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.     

Comments on solid state hydrogen storage systems design for fuel cell vehicles

In recent years, significant research and development efforts were spent on hydrogen storage technologies with the goal of realizing a breakthrough for fuel cell vehicle applications. This article scrutinizes design targets and material screening criteria for solid state hydrogen storage. Adopting an automotive engineering point of view, four important, but often neglected, issues are discussed: 1) volumetric storage capacity, 2) heat transfer for desorption, 3) recharging at low temperatures and 4) cold start of the vehicle. The article shall help to understand the requirements and support the research community when screening new materials.     

TiFe0.85Mn0.05 alloy produced at industrial level for a hydrogen storage plant

Moving from basic research to the implementation of hydrogen storage system based on metal hydride, the industrial production of the active material is fundamental. The alloy TiFe_0.85Mn_0.05 was selected as H₂-carrier for a storage plant of about 50 kg of H₂. In this work, a batch of 5 kg of TiFe_0.85Mn_0.05 alloy was synthesized at industrial level and characterized to determine the structure and phase abundance. The H₂ sorption properties were investigated, performing studies on long-term cycling study and resistance to poisoning. The alloy absorbs and desorbs hydrogen between 25 bar and 1 bar at 55 °C, storing 1.0H₂ wt.%, displaying fast kinetic, good resistance to gas impurities, and storage stability over 250 cycles. The industrial production promotes the formation of a passive layer and a high amount of secondary phases, observing differences in the H₂ sorption behaviour compared to samples prepared at laboratory scale. This work highlights how hydrogen sorption properties of metal hydrides are strictly related to the synthesis method.     

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.     

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

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

System modeling methodology and analyses for materials-based hydrogen storage

In the global efforts to develop advanced materials-based hydrogen storage, the various on-board reversible hydrides, adsorbents and chemical storage candidate materials and systems each have their individual strengths and weaknesses. An overarching challenge in associated research and development is to devise material/system architectures which satisfy all requirements for viability in a particular application area, such as light-duty vehicular transportation. System modeling at the level which encompasses not only the storage material and vessel/reactor, but also integration with a fuel cell and balance-of-plant components, provides a more complete assessment of viability and guides options for improvement. The current work covers the methodology developed for conducting such system modeling consistently across multiple organizations and will present performance results from studies focused on reversible hydride systems. Connecting this high level modeling to more detailed finite element design simulations will be one aspect of our framework approach. The complex hydride NaAlH₄ is representative of novel materials under development and will be used as the basis for properties, such as temperature dependent kinetics, which influence the integrated system configurations and component sizing. While system charging is included through the sizing of certain components, emphasis is placed on hydrogen discharge by the storage system, interrogated through drive cycle transients. Comparisons of performance relative to requirements, including effective gravimetric capacity, effective volumetric density and energy utilization, are given for the baseline material and for a sensitivity study on material density.     

Analysis of a metal hydride reactor for hydrogen storage

In this paper a two-dimensional model of an annular cylindrical reactor filled with metal hydride suitable for hydrogen storage is presented. Comparison of the computed bed temperatures with published experimental data shows a reasonably good agreement except for the initial period. Effects of hydrogen pressure and external fluid temperatures on heat transfer and entropy generation are obtained. Results show that the time required for hydrogen charging and discharging is higher when the thermal capacity of the reactor wall is considered. The time required for absorption and desorption can be reduced significantly by varying the hydrogen gas pressure and external fluid temperatures. However, along with reduction in time the entropy generated during hydrogen storage and discharge increases significantly. Results also show that for the given input conditions, heat transfer between the external fluid and hydride bed is the main source of entropy generation.     

Parametric investigations on LCC1 based hydrogen storage system intended for fuel cell applications

Considering the necessity for compact hydrogen storage system for fuel cell stacks, 41 embedded cooling tube (ECT) reactor with an outer cooling jacket (OCJ) is designed, fabricated and tested with 3.75 kg of LCC1® alloy. To analyse the sensitivity of the system performance at various operating conditions and the applicability of this prototype as storage system, an extensive parametric investigation was carried out at varying supply pressure (P_s), absorption temperature (T_a) and desorption temperature (T_d). LCC1® alloy achieved maximum hydrogen storage capacity (HSC) of 1.6 wt% within 420 s at P_s of 25 bar, T_a of 25 °C and heat transfer fluid (HTF) flow rate (HTF_a) of 6 LPM. Supply pressure is found to have greater influence than absorption temperature over absorption performance and heating output. With T_a of 25 °C, HTF_a of 6 LPM, HSC of 1.58 wt% and 1.6 wt% were achieved at P_s of 20 bar and 30 bar, respectively, resulting in corresponding specific heating power (SHP) of 497.7 W/kg and 544.9 W/kg. Varying T_a from 25 °C to 35 °C at P_s of 20 bar and HTF_a of 6 LPM resulted in 3% reduction in HSC. During desorption, desorption temperature of above 20 °C is found to be favourable with more than 95% of stored hydrogen being desorbed. It is further observed that the dehydriding rate of LCC1® was nearly steady which is potentially suitable for fuel cell applications, as the average dehydriding rate is estimated to be about 15.75 NLPM and 22.91 NLPM at T_d of 20 °C and 25 °C, respectively, with 6 LPM of HTF flow rate. The analysed module is proposed as a potential hydrogen supply unit for a 1 kW fuel cell reported in literature.     

