Enhanced hydrogen sorption in single walled carbon nanotube incorporated MIL-101 composite metal-organic framework

Metal-Organic Frameworks (MOFs) have emerged as potential hydrogen storage media due to their high surface area, pore volume and adjustable pore sizes. The large void space generated by cages in MOFs is not completely utilized for hydrogen storage application owing to weak interactions between the walls of MOFs and H₂ molecules. These unutilized volumes in MOFs can be effectively utilized by incorporation of other microporous materials such as single walled carbon nanotubes into the pores of MOFs which could effectively tune the pore size and pore volume of the material towards hydrogen sorption. Single walled carbon nanotubes (SWNT) incorporated MIL-101 composite MOF material (SWNT@MIL-101) was synthesized by adding purified single walled carbon nanotube (SWNT) in situ during the synthesis of MIL-101. The powder X-ray diffraction patterns of SWNT@MIL-101 showed the structure of MOF was not disturbed by SWNT incorporation. Hydrogen sorption capacities of MIL-101 was observed to increase from 6.37 to 9.18 wt% at 77 K up to 60 bar and from 0.23 to 0.64 wt% at 298 K up to 60 bar. The increment in the hydrogen uptake capacities of composite MOF materials was attributed to the decrease in the pore size and enhancement of micropore volume of MIL-101 by single walled carbon nanotube incorporation.     

Hybrid nickel-metal hydride/hydrogen battery

High capacity, high efficiency and resource-rich energy storage systems are required to store large scale excess electrical energy from renewable energy. We proposed “Hybrid Nickel-Metal Hydride/Hydrogen (Ni-MH/H₂) Battery” using high capacity AB₅-type hydrogen storage alloy and high-pressure H₂ gas as negative electrode active materials. It was experimentally confirmed that hydrogen gas can be utilized as an active material of negative electrode by the presence of the AB₅-type hydrogen storage alloy. The experimental average cell voltage suggested that H₂ gas passed through the alloy in the form of atoms. The calculated gravimetric energy density of this hybrid battery increased up to 1.5 times of the conventional Ni-MH battery with low content of rare-earth element which is 32 wt% of the Ni-MH battery.     

A review on current trends in potential use of metal-organic framework for hydrogen storage

Hydrogen can be a promising clean energy carrier for the replenishment of non-renewable fossil fuels. The set back of hydrogen as an alternative fuel is due to its difficulties in feasible storage and safety concerns. Current hydrogen adsorption technologies, such as cryo-compressed and liquefied storage, are costly for practical applications. Metal-organic frameworks (MOFs) are crystalline materials that have structural versatility, high porosity and surface area, which can adsorb hydrogen efficiently. Hydrogen is adsorbed by physisorption on the MOFs through weak van der Waals force of attraction which can be easily desorbed by applying suitable heat or pressure. The strategies to improve the MOFs surface area, hydrogen uptake capacities and parameters affecting them are studied. Hydrogen spill over mechanism is found to provide high-density storage when compared to other mechanisms. MOFs can be used as proton exchange membranes to convert the stored hydrogen into electricity and can be used as electrodes for the fuel cells. In this review, we addressed the key strategies that could improve hydrogen storage properties for utilizing hydrogen as fuel and opportunities for further growth to meet energy demands.     

Concepts for improving hydrogen storage in nanoporous materials

Hydrogen storage in nanoporous materials has been attracting a great deal of attention in recent years, as high gravimetric H₂ capacities, exceeding 10 wt% in some cases, can be achieved at 77 K using materials with particularly high surface areas. However, volumetric capacities at low temperatures, and both gravimetric and volumetric capacities at ambient temperature, need to be improved before such adsorbents become practically viable. This article therefore discusses approaches to increasing the gravimetric and volumetric hydrogen storage capacities of nanoporous materials, and maximizing the usable capacity of a material between the upper storage and delivery pressures. In addition, recent advances in machine learning and data science provide an opportunity to apply this technology to the search for new materials for hydrogen storage. The large number of possible component combinations and substitutions in various porous materials, including Metal-Organic Frameworks (MOFs), is ideally suited to a machine learning approach; so this is also discussed, together with some new material types that could prove useful in the future for hydrogen storage applications.     

