Latter, the particle swarm optimization algorithm is used to estimate the unknown model parameters from experimental data. Finally, a comparison between experimental data and simulation results demonstrates that the proposed model can reflect the dynamic characteristics of the metal hydride tank.

Techno-economic feasibility of integrating hybrid battery-hydrogen energy storage system into an academic building

Green hydrogen production and storage are vital in mitigating carbon emissions and sustainable transition. However, the high investment cost and management requirements are the bottleneck of utilizing hybrid hydrogen-based systems in microgrids. Given the necessity of cost-effective and optimal design of these systems, the present study examines techno-economic feasibility of integrating hybrid hydrogen-based systems into an outdoor test facility. With this perspective, several solar-driven hybrid scenarios are introduced at two energy storage levels, namely the battery and hydrogen energy storage systems, including the high-pressure gaseous hydrogen and metal hydride storage tanks. Dynamic simulations are carried out to address subtle interactions in components of the hybrid system by establishing a TRNSYS model coupled to a Fortran code simulating the metal hydride storage system. The OpenStudio-EnergyPlus plugin is used to simulate the building load, validate against experimental data, according to the measured data and monitored operating conditions. Aimed at enabling efficient integration of energy storage systems, a techno-enviro-economic optimization algorithm is developed to simultaneously minimize the levelized cost of the electricity and maximize the CO2 mitigation in each proposed hybrid scenario. The results indicate that integrating the gaseous hydrogen and metal hydride storages into the photovoltaic-alone scenario enhances 22.6% and 14.4% of the annual renewable factor. Accordingly, the inclusion of battery system to these hybrid scenarios gives a 30.4% and 20.3 % boost to the renewable factor value, respectively. Although the inclusion of battery energy storage into the hybrid systems increases the renewable factor, the results imply that it reduces the hydrogen production rate via electrolysis. The optimized values of the levelized cost of electricity and CO2 emission for different scenarios vary in the range of 0.376–0.789 $/kWh and 6.57–9.75 ton, respectively. The multi-criteria optimizations improve the levelized cost of electricity and CO2 emission by up to 46.2% and 11.3%, with respect to their preliminary design.

In situ TEM studies on hydrogen-related issues: hydrogen storage, hydrogen embrittlement, fuel cells and electrolysis.

Hydrogen is attracting attention as an energy carrier for realizing a low-carbon society, because it can directly convert the energy obtained from chemical reactions into electrical energy without carbon dioxide emissions. This paper presents in situ transmission electron microscopy (TEM) observations related to hydrogen storage in metal and metal hydrides, hydrogen embrittlement of metallic materials used for storing and transporting hydrogen in containers and pipes, and fuel cells and water electrolysis using metal catalysts and oxides as electrode materials. All of these processes are important for practical applications of hydrogen. Numerous in situ TEM studies have revealed the microscopic structural changes when hydrogen reacts with the materials, when hydrogen is solidly dissolved in the materials and during the operation of the material. This review is expected to facilitate further development of TEM operando observations of hydrogen-related materials.

Can hydrogen storage in metal hydrides be economically competitive with compressed and liquid hydrogen storage? A techno-economical perspective for the maritime sector

The aim of this work is to evaluate if metal hydride hydrogen storage tanks are a competitive alternative for onboard hydrogen storage in the maritime sector, when compared to compressed gas and liquid hydrogen storage. This is done by modelling different hydrogen supply and onboard storage scenarios and evaluating their levelized cost of hydrogen variables. The levelized cost of hydrogen for each case is calculated considering the main components that are required for the refueling infrastructure and adding up the costs of hydrogen production, compression, transport, onshore storage, dispensing, and the cost of the onboard tanks when known. The results show that the simpler refueling needs of metal hydride-based onboard tanks result in a significant cost reduction of the hydrogen handling equipment. This provides a substantial leeway for the investment costs of metal hydride-based storage, which, depending on the scenario, can be between 3400 - 7300 EUR/kgH2 while remaining competitive with compressed hydrogen storage.

