Hydrogen storage system based on hydride materials incorporating a helical-coil heat exchanger

Metal hydrides offer the potential to store hydrogen at modest pressures and temperatures with high volumetric efficiencies. The process of charging hydrogen into a metal powder to form the hydride is exothermic. The heat released by the reaction must be removed quickly in order to maintain a rapid charging rate. An effective method for heat removal is to embed a heat exchanger within the metal hydride bed. Here, we investigate the effectiveness of a helical coil heat exchanger tube to remove the heat generated during the absorption process. This paper presents a three-dimensional mathematical model formulated in Ansys Fluent 12.1 to evaluate the transient heat and mass transfer in a cylindrical metal hydride tank embedded with a helical-coil cooling tube. We present results from a parametric study of hydrogen storage efficiency as a function of helical coil pitch and convective heat transfer coefficient (h) within the cooling tube. We also explore the effect of adding aluminum foam to enhance the thermal conductivity of the metal hydride. The parametric study reveals that the mass of stored hydrogen is less sensitive to the coil pitch when aluminum foam is added. It is also found that the absorption rate increases with h as expected, although the rate of improvement diminishes at high values of h. Results were examined at filling times of 3 and 6 min to draw conclusions about the overall effectiveness of this hydrogen storage system. At 3 min, it is found that the addition of 5% Al foam is optimal, and h = 1000 W/m²-K is sufficient to bring the metal hydride to saturation; under these conditions a non-dimensional pitch of 0.5 maximizes the hydrogen absorption. Adding Al foam beyond 5% does not improve volumetric efficiency as the Al foam begins to displace the active hydrogen-absorbing material.     

Active disturbance rejection control of metal hydride hydrogen storage

Metal hydride (MH) hydrogen storage is used in both mobile and stationary applications. MH tanks can connect directly to high-pressure electrolyzers for on-demand charging, saving compression costs. To prevent high hydrogen pressure during charging, hydrogen generation needs to be controlled with consideration for unknown disturbances and time-varying dynamics. This work presents a robust control system to determine the appropriate mass flow rate of hydrogen, which the water electrolyzer should produce, to maintain the gaseous hydrogen pressure in the tank for the hydriding reaction. A control-oriented model is developed for MH hydrogen storage for control system design purposes. A proportional-integral (PI) and an active disturbance rejection control (ADRC) feedback controllers are investigated, and their performance is compared. Simulation results show that both the PI and ADRC controllers can reject both noises from the output measurements and unknown disturbances associated with the heat exchanger. ADRC excels in eliminating disturbances produced by the input mass flow rate, maintaining the pressure of the tank at the charging pressure with little oscillations. Additionally, the parameters estimated by the ADRC's extended state observer was used to predict the state-of-charge (SOC) of the MH.     

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.     

Role of heat pipes in improving the hydrogen charging rate in a metal hydride storage tank

Metal hydrides can store hydrogen at high volumetric efficiencies. As the process of charging hydrogen into a metal powder to form its hydride is exothermic, the heat released must be removed quickly to maintain a rapid charging rate. An effective heat removal method is to incorporate a heat exchanger such as a heat pipe within the metal hydride bed. In this paper, we describe a two-dimensional numerical study to predict the transient heat and mass transfer in a cylindrical metal hydride tank embedded with one or more heat pipes. Results from a parametric study of hydrogen storage efficiency are presented as a function of storage tank size, water jacket temperature and its convective heat transfer coefficient, and heat pipe radius and its convective heat transfer coefficient. The effect of enhancing the thermal conductivity of the metal hydride by adding aluminum foam is also investigated. The study reveals that the cooling water jacket temperature and the heat pipe's heat transfer coefficient are most influential in determining the heat removal rate. The addition of aluminum foam reduces the filling time as expected. For larger tanks, more than one heat pipe is necessary for rapid charging. It was found that using more heat pipes of smaller radii is better than using fewer heat pipes with larger radii. The optimal distribution of multiple heat pipes was also determined and it is shown that their relative position within the tank scales with the tank size.     

Accelerating hydrogen absorption in a metal hydride storage tank by physical mixing

A novel method to improve the hydrogen absorption rate in a metal hydride tank is proposed by introducing physical mixing of the metal hydride powder to promote heat removal and accelerate the kinetics of the hydriding process. Experiments were conducted with and without mixing to demonstrate that the hydrogen absorption rate can be improved significantly by mixing. Mixing was achieved by tilting the cylindrical metal hydride tank back and forth by 90° during charging. A mathematical model was also developed to simulate the effects of physical mixing. The model results indicate that physical mixing enhances heat transfer by redistributing the hydride powder from the hot core to the boundary and facilitates heat removal by convection at the tank walls. After validating the model against experimental results, the effect of physical mixing on accelerating hydrogen storage was explored by changing the mixing rate and the convection coefficient at the tank wall, and by increasing the thermal conductivity of the hydride bed by adding aluminum foam. It was found that while higher mixing rates generally improve the absorption rate, the benefits of mixing are reduced for higher convection coefficients, and for higher weight fractions of Al foam. Simulations were also conducted with and without mixing as a function of tank size. The results show that the benefit of physical mixing increases with tank size.     

