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.     

Polymer-based composite containing nanostructured LaNi5 for hydrogen storage: Improved air stability and processability

Safe and effective methods for hydrogen storage are still required to expand its usage as an energy carrier. One approach to contribute to solving this issue is to develop a polymer-based composite. In this study, an acrylonitrile-EPDM(ethylene/propylene/diene)-styrene (AES) composite containing nanostructured LaNi₅ was produced by wet ball milling (WM) for hydrogen storage, aiming operation at room temperature. The samples were processed as a cylindrical filament for the analyses performed. Improved particle dispersion was obtained for WM-AES/LaNi₅, which correlates with increasing the hydrogen sorption capacity. The polymer was able to maintain the specimen integrity after 20 hydriding cycles, avoiding the LaNi₅ pulverization and the reduction of LaNi₅ crystallite size. The crystallite size was in the nanoscale, reaching nearly 8 nm for WM-AES/LaNi₅. Fewer cycles were required to stabilize the hydrogen capacity for the composites. The samples were exposed to ambient air for up to 17 h, and their absorption kinetics were evaluated. The time required to reach 80% of hydrogen capacity after being exposed for 17 h increased 16.7x and 2.5x for ball-milled LaNi₅ and WM-AES/LaNi₅, respectively. Therefore, it is shown that the polymer reduces the effects of air exposure on its absorption kinetics. This study shows a promising method to produce a moldable polymer composite for hydrogen storage operational at room temperature.     

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%.     

A metal hydride–polymer composite for hydrogen storage applications

To address the issue of the breakdown into fine powders that occurs in the practical use of metal hydrides, the possibility of using a polymeric material as a matrix that contains the active metal particles was experimentally assessed. A ball milling approach in the tumbling mode was used to develop a metal hydride–polymer composite with a high metal to polymer weight ratio. The alloy powder was blended with the polymer and a coating of the metal particles was obtained. The composite was consolidated by hot pressing and the pellets were characterized in terms of their hydriding–dehydriding properties. The materials did not show significant losses in either loading capacity or kinetic properties. The polymeric matrix resulted as being stable under hydrogen cycling. Further, from SEM observation it was confirmed that the metal powders remained embedded in the polymeric matrix even after a number of cycles and that the overall dimensional integrity was retained.     

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.     

Zinc substituted MgH2 - a potential material for hydrogen storage applications

The search for efficient materials for onboard hydrogen storage applications is an emerging research field. Using density functional calculations, we demonstrate Zn substituted MgH₂ as a potential material for hydrogen storage. We predicted the ground state crystal structure of ZnH₂ which is found to be Pna2₁ (orthorhombic) structure with meta-stable behavior. The structural phase stability and phase transition of Mg_1−xZn_xH₂ systems have been analyzed. The H site energy of Mg_1−xZn_xH₂ systems is calculated to understand the hydrogen desorption process. Our calculations suggest that Zn substitution reduces the stability of MgH₂, thereby it may reduce the decomposition temperature of MgH₂. The band structure and density of states calculations reveal that the Mg_1−xZn_xH₂ systems are insulators. The chemical bonding behavior of Mg_1−xZn_xH₂ systems is established as iono-covalent in nature. Moreover, Zn substitution in MgH₂ induces disproportionate MgH bonds which could also contribute the reduction in the decomposition temperature as well as H sorption kinetics.     

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.     

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.     

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.     