Techno-economic analysis and optimization of green hydrogen production and liquefaction with metal hydride storage

A techno-economic analysis and three-objective optimization are reported for a system that uses a renewable energy source (RES) for hydrogen production and liquefaction in which all the produced hydrogen enters the liquefaction cycle. The system works in three phases; hydrogen liquefaction, hydrogen storage and fuel cell power generation. Every second, the mass of produced hydrogen from the electrolyzer is calculated and immediately injected into the liquefaction cycle. This happens for 3600 s during each hour and for 12 h during the day. To reduce the execution time and increase the accuracy, six different artificial neural network (ANN) models have been used, which are optimized using genetic algorithm (GA). Decision variables for optimization include solar irradiation intensity, ambient temperature, heat exchanger efficiency, and isothermal compressor output pressure. The objective functions are chosen to be total exergy efficiency, liquefaction efficiency, and total cost rate, and the optimal values of the objective functions are found to be 19.3%, 19.8%, and 10.6 $/hr, respectively. The objective functions are illustrated in terms of daily time, as well as decision variables. Also, the effect of liquefaction efficiency and specific work consumption on liquefaction cycle parameters and electrolyzer temperature have been investigated. The results show that in the range of compressor output pressure between 5 and 15 MPa, for every n % increase in heat exchanger efficiency, the liquefaction efficiency increases by (n/2) % and the amount of liquid hydrogen production at steady-state becomes 0.162 kg/h. It is also found that if the storage system is turned off and all the produced power is given to the liquefaction system, the mass of liquefied hydrogen will increase by 17% at the end of the day.

A Newly Proposed Method for Hydrogen Storage in a Metal Hydride Storage Tank Intended for Maritime and Inland Shipping

The utilisation of hydrogen in ships has important potential in terms of achieving the decarbonisation of waterway transport, which produces approximately 3% of the world’s total emissions. However, the utilisation of hydrogen drives in maritime and inland shipping is conditioned by the efficient and safe storage of hydrogen as an energy carrier on ship decks. Regardless of the type, the constructional design and the purpose of the aforesaid vessels, the preferred method for hydrogen storage on ships is currently high-pressure storage, with an operating pressure of the fuel storage tanks amounting to tens of MPa. Alternative methods for hydrogen storage include storing the hydrogen in its liquid form, or in hydrides as adsorbed hydrogen and reformed fuels. In the present article, a method for hydrogen storage in metal hydrides is discussed, particularly in a certified low-pressure metal hydride storage tank—the MNTZV-159. The article also analyses the 2D heat conduction in a transversal cross-section of the MNTZV-159 storage tank, for the purpose of creating a final design of the shape of a heat exchanger (intensifier) that will help to shorten the total time of hydrogen absorption into the alloy, i.e., the filling process. Based on the performed 3D calculations for heat conduction, the optimisation and implementation of the intensifier into the internal volume of a metal hydride alloy will increase the performance efficiency of the shell heat exchanger of the MNTZV-159 storage tank. The optimised design increased the cooling power by 46.1%, which shortened the refuelling time by 41% to 2351 s. During that time, the cooling system, which comprised the newly designed internal heat transfer intensifier, was capable of eliminating the total heat from the surface of the storage tank, thus preventing a pressure increase above the allowable value of 30 bar.

Nanoparticulate ZrNi: In Situ Disproportionation Effectively Enhances Hydrogen Cycling of MgH2.

High thermal stability and sluggish absorption/desorption kinetics are still important limitations for using magnesium hydride (MgH2) as a solid-state hydrogen storage medium. One of the most effective solutions in improving hydrogen storage properties of MgH2 is to introduce a suitable catalyst. Herein, a novel nanoparticulate ZrNi with 10-60 nm in size was successfully prepared by co-precipitation followed by a molten-salt reduction process. The 7 wt % nano-ZrNi-catalyzed MgH2 composite desorbs 6.1 wt % hydrogen starting from ∼178 °C after activation, lowered by 99 °C relative to the pristine MgH2 (∼277 °C). The dehydrided sample rapidly absorbs ∼5.5 wt % H2 when operating at 150 °C for 8 min. The remarkably improved hydrogen storage properties are reasonably ascribed to the in situ formation of ZrH2, ZrNi2, and Mg2NiH4 caused by the disproportionation reaction of nano-ZrNi during the first de-/hydrogenation cycle. These catalytic active species are uniformly dispersed in the MgH2 matrix, thus creating a multielement, multiphase, and multivalent environment, which not only largely favors the breaking and rebonding of H-H bonds and the transfer of electrons between H- and Mg2+ but also provides multiple hydrogen diffusion channels. These findings are of particularly scientific importance for the design and preparation of highly active catalysts for hydrogen storage in light-metal hydrides.

