Experimental study of hydrogen storage with reaction heat recovery using metal hydride in a totalized hydrogen energy utilization system

Experimental results for hydrogen storage tanks with metal hydrides used for load leveling of electricity in commercial buildings are described. Variability in electricity demand due to air conditioning of commercial buildings necessitates installation of on-site energy storage. Here, we propose a totalized hydrogen energy utilization system (THEUS) as an on-site energy storage system, present feasibility test results for this system with a metal hydride tank, and discuss the energy efficiency of the system. This system uses a water electrolyzer to store electricity energy via hydrogen at night and uses fuel cells to generate power during the day. The system also utilizes the cold heat of reaction heat during the hydrogen desorption process for air conditioning. The storage tank has a shell-like structure and tube heat exchangers and contains 50 kg of metal hydride. Experimental conditions were specifically designed to regulate the pressure and temperature range. Absorption and desorption of 5,400 NL of hydrogen was successfully attained when the absorption rate was 10 NL/min and desorption rate was 6.9 NL/min. A 24-h cycle experiment emulating hydrogen generation at night and power generation during the day revealed that the system achieved a ratio of recovered thermal energy to the entire reaction heat of the hydrogen storage system of 43.2% without heat loss.     

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.     

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

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

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.     

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.     

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.     

Numerical simulation of heat and mass transfer in metal hydride hydrogen storage tanks for fuel cell vehicles

This paper presents a two-dimensional mathematical model to optimized heat and mass transfer in metal hydride storage tanks (hereinafter MHSTs) for fuel cell vehicles, equipped with finned spiral tube heat exchangers. This model which considers complex heat and mass transfer was numerically solved and validated by comparison with experimental data and a good agreement is obtained.     

A hydrogen purification and storage system using metal hydride

This work is to develop a new hydrogen purification and storage system for daily start and stop (DSS) operations. The new system enables us to minimize emissions of carbon dioxide by using compact and highly efficient fuel cells. The new system first removes carbon monoxide, which is poisonous to metal hydride, from reformed gas by using a special carbon monoxide adsorbent. After removing carbon monoxide, the reformed gas is introduced to a metal hydride bed to purify and store hydrogen. Some 100 NL/h Laboratory scale apparatus was operated in daily start and stop operations for 100 cycles for a total of 150 h with quite good efficiency. The new process has achieved an 83% hydrogen recovery ratio in one-month DSS operations.     

Three-dimensional modeling and simulation of hydrogen absorption in metal hydride hydrogen storage vessels

In this paper, a three-dimensional hydrogen absorption model is developed to precisely study the hydrogen absorption reaction and resultant heat and mass transport phenomena in metal hydride hydrogen storage vessels. The 3D model is first experimentally validated against the temperature evolution data available in the literature. In addition to model validation, the detailed 3D simulation results show that at the initial absorption stage, the vessel temperature and H/M ratio distributions are uniform throughout the entire vessel, indicating that hydrogen absorption is very efficient early during the hydriding process; thus, the local cooling effect is not influential. On the other hand, non-uniform distributions are predicted at the subsequent absorption stage, which is mainly due to differential degrees of cooling between the vessel wall and core regions. In addition, a parametric study is carried out for various designs and hydrogen feed pressures. This numerical study provides a fundamental understanding of the detailed heat and mass transfer phenomena during the hydrogen absorption process and further indicates that efficient design of the storage vessel and cooling system is critical to achieve rapid hydrogen charging performance.     

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.     

Model-based design of an automotive-scale,metal hydride hydrogen storage system

Sandia and General Motors have successfully designed, fabricated, and experimentally operated a vehicle-scale hydrogen storage demonstration system using sodium alanates. The demonstration system module design and the system control strategies were enabled by experiment-based, computational simulations that included heat and mass transfer coupled with chemical kinetics. Module heat exchange systems were optimized using multi-dimensional models of coupled fluid dynamics and heat transfer. Chemical kinetics models were coupled with both heat and mass transfer calculations to design the sodium alanate vessels. Fluid flow distribution was a key aspect of the design for the hydrogen storage modules and computational simulations were used to balance heat transfer with fluid pressure requirements.     