Comparisons between MgH2- and LiH-containing systems for hydrogen storage applications

The present study compares the dehydrogenation kinetics of (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ and (_LiNH2+LiH)$({\mathrm{LiNH}}_2+\mathrm{LiH})$ systems and their vulnerabilities to the NH₃ emission problem. The (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ and (_LiNH2+LiH)$({\mathrm{LiNH}}_2+\mathrm{LiH})$ mixtures with different degrees of mechanical activation are investigated in order to evaluate the effect of mechanical activation on the dehydrogenation kinetics and NH₃ emission rate. The activation energy for dehydrogenation, the phase changes at different stages of dehydrogenation, and the level of NH₃ emission during the dehydrogenation process are studied. It is found that the (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ mixture has a higher rate for hydrogen release, slower rate for approaching a certain percentage of its equilibrium pressure, higher activation energy, and more NH₃ emission than the (_LiNH2+LiH)$({\mathrm{LiNH}}_2+\mathrm{LiH})$ mixture. On the basis of the phenomena observed, the reaction mechanism for the dehydrogenation of the (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ system has been proposed for the first time. Approaches for further improving the hydrogen storage behavior of the (2_LiNH2+_MgH2)$(2{\mathrm{LiNH}}_2+{\mathrm{MgH}}_2)$ system are discussed in light of the newly proposed reaction mechanism.     

Nanomaterials for on-board solid-state hydrogen storage applications

Hydrogen has the highest gravimetric density (energy density per unit mass) of any fuel. The combustion of hydrogen releases energy in the form of heat. When hydrogen reacts with oxygen in a fuel cell, the reaction releases energy in the form of electricity. Unlike hydrocarbon-based fuels, the generation of energy from either the combustion of hydrogen or the reaction of hydrogen with oxygen in a fuel cell is not accompanied by the emission of greenhouse gases. This makes hydrogen a promising solution to solve global warming issues. However, hydrogen has a low volumetric density (low energy density per unit volume) which makes storing or transporting hydrogen extremely difficult and expensive. To accelerate the utilization of hydrogen as an energy carrier, it is necessary to develop advanced hydrogen storage methods that have the potential to have a higher energy density.The hydrogen storage market is segmented by application into: (1) Stationary power: stored hydrogen is consumed for example in a fuel cell for use in backup power stations, refueling stations, power stations; (2) Portable power: hydrogen storage applications for electronic devices such as mobile phones, flash lights, and portable generators; and (3) Transportation: industries including automobiles, aerospace, unmanned aerial systems, and hydrogen tanks used throughout the hydrogen supply chain. The increasing development of light and heavy fuel cell vehicles is expected to drive the development of on-board solid-state hydrogen technologies.A large number of research groups worldwide for many years have been trying to develop materials having the right set of thermodynamic and kinetic properties, along with all of the physical properties (high gravimetric density, high volumetric density, etc.) to allow for low-pressure storage system in ambient conditions. However, to date, no material has been found that satisfies all the desired properties to be viably used in many applications. Even if we consider only three parameters namely gravimetric density, volumetric density, and system cost, no materials that can meet the ultimate targets of the U.S. Department of Energy (DOE) or the 2030 targets of the European Union's Fuel Cells and Hydrogen Joint Undertaking (FCH JU) and the New Energy and Industrial Technology Development Organization (NEDO) in Japan.The present article reviews advances in solid-state hydrogen storage technology and compares the opportunities and challenges of selected materials. The materials reviewed in this article have a wider spectrum than the materials reviewed in other existing articles, including carbon nanotubes (CNTs), metal–organic frameworks (MOFs), graphene, boron nitride (BN), fullerene, silicon, amorphous manganese hydride molecular sieve, and metal hydrides. Pioneering works, important breakthroughs, as well as the latest developments for promising materials are also reviewed.In addition, for the first time the targets set by several official regulatory agencies for solid-state hydrogen storage are summarized. Achievements in academic and industrial research are compared against these targets.The future prospects of promising materials are analyzed based on how its practical application can be implemented according to market needs.     

Fundamentals and recent advances in polymer composites with hydride-forming metals for hydrogen storage applications

Hydrogen has unique properties that make it a promising energy vector to replace fossil fuels. However, it is still required to develop safe and efficient storage methods before being widely implemented. Storing hydrogen in hydride-forming metals (HFM) is an approach that has been extensively studied in the last decades. But only recently the preparation of polymer composites with HFM have been explored. Air resistance, volumetric stability and processability are some of the HFM properties that could be improved by incorporating a polymer phase. This review presents the fundamentals concepts of gas transport in dense polymers, and the evolution and trends of incorporating HFM particles into a polymer matrix. The most recent findings are summarized and discussed. The potential improvement of the most relevant classes of HFM and the mechanisms of how different classes of polymers could be advantageously used are reported.     