The problem of solid state hydrogen storage

A short review of the materials under investigation suitable for solid state hydrogen storage is presented, with particular reference to the experimental activity carried out at the laboratory of Hydrogen Group of Padova University.     

Multi-variable optimization of metal hydride hydrogen storage reactor with gradient porosity metal foam and evaluation of comprehensive performance

Hydrogen storage performance for metal hydride (MH) reactor is restricted by the poor thermal conductivity of MH. In this study, the gradient porosity metal foam was added into MH reactor for enhancing heat transportation (GMF reactor), and its hydrogen absorption performance was investigated numerically in detail. Then, thermal resistance analysis was conducted to analyze the heat transportation in GMF reactor, and Genetic Algorithm was applied for optimizing metal foam distribution under different conditions. It was indicated that the hydrogenation performance for optimized two-layer GMF reactor was increased by 11.5% compared with uniform metal foam reactor (UMF reactor). The optimization results indicated that the optimal volumetric fractions of metal foam (VFMF) are about 0.08 for both optimized GMF reactor and UMF reactor with the trade-off of hydrogen storage capacity and hydrogen absorption rate. Then, a new indicator of comprehensive hydrogen storage performance (CHSP) for MH reactor was proposed, which includes the influence of hydrogen storage rate, hydrogen storage capacity, volumetric storage density and gravimetric storage density. Besides, the hydrogenation performance for optimized GMF reactor was improved with metal foam layer increasing, and the optimal porosity distribution was gradually approaching a specific power exponent trend. It was showed that the hydrogenation performance for power-exponent GMF reactor was increased by 2.8% and 18.2% compared with that of optimized four-layer GMF reactor and UMF reactor, respectively.     

Design and validation of Clathrate-CNT systems for solid state hydrogen storage

Solid state hydrogen storage addresses the problems of high pressurization in compressed gaseous state and energy intensive liquefaction in liquid state. Clathrate structures have shown promising results as host material for storing hydrogen as hydrate. The effect of different promoters on improving storage capabilities of clathrates have been studied at 263 K and 10 MPa hydrogen pressure. Hydrogen adsorption kinetics of four different clathrates using promoters Tetrahydrofuran, Tetrahydropyran, 1,3 Dioxolane and 2,3 Dihydrofuran with Multiwall Carbon nanotube as substrate was carried out. The results showed ～1.5 wt% hydrogen adsorption within 90 min using CNT substrate. This is one of the first reports on usage of CNT as a substrate material for hydrogen storage in clathrate systems. It was observed that CNT shows synergitic effect in the hydrogen adsorption with fast kinetics (less than 90 min). The weight of substrate material (CNT) was also taken into consideration while calculating the weight % of hydrogen adsorption. The present study also involves design and simulation of a hydrogen storage canister (using CNT based clathrate) with embedded helical coolant coils on COMSOL Multiphysics software to analyse the effects of temperature management on improving hydrogen storage capability of the clathrate reactor bed. Results of simulation includes variation of hydrate concentration and temperature in clathrate reactor bed with the passage of time. The theoretical studies pave way for validating the scalability of clatharates as a viable hydrogen energy system.     

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.     

A hybrid method for hydrogen storage and generation from water

This communication describes a new hybrid method for storing hydrogen in solid inorganic hydride materials as well as producing it from water based on the reaction between LiOH/LiOH·H₂O and LiH. As a hydrogen storage method, the release and uptake of hydrogen in this method are accomplished via a series of simple reactions with good kinetics within a practically reasonable temperature range. The reversible hydrogen storage capacity of the material system is 6–8.8 wt.% at <350 °C. This capacity is one of the highest among all other metal hydrides known to date in the same temperature range. As a hydrogen production method, 100% of hydrogen generated by this method comes from water by its reaction with alkali metal oxides. This method is also an environmentally friendly alternative to the current commercial processes for hydrogen production. The preliminary thermodynamic calculation on energy required for complete regeneration shows that the current system is energetically favorable.     