NADH-Type Hydride Storage and Release on a Functional Ligand for Efficient and Selective Hydrogenation Catalysis

NADH-Type Hydride Storage and Release on a Functional Ligand for Efficient and Selective Hydrogenation Catalysis

The Effect of Severe Plastic Deformation on the Hydrogen Storage Properties of Metal Hydrides

Solid-state hydrogen storage in various metal hydrides is among the most promising and clean way of storing energy, however, some problems, such as sluggish kinetics and high dehydrogenation temperature should be dealt with. In the present paper the advances of severe plastic deformation on the hydrogenation performance of metal hydrides will be reviewed. Techniques, like high-pressure torsion, equal-channel angular pressing, cold rolling, fast forging and surface modification have been widely applied to induce lattice defects, nanocrystallization and the formation of abundant grain boundaries in bulk samples and they have the potential to up-scale material production. These plastically deformed materials exhibit not only better H-sorption properties than their undeformed counterparts, but they possess better cycling performance, especially when catalysts are mixed with the host alloy promoting potential future applications.

A comprehensive assessment of energy storage options for green hydrogen

The current study investigates suitable hydrogen storage technologies for hydrogen produced by renewable energy resources in a green manner. Type-I, III, and IV high-pressure tanks, adsorbent storage, metal hydride storage and chemical storage options are investigated and compared based on their hydrogen storage capacities, costs, masses and greenhouse gas (GHG) emissions. The results of this study show that in a Type-IV hydrogen storage tank (i.e., composite material tank of carbon fiber with thermoplastic polymer liners), increasing the tank pressure from 100 bar to 800 bar increases the hydrogen holding capacity by 457.7%. Regarding the environmental impact, the lowest GHG emissions appear to be the lowest for liquid hydrogen storage with an average of 3.5 CO2eq/kg-H2 while the respective emissions become the highest in metal hydride storage tanks as 113.6 CO2eq/kg-H2. Furthermore, hydrogen storage capacity for Type-IV tanks varies from 1.94 kg at 100 bar to 15.69 kg at 1500 bar in a 250 L tank. In chemical hydride storage tanks, the stored H2 mass will be 40.75 kg for 100 L, 128.39 kg for 200 L, 216.03 kg for 300 L, 303.67 kg for 400 L, 391.31 kg for 500 L and 478.96 kg for 600 L, respectively. Moreover, hydrogen storage, distribution and dispensing are considered critically important in hydrogen logistics and the results of this study will help better guide policymakers to establish effective policies and increase renewable energy penetration in the energy market.

Graphene Supports for Metal Hydride and Energy Storage Applications

Energy production, distribution, and storage remain paramount to a variety of applications that reflect on our daily lives, from renewable energy systems, to electric vehicles and consumer electronics. Hydrogen is the sole element promising high energy, emission-free, and sustainable energy, and metal hydrides in particular have been investigated as promising materials for this purpose. While offering the highest gravimetric and volumetric hydrogen storage capacity of all known materials, metal hydrides are plagued by some serious deficiencies, such as poor kinetics, high activation energies that lead to high operating temperatures, poor recyclability, and/or stability, while environmental considerations related to the treatment of end-of-life fuel disposal are also of concern. A strategy to overcome these limitations is offered by nanotechnology, namely embedding reactive hydride compounds in nanosized supports such as graphene. Graphene is a 2D carbon material featuring unique mechanical, thermal, and electronic properties, which all recommend its use as the support for metal hydrides. With its high surface area, excellent mechanical strength, and thermal conductivity parameters, graphene can serve as the support for simple and complex hydrides as well as RHC (reactive hydride composites), producing nanocomposites with very attractive hydrogen storage properties.

A 2-Anilidomethylpyridine Ligand Framework Showcasing Hydride Storage and Transfer Abilities in Its Aluminum Chemistry.