Machine learning analysis of alloying element effects on hydrogen storage properties of AB2 metal hydrides

Zirconium-titanium-based AB₂ is a potential candidate for hydrogen storage alloys and NiMH battery electrodes. Machine learning (ML) has been used to discover and optimize the properties of energy-related materials, including hydrogen storage alloys. This study used ML approaches to analyze the AB₂ metal hydrides dataset. The AB₂ alloy is considered promising owing to its slightly high hydrogen density and commerciality. This study investigates the effect of the alloying elements on the hydrogen storage properties of the AB₂ alloys, i.e., the heat of formation (ΔH), phase abundance, and hydrogen capacity. ML analysis was performed on the 314 pairs collected and data curated from the literature published during 1998–2019, comprising the chemical compositions of alloys and their hydrogen storage properties. The random forest model excellently predicts all hydrogen storage properties for the dataset. Ni provided the most contribution to the change in the enthalpy of the hydride formation but reduced the hydrogen content. Other elements, such as Cr, contribute strongly to the formation of the C14-type Laves phase. Mn significantly affects the hydrogen storage capacity. This study is expected to guide further experimental work to optimize the phase structure of AB₂ and its hydrogen sorption properties.     

Electrochemical behaviour of intermetallic-based metal hydrides used in Ni/metal hydride (MH) batteries: a review

Hydrogen storage alloys are a group of new functional intermetallics which can be used in heat pumps, catalysts, hydrogen sensors and Ni/MH batteries. The development of Ni/MH (Metal Hydride) batteries based on MH negative electrodes has seen considerable activity in recent years. Batteries based on such hydride materials have some major advantages over the more conventional lead–acid and nickel–cadmium systems. These advantages include: high-energy density; high-rate capability; tolerance to overcharge and over-discharge; the lack of any poisonous heavy metals; and no electrolyte consumption during charge/discharge cycling. The most important electrochemical characteristics of the hydrogen storage compounds used in these batteries include capacity, cycle lifetime, exchange current density and equilibrium potential. These characteristics can be changed by designing the composition of the hydrogen storage alloy to provide optimum performance of the Ni/MH batteries. The electrochemical behaviour of such intermetallics depends on the types of intermetallics (mainly AB₂ and AB₅), microstructure, the nature and amount of each element in the intermetallic compound, and the electrochemical process(es) taking place. The addition of some highly electrocatalytic materials for the hydrogen evolution reaction (h.e.r.) are beneficial in generating optimum performance for the MH electrodes. In this paper, we present some recent results on the electrochemical behaviour of such compounds and the mechanisms of the electrochemical reactions.     

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

This work combines materials development with hydrogen storage technology advancements to address onboard hydrogen storage challenges in light-duty vehicle applications. These systems are comprised of the vehicle requirements design space, balance of plant requirements, storage system components, and materials engineering culminating in the development of an Adsorbent System Design Tool that serves as a preprocessor to the storage system and vehicle-level models created within the Hydrogen Storage Engineering Center of Excellence. Computational and experimental efforts were integrated to evaluate, design, analyze, and scale potential hydrogen storage systems and their supporting components against the Department of Energy 2020 and Ultimate Technical Targets for Hydrogen Storage Systems for Light Duty Vehicles. Ultimately, the Adsorbent System Design Tool was created to assist material developers in assessing initial design parameters that would be required to estimate the performance of the hydrogen storage system once integrated with the full fuel cell system.     