Thermal management of metal hydride hydrogen storage reservoir using phase change materials

Metal hydride hydrogen storage reservoir should be carefully designed to achieve acceptable performance due to significant thermal effect on the system during hydriding/dehydriding. Phase change materials can be applied to metal hydride hydrogen storage system in order to improve the system performance. A transient two-dimensional axisymmetric numerical model for the metal hydride reservoir packed with LaNi₅ has been developed on Comsol platform, which was validated by comparing the simulation results with the experiment data from other work. Then, the performances of metal hydride hydrogen storage reservoir using phase change materials were predicted. The effects of some parameters, such as the thermal conductivity, the mass and the latent heat of fusion of the phase change materials, on the metal hydride hydrogen storage reservoir were discussed. The results shown that it was good way to improve the efficiency of the system by increasing the thermal conductivity of phase change materials and selecting a relatively larger latent heat of fusion. Due to the relatively lower thermal conductivity of phase change materials, different metal foams were composited with the phase change materials in order to improve the heat transfer from the metal hydride bed to the phase change materials and the hydrogen storage efficiency. The effect of aluminium foam on the metal hydride reservoir was studied and validated. The phase change materials composited with copper foam shown better performance than that composited with aluminium foam.     

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.     

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.     

Design tool for estimating metal hydride storage system characteristics for light-duty hydrogen fuel cell vehicles

The U.S. Department of Energy (DOE) has developed the Framework model to simulate fuel cell-based light-duty vehicle operation for various hydrogen storage systems. This transient model simulates the performance of the storage system, fuel cell, and vehicle for comparison to DOE's Technical Targets using four drive cycles. Metal hydride hydrogen storage models have been developed for the Framework model. Despite the utility of this model, it requires that material researchers input system design specifications that cannot be easily estimated. To address this challenge, a design tool has been developed that allows researchers to directly enter physical and thermodynamic metal hydride properties into a simple sizing module that then estimates the systems parameters required to run the storage system model. This design tool can also be used as a standalone MS Excel model to estimate the storage system mass and volume outside of Framework and compare it to the DOE Technical Targets. This model will be explained and exercised with existing hydrogen storage materials.     

Mathematical modeling,numerical simulation and experimental comparison of the desorption process in a metal hydride hydrogen storage system

A two-dimensional axisymmetric model is developed to study the hydrogen desorption reaction and its subsequent discharge in a metal hydride canister. Experimental tests are performed on an in-house fabricated setup. An extensive study on the effects of the metal properties and boundary conditions on discharging performance is carried out through non-destructive testing (NDT). Results show that the desorption process is more effective if the activation energy for desorption (E_d) and the reaction enthalpy (ΔH) decrease, and when the desorption rate coefficient (C_d) and the external convection heat transfer coefficient when the bottle is being heated (h) increase. Furthermore, porosity (ε) can be useful for the design of hydrogen storage systems, with a trade-off between charge/discharge time and storage capacity. Numerical and experimental results are compared achieving a good agreement. These results can be used to select metal hydride materials and also for the future evaluation of metal hydride degradation.     

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.     

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.     

Experimental analysis of a metal hydride hydrogen storage system with hexagonal honeycomb-based heat transfer enhancements-part B

This study is a continuation of the computational analysis of the reactor equipped with hexagonal honeycomb based heat transfer enhancements, performed in Part A of the study. In the present study, the performance of the metal alloy and the reactor is investigated experimentally. The gravimetric capacity and reaction kinetics of the alloy La_0.9Ce_0.1Ni₅ are determined. The performance of the reactor under different external environments is noted. The influence of operating conditions such as supply pressure, heat transfer fluid, heat transfer fluid temperature on the reactor performance is investigated. Evaporative cooling as a heat removal technique for metal hydride based hydrogen storage reactors is tested for the first time and compared to conventional heat removal methods. It is found to improve the heat transfer from the alloy bed significantly.