Thermal design of a hydrogen storage system using La(Ce)Ni5

Hydrogen storage within a metal hydride involves exothermic and endothermic processes for hydrogen absorption and desorption, respectively. In addition, the thermal conductivity of the particulate metal hydride (i.e., powder) after repeated absorption processes is extremely low compared to its bulk phase. Low heat conduction through the metal hydride powder makes the hydrogen charging slow; thus, appropriate thermal management is necessary to achieve the fast charging time with the maximum energy density. In this work, we propose a thermal design of a portable hydrogen storage system made of a 300-mL vessel by balancing the internal and external thermal resistances. A copper-mesh structure is employed inside the vessel for enhancing the effective thermal conductivity of metal hydride powder (i.e., reducing the internal thermal resistance). On the other hand, a compact fan is used for enhancing the forced convection heat transfer from the vessel (i.e., reducing the external thermal resistance). Consequently, a copper-mesh structure sacrificing 4.3% of the internal vessel volume was manufactured by following the thermal design. In addition, the effect of the proposed thermal design was confirmed by actual hydrogen-charging experiments that showed 73.5% reduction of the charging time.     

Experimental studies on the poisoning properties of a low-plateau hydrogen storage alloy LaNi4.3Al0.7 against CO impurities

Metal hydride (MH) material can be used for effective separation of hydrogen from gas mixture. However, some impurities in the feedstock gas may cause the poisoning of the material and hence failure of the MH-based hydrogen separation system. In this paper, the hydrogen storage alloy LaNi_4.3Al_0.7, which has low-plateau pressure and was supposed to be used for hydrogen separation from the semi-coke oven gas, was tested in the atmosphere with relatively high concentration of CO impurities (～0.1%v/v) by cycling experiments. Interestingly, the hydrogen storage capacity of the material shows quite mild decline during contact with CO at the temperature of 363 K or higher, and relatively fast kinetics can be kept, highlighting its application potential for hydrogen separation on a variety of occasions.     

Hybrid fuel cell-based energy system with metal hydride hydrogen storage for small mobile applications

This paper describes the general architecture of a hybrid energy system, whose main components are a proton exchange membrane fuel cell, a battery pack and an ultracapacitor pack as power sources, and metal hydride canisters as energy storage devices, suitable for supplying power to small mobile non-automotive devices in a flexible and variable way. The first experimental results carried out on a system prototype are described, showing that the extra components, required in order to manage the hybrid system, do not remarkably affect the overall system efficiency, which is always higher than 36% in all the test configurations examined. In fact, the system allows the fuel cell to work most often at quasi-optimal conditions, near its maximum efficiency (i.e. at low/medium loads), because high external loads are met by the combined effort of the fuel cell and the ultracapacitors. For the same reason, the metal hydride storage system can be used also under highly dynamic operating conditions, notwithstanding its usually poor kinetic performance.     

Influence of electrostatic field on the interaction of AB5-type alloy LaNi4.4Al0.3Fe0.3 with hydrogen

The effect of the electrostatic field on hydrogen absorption is experimentally studied for the case of AB₅-type intermetallic compound LaNi_4.4Al_0.3Fe_0.3 with low equilibrium pressure. Experimental facility contained control and measurement system for PCT-isotherms and a non-conductive polymer vessel immersed in a bath of a thermostat with transformer oil. The test sample with 100 g of the activated alloy powder was used. Electrostatic field was created between a copper tube, which simultaneously served as a hydrogen inlet, connected to a high voltage source and a grounded nickel plate rolled in the form of a cylinder around the outer wall of the vessel. The electrodes were arranged coaxially, the maximum voltage on the internal electrode was 15 kV. The high voltage source also allowed changing the polarity on the internal electrode.It was found that the electrostatic field had no effect on the already established equilibrium in the hydrogen-alloy system at a voltage at the electrode up to 15 kV, regardless of the polarity. However, the process of hydrogen absorption is noticeably slowed down when a voltage of up to 15 kV with negative polarity is applied to the internal electrode, and the effect increases with increasing voltage. At a voltage of 15 kV and the positive polarity of the internal electrode, there was no noticeable effect on the hydrogen absorption process.     