Empirical profiling of cold hydrogen plumes formed from venting of LH2 storage vessels

Liquid hydrogen (LH₂) storage is viewed as a viable approach to assure sufficient hydrogen capacity at commercial fuelling stations. Presently, LH₂ is produced at remote facilities and then transported to the end-use site by road vehicles (i.e., LH₂ tanker trucks). Venting of hydrogen to depressurize the transport storage tank is a routine part of the LH₂ delivery and site transfer process. The behavior of cold hydrogen plumes has not been well characterized because of the sparsity of empirical field data, which can lead to overly conservative safety requirements. Committee members of the National Fire Protection Association (NFPA) Standard 2 [1] formed the Hydrogen Storage Safety Task Group, which consists of hydrogen producers, safety experts, and computational fluid dynamics modellers, has identified the lack of understanding of hydrogen dispersion during LH₂ venting of storage vessels as a critical gap for establishing safety distances at LH₂ facilities, especially commercial hydrogen fuelling stations. To address this need, the National Renewable Energy Laboratory Sensor Laboratory, in collaboration with the NFPA Hydrogen Storage Task Group, developed a prototype Cold Hydrogen Plume Analyzer to empirically characterize the hydrogen plume formed during LH₂ storage tank venting. The prototype analyzer was field deployed during an actual LH₂ venting process. Critical findings included:

• •Hydrogen above the lower flammable limit (LFL) was detected as much as 2 m lower than the release point, which is not predicted by existing models.
• •Personal monitors detected hydrogen at ground level, although at levels below the LFL.
• •A small but inconsistent correlation was found between oxygen depletion and the hydrogen concentration.
• •A negligible to non-existent correlation was found between in-situ temperature measurements and the hydrogen concentration.

The prototype analyzer is being upgraded for enhanced metrological capabilities, including improved real-time spatial and temporal profiling of hydrogen plumes and tracking of prevailing weather conditions. Additional deployments are planned to monitor plume behavior under different wind, humidity, and temperature conditions. The data will be shared with the Hydrogen Storage Task Group and ultimately will be used support theoretical models and code requirements prescribed in NFPA 2.     

Metal organic frameworks for hydrogen purification

High purity hydrogen is one of the key factors in determining the lifetime of proton exchange membrane (PEM) fuel cells. However, the current industrial processes for producing high purity hydrogen are not only expensive, but also come with low energy efficiencies and productivity. Finding more cost-effective methods of purifying hydrogen is essential for ensuring wider scale deployment of PEM fuel cells. Among various hydrogen purification methods, adsorption in porous materials and membrane technologies are seen as two of the most promising candidates for the current industrial hydrogen purification methods, with metal organic frameworks (MOF) being particularly popular in research over the last decade. Despite many available reviews on MOFs, most focus on synthesis and production, with few reports focused on performance for hydrogen purification. This review describes the working principle and performance parameters of adsorptive separations and membrane materials and identifies MOFs that have been reported for hydrogen purification. The MOFs are summarised and their performance in separating hydrogen from common impurities (CO₂, N₂, CH₄, CO) is compared systematically. The challenges of commercial application of MOFs for hydrogen purification are discussed.     

Estimation of system-level hydrogen storage for metal-organic frameworks with high volumetric storage density

Metal organic framework (MOF) materials have emerged as the adsorbent materials with the highest H₂ storage densities on both a volumetric and gravimetric basis. While measurements of hydrogen storage at the material level (primarily at 77 K) have been published for hundreds of MOFs, estimates of the system-level hydrogen storage capacity are not readily available. In this study, hydrogen storage capacities are estimated at the system-level for MOFs with the highest demonstrated volumetric and gravimetric H₂ storage densities. System estimates are based on a single tank cryo-adsorbent system that utilizes a type-1 tank, multi-layer vacuum insulation, liquid N₂ cooling channels, in-tank heat exchanger, and a packed MOF powder inside the tank. It is found that with this powder-based system configuration, MOFs with ultra-high gravimetric surface areas and hydrogen adsorption amounts do not necessarily provide correspondingly high volumetric or gravimetric storage capacities at the system-level. Meanwhile, attributes such as powder packing efficiency and system cool-down temperature are shown to have a large impact on the system capacity. These results should shed light on the material properties that must to be optimized, as well as highlight the important design challenges for cryo-adsorbent hydrogen storage systems.     