Performance analysis of LaNi5 added with expanded natural graphite for hydrogen storage system

This paper presents a comparative study of two cases of metal hydride hydrogen storage units working on (i) LaNi₅ (ii) Compacts of LaNi₅ incorporated with expanded natural graphite (ENG). It has been observed from the previous studies that the hydriding/dehydriding reactions eventually causes large strain changes, due to which the hydride forming metal alloys disintegrate and form a powder bed. Such reactor beds usually have a low thermal conductivity which minimizes the heat transfer phenomenon occurring during the absorption of hydrogen gas. Therefore, there is a need to implement heat augmentation methods to significantly enhance the thermal conductivity. The objective of this research is to present a 2-D numerical model using Finite Volume Method (FVM) and estimate the hydrogen storage performance of a cylindrical metal hydride bed for both the cases, i.e. powdered metal hydride bed and ENG compacts-based reactor bed at different values of inlet pressure and heat transfer fluid temperature. In this study, a detailed investigation on the absorption process reveals that reactor beds with compacted disks of LaNi₅ and ENG demonstrate an enhanced effective thermal conductivity and efficient mass transfer. The simulation results show that a remarkable improvement in the heat transfer and hydrogen storage capacity with reduced absorption time can be achieved by using LaNi₅ and ENG compacts. It was observed that the average reactor bed temperature dropped from 345.13 K to 337.37 K when the ENG based compacted disks was introduced into the reactor bed. Moreover, for supply pressure of 24 bar and fluid temperature of 293 K, the time taken to absorb hydrogen into the rector to achieve stabilized hydrogen storage capacity was estimated to be 446s and 232 s for the case of metal hydride and ENG compacts-based bed, respectively.     

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.     

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.     

Design and optimization of single particle electrodes for the kinetic analysis of hydrogen evolution and absorption on hydrogen storage alloys

In the literature, there is a large discrepancy between reported values of electrochemical, kinetic and transport parameters of hydrogen storage alloys. These discrepancies arise, because in most cases, electrodes are prepared with the powdered alloy supported within a porous matrix, constituted by carbon and additive binders such as PTFE. The main drawback, of this preparation technique, for the identification of kinetic parameters, is the uncertainty in the specific active area value, where the hydrogen evolution and absorption processes take place. To overcome the disadvantages described, a new type of electrode, was designed, using a single particle of AB₅ and AB₂ hydride forming alloys. The data obtained from electrochemical impedance measurements were adjusted in terms of a physicochemical model that takes into account the processes of hydrogen evolution and absorption coupled to hydrogen diffusion. From the study it can be concluded that the differences in the behavior of the AB₅ and AB₂ alloys, presenting the first best performance during the activation and operation at high discharge currents, are mainly due to higher values of the exchange current density and the diffusion coefficient of H for the AB₅ alloy.     

On-board and Off-board performance of hydrogen storage options for light-duty vehicles

Leading physical and materials-based hydrogen storage options are evaluated for their potential to meet the vehicular targets for gravimetric and volumetric capacity, cost, efficiency, durability and operability, fuel purity, and environmental health and safety. Our analyses show that hydrogen stored as a compressed gas at 350–700 bar in Type III or Type IV tanks cannot meet the near-term volumetric target of 28 g/L. The problems of dormancy and hydrogen loss with conventional liquid H₂ storage can be mitigated by deploying pressure-bearing insulated tanks. Alane (AlH₃) is an attractive hydrogen carrier if it can be prepared and used as a slurry with >50% solids loading and an appropriate volume-exchange tank is developed. Regenerating AlH₃ is a major problem, however, since it is metastable and it cannot be directly formed by reacting the spent Al with H₂. We have evaluated two sorption-based hydrogen storage systems, one using AX-21, a high surface-area superactivated carbon, and the other using MOF-177, a metal-organic framework material. Releasing hydrogen by hydrolysis of sodium borohydride presents difficult chemical, thermal and water management issues, and regenerating NaBH₄ by converting B–O bonds is energy intensive. We have evaluated the option of using organic liquid carriers, such as n-ethylcarbazole, which can be dehydrogenated thermolytically on-board a vehicle and rehydrogenated efficiently in a central plant by established methods and processes. While ammonia borane has a high hydrogen content, a solvent that keeps it in a liquid state needs to be found, and developing an AB regeneration scheme that is practical, economical and efficient remains a major challenge.     

Performance analysis of a high-temperature magnesium hydride reactor tank with a helical coil heat exchanger for thermal storage

Metal hydrides are regarded as one of the most attractive options for thermal energy storage (TES) materials for concentrated solar thermal applications. Improved thermal performance of such systems is vitally determined by the effectiveness of heat exchange between the metal hydride and the heat transfer fluid (HTF). This paper presents a numerical study supported by experimental validation on a magnesium hydride reactor fitted with a helical coil heat exchanger for enhanced thermal performance. The model incorporates hydrogen absorption kinetics of ball-milled magnesium hydride, with titanium boride and expanded natural graphite additives obtained by Sievert's apparatus measurements and considers thermal diffusion within the reactor to the heat transfer fluid for a realistic representation of its operation. A detailed parametric analysis is carried out, and the outcomes are discussed, examining the ramifications of hydrogen supply pressure and its flow rate. The study identifies that the enhancement of thermal conductivity in magnesium hydride has an insignificant impact on current reactor performance.