Dearomatized 1,4-dihydropyridyl motifs are significant in both chemistry and biology for their potential abilities to deliver the stored hydride, driven by rearomatization. Biological cofactors like nicotinamide adenine dinucleotide (NADH) and organic 'hydride sources' like Hantzsch esters are prime examples. An organoaluminum chemistry on a 2-anilidomethylpyridine framework is reported, where such hydride storage and transfer abilities are displayed by the ligand's pyridyl unit. The pyridylmethylaniline proligand (NN LH) is simultaneously deprotonated and 1,4-hydroaluminated by AlH3 (NMe2 Et) to [(NN Lde )AlH(NMe2 Et)] (1; NN Lde =hydride-inserted dearomatized version of NN L). A hydride abstraction by B(C6 F5 )3 rearomatizes the pyridyl moiety to give the cationic aluminum hydride [(NN L)AlH(NMe2 Et)][HB(C6 F5 )3 ] (6). Notably, such chemical non-innocence is priorly unseen in this established ligand class. The hydroalumination mechanism is investigated by isolating the intermediate [(NN L)AlH2 ] (2) and by control experiments, and is also analyzed by DFT calculation. The results advocate an intriguing 'self-promoting' pathway, which underlines alane's Lewis acid/Brønsted base duality. NMe2 Et carrying the alane also plays a crucial role. In contrast, the chemistry between NN LH and AlMe3 is much different, giving only [(NN L)AlMe2 ] (4) from the adduct [(NN LH)AlMe3 ] (3) by deprotonation but not a subsequent pyridyl dearomatization in the presence or absence of NMe2 Et. This divergence is also justified by DFT analyses.

Experimental studies on novel multi tubular reactor with shell having integrated buffer storage

This study concentrates on experimental analysis of a large scale metal hydride based hydrogen storage reactor having 50 kg LaNi5. In order to cater the heat transfer limitations of hydrogen storage in large scale systems, the present design have been developed as multi tubular reactor with shell having integrated buffer storage configuration with 7 tubes supported by means of 4 baffles having total 50 kg LaNi5 distributed equally among them and water as heat transfer fluid flows across the shell for heat transfer. The experimental study was performed for studying the absorption and desorption performance of the present hydrogen reactor wherein in case of absorption the parameters varied were HTF flow rate at 30 °C and supply pressure of hydrogen and in case of desorption which was carried out at atmospheric pressure, HTF flow rate and HTF temperature were varied. The metal hydride reactor reversibly stores 680 g of hydrogen amounting to 1.34 wt% of gravimetric capacity of metal hydride and equivalent energy storage of 10.4 MJ. In case of absorption, when the flow rate selected was 20 LPM the absorption time for 90 % reaction completion was observed to be 1286 s (21.4 min) at 30 bar H2 supply pressure. In case of desorption studies, it was observed that the varying flow rate from 15 to 25 LPM has negligible effect on hydrogen desorption hence 15 LPM was selected as flow rate for further desorption experiments. Further increasing HTF temperature from 60 °C to 80 °C improves the performance significantly.

Dehydrogenation and low-pressure hydrogenation properties of NaAlH4 confined in mesoporous carbon black for hydrogen storage

For hydrogen to be successfully used as an energy carrier in a new renewable energy driven economy, more efficient hydrogen storage technologies have to be found. Solid-state hydrogen storage in complex metal hydrides, such as sodium alanate (NaAlH4), is a well-researched candidate for this application. A series of NaAlH4/mesoporous carbon black composites, with high NaAlH4 content (50–90 wt%), prepared via ball milling have demonstrated significantly lower dehydrogenation temperatures with intense dehydrogenation starting at ∼373 K compared to bulk alanate's ≥ 456 K. Dehydrogenation/hydrogenation cycling experiments have demonstrated partial hydrogenation at 6 MPa H2 and 423 K. The cycling experiments combined with temperature-programmed dehydrogenation and powder X-ray diffraction have given insight into the fundamental processes driving the H2 release and uptake in the NaAlH4/carbon composites. It is established that most of the hydrogenation behavior can be attributed to the Na3AlH6 ↔ NaH transition.

Constructal design of weight optimized metal hydride storage device embedded with ribbed honeycomb

Solid state storage of hydrogen offers few advantages over compressed and liquefied forms. As heat transfer being the major factor controlling charging and discharging, several thermal enhancement methods were reported in literature. However parasitic weight of thermal enhancement structures embedded to the storage bed can reduce its gravimetric storage capacity. As total weight of the device for given hydrogenation capacity and charging rate being an important factor, these structures needs to be weight optimized. The present study propose a ribbed honeycomb embedded to the multi-tubular storage device with sodium alanate as the storage alloy. The shape and size of this conform to the constructal law, analogous to bio transport systems. This ensures efficient transfer of sorption heat from the point of maximum temperature in the hydride bed to the coolant. The device designed for charging 0.01 kg of hydrogen in 10 min weighs 1.2 kg at optimum length/thickness ratio. This numerical study is conducted using COMSOL Multiphysics™ commercial code.