Magnesium based materials for hydrogen based energy storage: Past,present and future

Magnesium hydride owns the largest share of publications on solid materials for hydrogen storage. The “Magnesium group” of international experts contributing to IEA Task 32 “Hydrogen Based Energy Storage” recently published two review papers presenting the activities of the group focused on magnesium hydride based materials and on Mg based compounds for hydrogen and energy storage. This review article not only overviews the latest activities on both fundamental aspects of Mg-based hydrides and their applications, but also presents a historic overview on the topic and outlines projected future developments. Particular attention is paid to the theoretical and experimental studies of Mg-H system at extreme pressures, kinetics and thermodynamics of the systems based on MgH₂, nanostructuring, new Mg-based compounds and novel composites, and catalysis in the Mg based H storage systems. Finally, thermal energy storage and upscaled H storage systems accommodating MgH₂ are presented.     

Hydrogen storage properties of new A3B2-type TiZrNbCrFe high-entropy alloy

Crystal structure and hydrogen storage properties of a novel equiatomic TiZrNbCrFe high-entropy alloy (HEA) were studied. The selected alloy, which had a A₃B₂-type configuration (A: elements forming hydride, B: elements with low chemical affinity with hydrogen) was designed to produce a hydride with a hydrogen-to-metal atomic ratio (H/M) higher than those for the AB₂- and AB-type alloys. The phase stability of alloy was investigated through thermodynamic calculations by the CALPHAD method. The alloy after arc melting showed the dominant presence of a solid solution C14 Laves phase (98.4%) with a minor proportion of a disordered BCC phase (1.6%). Hydrogen storage properties investigated at different temperatures revealed that the alloy was able to reversibly absorb and fully desorb 1.9 wt% of hydrogen at 473 K. During the hydrogenation, the initial C14 and BCC crystal structures were fully converted into the C14 and FCC hydrides, respectively. The H/M value was 1.32 which is higher than the value of 1 reported for the AB₂- and AB-type HEAs. The present results show that good hydrogen storage capacity and reversibility at moderate temperatures can be attained in HEAs with new configurations such as A₃B₂/A₃B₂H₇.     

Investigations on calculation of heat of formation for multi-element AB5-type hydrogen storage alloy

With development in hydrogen energy research, more and more applications of hydrogen storage materials have been put forward. This requires synthesis of new materials for specific purpose. In context to designing of metal hydride bed, thermodynamic parameter ‘Heat of formation’ (ΔH) for hydrogen storage alloy is very important. Theoretical calculation of ΔH for binary compound or ternary hydride is accomplished by well known ‘Miedema's Rule of Reverse Stability’. Experimentally ΔH may be determined using Van't Hoff Equation. So far, theoretical calculation of ΔH for multi-element alloy is not known. In the present investigation simple phenomenological formulae have been proposed to calculate ΔH for multi-element alloy including AH_m, BH_m, AB_n, AB_nH_2m, AB_n-xC_x, AB_n-xC_xH_2m, AB_n-x-yC_xD_y, AB_n-x-yC_xD_yH_2m and so on. The calculated values of ΔH in present investigation have been compared with the experimental reported value or calculated by any other model reported in literature. An excellent agreement has been observed between the two.     