Numerical analysis on the thermal behavior of high temperature latent heat thermal energy storage system

High temperature latent heat thermal energy storage technology is a promising option for future cost reduction in parabolic trough or tower power plant. However, low thermal conductivity of phase-change material (PCM) is the major shortage of latent heat thermal energy storage. This paper proposed a new thermal energy storage system (TESS) that metal foam and fins were used to enhance the effective conductivity of PCM. Three-dimensional physical model was established for representative element extracted from TESS. Considering the natural convection in the liquid part of PCM, volume-averaged mass and momentum equations were employed with the Brinkman–Forchheimer extension to Darcy law to simulate the porous resistance. A local thermal equilibrium model was developed to obtain temperature field. The governing equations were solved with finite-volume approach and enthalpy method was employed to account for phase change. The model was firstly validated against low temperature experiments from the literature and then used to predict the charging and discharging behavior of the present TESS. The position of solid/liquid interface was explored and the effects of design parameters, including that of metal foam pore density and porosity, configuration of fin and Rayleigh number, on melting and solidifying rate and energy stored in each time step were revealed and discussed. The results indicate that metal foam and fins can effectively improve the heat transfer performance for thermal storage system and decrease charging and discharging time.     

Experimental studies on industrial scale metal hydride based hydrogen storage system with embedded cooling tubes

The present article reports the activation and testing of large scale metal hydride based hydrogen storage system (MHHSS) for industrial application. The metal hydride reactor is fabricated using SS316 material with 99 embedded cooling tube and filled with 40 kg of LaNi_4.7Al_0.3. The activation was carried out by successive absorption and desorption processes. In the third absorption cycle, MHHSS had absorbed 552.356 g of hydrogen to reach a maximum storage capacity of 1.4 wt% at 40 bar pressure and 30 °C temperature. The testing of MHHSS was carried out by varying H₂ supply pressure, absorption and desorption temperatures and heat transfer fluid (HTF) flow rate. It was observed that the supply pressure has significant effect on absorption rate, and the optimum supply pressure was observed in the range of 10–15 bar. Similarly, during the desorption cycle, optimum desorption temperature was found in the range of 80–90 °C. The optimum flow velocity for HTF was observed in the range of 20–30 lpm.     

Metal hydride material requirements for automotive hydrogen storage systems

The United States Department of Energy (DOE) has published a progression of technical targets to be satisfied by on-board rechargeable hydrogen storage systems in light-duty vehicles. By combining simplified storage system and vehicle models with interpolated data from metal hydride databases, we obtain material-level requirements for metal hydrides that can be assembled into systems that satisfy the DOE targets for 2017. We assume minimal balance-of-plant components for systems with and without a hydrogen combustion loop for supplemental heating. Tank weight and volume are driven by the stringent requirements for refueling time. The resulting requirements suggest that, at least for this specific application, no current on-board rechargeable metal hydride satisfies these requirements.     

Development of hydrogen storage reactor using composite of metal hydride materials with ENG

Hydrogen is widely accepted as a promising energy carrier replacing fossil fuels. In this context hydrogen storage is one of the critical challenges in realizing hydrogen economy which relies on hydrogen as the commercial fuel. Due to very low volumetric energy density of pure hydrogen, it is highly compressed as a gas phase or liquified at extremely low temperature. However, chemically combined state in other materials has advantages in terms of storage conditions and associated safety concerns.The present study focuses on a development of a hydrogen storage applicable to special fuel cell (FC) mobilities such as forklift but not limited to. We adopts a solid-state storage method using metal hydride composite prepared by processing La_0.9Ce_0.1Ni₅ and extended natural graphite (ENG). The isothermal hydrogen absorption/desorption behavior of the composite is measured at 20–80 °C. The results suggest that around 10 bar is sufficient to store 1.2 wt% of hydrogen. A cylindrical reactor is manufactured and experiments are carried out with the fabricated hydrogen storage material by changing operation conditions. The results of satisfaction are obtained in terms of the amount of hydrogen storage (>83 standard liter) and the absorption time (~10 min) under relatively moderate conditions of temperature (~19 °C) and pressure (~11 bar).As for scaling-up, a reactor of 2.0 kWh is designed based on the experimental results. CFD analysis is performed based on the hottest operation conditions focusing on a cooling water flow. The flow pattern and the temperature distribution of the cooling water are expected to be adequate not deviating from the stable operating conditions. CFD would be further applied to optimize the incorporated modular reactors.     