Excellent catalytic effect of LaNi5 on hydrogen storage properties for aluminium hydride at mild temperature

The catalytic effect of rare-earth hydrogen storage alloy is investigated for dehydrogenation of alane, which shows a significantly reduced onset dehydrogenation temperature (86 °C) with a high-purity hydrogen storage capacity of 8.6 wt% and an improved dehydrogenation kinetics property (6.3 wt% of dehydrogenation at 100 °C within 60 min). The related mechanism is that the catalytic sites on the surface of the hydrogen storage alloy and the hydrogen storage sites of the entire bulk phase of the hydrogen storage reduce the dehydrogenation temperature of AlH₃ and improve the dehydrogenation kinetic performance of AlH₃. This facile and effective method significantly improves the dehydrogenation of AlH₃ and provides a promising strategy for metal hydride modification.     

Improvement of Mg–Al alloys for hydrogen storage applications

In the context of energy carrier, storage of hydrogen is one of the key challenges for research today. The group of Mg-based hydrides stands as a promising candidate for competitive hydrogen storage with high reversible hydrogen capacity.     

AB5/ABS composite material for hydrogen storage

AB5 metal hydride (MH) particles were polymer dispersed in order to entrap the micro and nanoparticles produced by repeated fragmentations of the metal phase during the hydrogen charging/discharging cycles. Acrylonitrile-butadiene-styrene copolymer (ABS) was selected as a matrix on the basis of its physical and chemical properties. AB5/ABS composite pellets were obtained by using a dry mechanical particle coating approach in a tumbling-mill apparatus and successive consolidation by uniaxial hot pressing. A number of characterization techniques were used to assess the morphological, chemical and structural properties of the composites. High pressure DSC measurements, conducted at different pressure values, were used to assess the H₂ absorption properties and profile the Van't Hoff plots of the material. The overall results indicated that the AB5/ABS composite well tolerated the hydriding effects on metal particles, with no losses in hydriding kinetics. The material characteristics were found to be compatible with its application in developing MH-based H₂ storage devices.     

Thermodynamical properties of La–Ni–T (T = Mg, Bi and Sb) hydrogen storage systems

The hydrogen absorption properties of LaNi_4.8T_0.2 (T = Mg, Bi and Sb) alloys are reported. The effects of the substitution of Ni in the LaNi₅ compound with Mg, Bi and Sb are investigated. The ability of alloys to absorb hydrogen is characterized by the pressure–composition (p–c) isotherms. The p–c isotherms allow the determining thermodynamic parameters enthalpy (ΔH^des) and entropy (ΔS^des) of the dehydrogenation processes. The calculated ΔH^des and ΔS^des data helps to explain the decrease of hydrogen equilibrium pressure in alloys doped with Al, Mg and Bi and its increase in the Sb-doped LaNi₅ compound. Generally, partial substitution of Ni in LaNi₅ compound with Mg, Bi and Sb cause insignificant changes of hydrogen storage capacity compared to the hydrogen content in the initial LaNi₅H₆ hydride phase. However, it is worth to stress that, in the case of LaNi_4.8Bi_0.2, a small increase of H/f.u. up to 6.8 is observed. The obtained results in these investigations indicate that the LaNi_4.8T_0.2 (T = Al, Mg and Bi) alloys can be very attractive materials dedicated for negative electrodes in Ni/MH batteries.