Metal-organic-framework based catalyst for hydrogen production: Progress and perspectives

Fossil fuel shortage and global warming have inspired scientists to search for alternative energy sources which are green, renewable, and sustainable. Hydrogen formed from water splitting has been considered as one of the most promising candidates to replace traditional fuels due to its low production cost and zero-emission. Metal-organic frameworks (MOFs) have been considered as potential catalysts for hydrogen production from water splitting account for their flexible structure, ultra-large surface area, and chemical component diversification. This paper reviews different kinds of MOF-related electrocatalysts, involving metals, metal oxides, single atoms, metal phosphides, metal nitrides, and metal dichalcogenides for hydrogen production. Also, MOF-based photocatalysts consisting of pristine MOFs, MOFs as supporters, and MOF-derived heterojunction architectures are reviewed. The finding of MOF-based catalysts for hydrogen generation is summarized. The pros and cons of different MOF-based materials as catalysts for water splitting are discussed. Finally, current challenges and the potential developments of these unique materials as catalysts are also provided.     

Rapid activation of MmNi5−xMx based MH alloy through Pd nanoparticle impregnation

Faster activation of a multi-component AB₅ based alloy metal hydride electrode through Pd nanoparticle (NP) impregnation is demonstrated. Pd nanoparticle impregnated MmNi_5−xM_x based alloy was prepared and characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and elemental mapping techniques. Electro-catalytic activity of laminar metal hydride electrodes containing Pd nanoparticles and micrometer size Ni particles was studied. Hydrogen absorption efficiency of the nanocomposite electrodes was compared with the metal hydride electrodes without Pd nanoparticles. The incorporation of nanostructured materials in the metal hydride alloy increased its hydrogen absorption capacity at the initial stage and activated much faster, indicating its good prospect for energy storage applications.     

Metal hydride hydrogen storage and compression systems for energy storage technologies

Along with a brief overview of literature data on energy storage technologies utilising hydrogen and metal hydrides, this article presents results of the related R&D activities carried out by the authors. The focus is put on proper selection of metal hydride materials on the basis of AB₅- and AB₂-type intermetallic compounds for hydrogen storage and compression applications, based on the analysis of PCT properties of the materials in systems with H₂ gas. The article also presents features of integrated energy storage systems utilising metal hydride hydrogen storage and compression, as well as their metal hydride based components developed at IPCP and HySA Systems.     

Li-Crown ether complex inclusion in MOF materials for enhanced H2 volumetric storage capacity at room temperature

The organometallic Li-Crown ether species, formed by the complexation of lithium cation with the hydrophobic 18Crown6 ether, has been included in three Metal-Organic-Frameworks (MOF) structures with different pore size: Cr-MIL-101, Fe-MIL100 and Ni-MOF-74. X-ray powder diffraction, thermogravimetric analysis, proton nuclear magnetic resonance, infrared spectroscopy and inductively coupled plasma atomic emission spectroscopy measurements have proved the successful incorporation of the organometallic units to the three MOFs without altering their crystalline structure. Hydrogen adsorption properties of the post-synthesis modified materials have been evaluated in a wide temperature (77–298 K) and pressure (1–170 bar) range conditions. The post-synthetic modification method used based on the MOF impregnation with a Li-Crown ether complex solution produced a partial pore blocking effect on the microporous Ni-MOF-74, reducing its hydrogen adsorption capacity. However, the inclusion of the crown-ether and particularly the Li-Crown ether complex resulted in an increase of the volumetric hydrogen adsorption capacity at room temperature for Cr-MIL101 and Fe-MIL-100, due to the pore volume reduction, higher confinement of H₂ molecules in the cavities and the formation of new specific binding sites for H₂ molecules. The inclusion of Li-Crown ether complex also enhances the H₂ interaction with the mesoporous MOF structures, attributed to the additional electrostatic interactions produced by the presence of Li⁺ ions complexed to the crown ether molecules. Further work following this strategy to improve hydrogen adsorption capacity of mesoporous MOFs at room temperature should be extended to other MOF materials, checking its influence on their capacity for gas separation purposes.     