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

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

Hydrogen desorption from a hydride container under different heat exchange conditions

The desorption behavior of a hydrogen storage prototype loaded with AB₅H₆ hydride, whose equilibrium pressure makes it suitable for both feeding a PEM fuel cell and being charged directly from a low pressure water electrolyzer without need of additional compression, was studied. The nominal 70 L hydrogen storage capacity of the container (T = 20 °C, P = 101.3 kPa) suffices for ca. 2.5 h operation of a 50 W hydrogen/oxygen fuel cell stack. The hydride container is provided with aluminum extended surfaces to enhance heat exchange with the surrounding medium. These surfaces consist of internal disk-shaped metal foils and external axial fins. The characterization of the storage prototype at different hydrogen discharge flow rates was made by monitoring the internal pressure and the temperatures of the external wall and at the center inside the container.     

Hydrogen storage and thermal conductivity properties of Mg-based materials with different structures

Mg-based hydrogen storage materials can be very promising candidates for stationary energy storage application due to the high energy density and low cost of Mg. Hydrogen storage kinetics and thermal conductivity are two important factors for the material development for this kind of application. Here we studied several types of Mg-based materials with different structure-micrometer scale Mg powders, Mg nanoparticles, single crystal Mg, nanocrystalline Mg₅₀Co₅₀ BCC alloy and Mg thin film samples. It seems the Mg materials with good kinetics usually are the ones with nanostructure and tend to show poor thermal conductivity due to electron/phonon scattering resulting from more interfaces and boundaries in nanomaterials. Based on this work, good crystallinity Mg phase incorporated in carbon nano framework could be one promising option for energy storage.     

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

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

Optimization of heat exchanger designs in metal hydride based hydrogen storage systems

Design of the heat exchanger in a metal hydride based hydrogen storage system influences the storage capacity, gravimetric hydrogen storage density, and refueling time for automotive on-board hydrogen storage systems. The choice of a storage bed design incorporating the heat exchanger and the corresponding geometrical design parameters is not obvious. A systematic study is presented to optimize the heat exchanger design using computational fluid dynamics (CFD) modeling. Three different shell and tube heat exchanger designs are chosen. In the first design, metal hydride is present in the shell and heat transfer fluid flows through straight parallel cooling tubes placed inside the bed. The cooling tubes are interconnected by conducting fins. In the second design, heat transfer fluid flows through helical tubes in the bed. The helical tube design permits use of a specific maximum distance between the metal hydride and the coolant for removing heat during refueling. In the third design, the metal hydride is present in the tubes and the fluid flows through the shell. An automated tool is generated using COMSOL-MATLAB integration to arrive at the optimal geometric parameters for each design type. Using sodium alanate as the reference storage material, the relative merits of each design are analyzed and a comparison of the gravimetric and volumetric hydrogen storage densities for the three designs is presented.     

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.     

Hydrogen storage property of sandwiched magnesium hydride nanoparticle thin film

Hydrogen sorption property of magnesium (Mg) in the form of sandwiched Pd/Mg/Pd films is investigated. Pulsed laser deposition method was applied to deposit the samples consisting of films of nanoparticles. The enthalpy of formation of MgH₂ was found to be −68 kJ/mol H₂ for films with nanoparticle size on the order of 50 nm, which is smaller than the value for bulk MgH₂ and may be explained by the concept of excess volume.     

Numerical study on hydrogen and thermal storage performance of a sandwich reaction bed filled with metal hydride and thermochemical material

Hydrogen storage and release process of metal hydride (MH) accompany with large amount of reaction heat. The thermal management is very important to improve the comprehensive performance of hydrogen storage unit. In present paper, thermochemical material (TCM) is used to storage and release the reaction heat, and a new sandwich configuration reaction bed of MH-TCM system was proposed and its superior hydrogen and thermal storage performance were numerically validated. Firstly, the optimum TCM distribution with a volume ratio (TCM in inner layer to total) of 0.4 was derived for the sandwich bed. Then, comparisons between the sandwich reaction bed and the traditional reaction bed were performed. The results show that the sandwich MH-TCM system has faster heat transfer and reaction rate due to its larger heat transfer area and smaller thermal resistance, which results in the hydrogen storage time is shortened by 61.1%. The heat transfer in the reaction beds have significant effects on performance of MH-TCM systems. Increasing the thermal conductivity of the reaction beds can further reduce the hydrogen storage time. Moreover, improving the hydrogen inflation pressure can result in higher equilibrium temperature, which is beneficial for the enhancing heat transfer and hydrogen absorption rates.