Hydrogen storage in Mg: A most promising material

In the last one decade hydrogen has attracted worldwide interest as an energy carrier. This has generated comprehensive investigations on the technology involved and how to solve the problems of production, storage and applications of hydrogen. The interest in hydrogen as energy of the future is due to it being a clean energy, most abundant element in the universe, the lightest fuel and richest in energy per unit mass. It will provide, Cheap Electricity, Cook Food, Drive Car, Run Factories, Jet Planes, Hydrogen Village and for all our domestic energy requirements. In short hydrogen shows the solution and also allows the progressive and non-traumatic transition of today's energy sources, towards feasible safe reliable and complete sustainable energy chains. The present article deals with the hydrogen storage in metal hydrides with particular interest in Mg as it has potential to become one of the most promising storage materials. Many metals combine chemically with Hydrogen to form a class of compounds known as Hydrides. These hydrides can discharge hydrogen as and when needed by raising their temperature or decreasing the external pressure. An optimum hydrogen-storage material is required to have various properties viz. high hydrogen capacity per unit mass and unit volume which determines the amount of available energy, low dissociation temperature, moderate dissociation pressure, low heat of formation in order to minimize the energy necessary for hydrogen release, low heat dissipation during the exothermic hydride formation, reversibility, limited energy loss during charge and discharge of hydrogen, fast kinetics, high stability against O₂ and moisture for long cycle life, cyclibility, low cost of recycling and charging infrastructures and high safety. So far the most of hydrogen storage alloys such as LaNi₅, TiFe, TiMn₂, have hydrogen storage capacities, not more than 2 wt% which is not satisfactory for practical application as per DOE Goal. A group of Mg based hydrides stand as promising candidate for competitive hydrogen storage with reversible hydrogen capacity upto 7.6 wt% for on board applications. Efforts have been devoted to these materials to decrease their desorption temperature, enhance the kinetics and cycle life. The kinetics has been improved by adding an appropriate catalyst into the system as well as by ball milling that introduces defects with improved surface properties. The studies reported promising results, such as improved kinetics and lower desorption temperatures, however, the state of the art materials are still far from meeting the aimed target for their transport applications. Therefore further research work is needed to achieve the goal by improving development on hydrogenation, thermal and cyclic behavior of metal hydrides. In the present article the possibility of commercialization of Mg based alloys has been discussed.     

Thermally stable nanoporous palladium alloy powders by hydrogen reduction in surfactant templates

Nanometer-scale pores in metals used for hydrogen storage are expected to facilitate mass transport in the materials – in particular, the release of helium decay products when tritium is stored. Scalable methods for production of bulk powders of nanoporous metals typically use chemical reducing agents that can leave impurities in the product. Hydrogen gas can be used as the reducing agent in such procedures. This not only improves purity, but also expands the range of accessible pore and particle sizes and particle compositions. Powders of nanoporous palladium and its alloys with rhodium are synthesized by chemical reduction of chloride complexes by hydrogen in a concentrated nonionic aqueous surfactant at room temperature. Particle diameters are typically several micrometers and each particle is perforated by 2–3 nm pores, as determined by electron microscopy and nitrogen porosimetry. Alloys show major improvement in thermal stability and pore regularity compared to pure palladium. In addition to facilitating heavier isotope storage, the high surface areas of these materials may allow development of metal hydride batteries with high power density.     

Electric system management through hydrogen production – A market driven approach in the French context

Hydrogen is usually presented as a promising energy carrier that has a major role to play in low carbon transportation, through the use of fuel cells. However, such a development is not expected in the short term. In the meantime, hydrogen may also contribute to reduce carbon emissions in diverse sectors among which methanol production. Methanol can be produced by combining carbon dioxide and hydrogen, hence facilitating carbon dioxide emission mitigation while providing a beneficial tool to manage the electric system, if hydrogen is produced by alkaline electrolysis operated in a variable way driven by the spot and balancing electricity markets. Such a concept is promoted by the VItESSE² project (Industrial and Energy value of CO₂ through Efficient use of CO₂-free electricity - Electricity Network System Control & Electricity Storage). Through the proposed market driven approach, hydrogen production offers a possibility to help managing the electric system, together with an opportunity to reduce hydrogen production costs.