Hydrogen storage materials for hydrogen and energy carriers

Hydrogen storage technology is essentially necessary to promote renewable energy. Many kinds of hydrogen storage materials, which are hydrogen storage alloys, inorganic chemical hydrides, carbon materials and liquid hydrides have been studied. In those materials, ammonia (NH₃) is easily liquefied by compression at 1 MPa and 298 K, and has a highest volumetric hydrogen density of 10.7 kg H₂/100 L. It also has a high gravimetric hydrogen density of 17.8 wt%. The theoretical hydrogen conversion efficiency is about 90%. NH₃ is burnable without emission of CO₂ and has advantages as hydrogen and energy carriers.     

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.     

Comparison of theoretical methods of the hydrogen storage capacities of nanoporous carbons

The hydrogen storage capacities of nanoporous carbons, simulated as graphene slit-shaped pores, have been calculated using simple theoretical methods that do not involve computationally expensive calculations. The theoretical methods calculate the storage of hydrogen molecules on a solid porous material by using the Equation Of State, EOS, of the hydrogen gas and the interaction potential energy of H₂ with the surfaces of the pores of the material. Calculations have been carried out using the same interaction potential energy and empirical EOS. The interaction potential energy is obtained from calculations of H₂ on graphene, using a DFT-based method that includes the dispersion interactions. The storage capacities have been calculated as a function of pressure in the range 0.1–25 MPa, of pore width in the range 4.7–20 Å and at 80.15 and 298.15 K. The storage capacities obtained with the methods are compared and the advantages and limitations of the methods are discussed, as well as the storage capacities predicted by the methods for wide pores. These simple theoretical methods are useful to design novel materials for hydrogen storage.     

Performances comparison of adsorption hydrogen storage tanks at a wide temperature and pressure zone

Large-scale application of hydrogen requires safe, reliable and efficient storage technologies. Among the existing hydrogen storage technologies, cryo-compressed hydrogen (CcH₂) storage has the advantages of high hydrogen storage density, low energy consumption and no ortho-para hydrogen conversion. But it still needs higher hydrogen storage pressure when reaching higher hydrogen storage density. In order to reduce hydrogen storage pressure and improve storage density, solid adsorption technology is introduced in CcH₂. Activated carbon and metal-organic framework materials (MOFs) are employed as adsorbents in this paper. The gravimetric/volumetric hydrogen storage capacities of different adsorption tanks are studied and compared with the hydrogen storage conditions of 1–55 MPa at 77–298 K. The results show that the hydrogen storage density of CcH₂ combined with adsorption is higher than that of pure adsorption hydrogen storage, and the storage pressure is lower than that of pure CcH₂ under the same hydrogen storage capacity. And the combination of two hydrogen storage technologies can achieve a high hydrogen storage capacity equivalent to that of liquid hydrogen at a lower pressure.     

Grand Canonical Monte Carlo simulations of the hydrogen storage capacities of slit-shaped pores,nanotubes and torusenes

Grand Canonical Monte Carlo, GCMC, simulations are used to study the gravimetric and volumetric hydrogen storage capacities of different carbon nanopores shapes: Slit-shaped, nanotubes and torusenes at room temperature, 298.15 K, and at pressures between 0.1 and 35 MPa, and for pore diameter or width between 4 and 15 Å. The influence of the pore shape or curvature on the storage capacities as a function of pressure, temperature and pore diameter is investigated and analyzed. A large curvature of the pores means, in general, an increase of the storage capacities of the pores. While torusenes and nanotubes have surfaces with more curvature than the slit-shaped planar pores, their capacities are lower than those of the slit-shaped pores, according to the present GCMC simulations. Torusene, a less studied carbon nanostructure, has two radii or curvatures, but their storage capacities are similar or lower than those of nanotubes, which have only one radius or curvature. The goal is to obtain qualitative and quantitative relationships between the structure of porous materials and the hydrogen storage capacities, in particular or especially the relationship between shape and width of the pores and the hydrogen storage capacities of carbon-based porous materials.     

A high-performance ternary ferrite-spinel material for hydrogen storage via chemical looping redox cycles

Chemical looping has been proposed as an emerging technology for large-scale hydrogen storage with the advantages of high volumetric hydrogen storage density, environmental compatibility, and safety. However, to ensure sufficient redox activity, conventional oxygen carrier materials must be operated at a temperature higher than 800 °C, leading to the rapid deterioration on the storage capacity over several cycles. In this work, we report a ternary ferrite-spinel material Cu_0.5Co_0.5Fe₂O₄ for chemical looping hydrogen storage and production. The material exhibits high volumetric hydrogen storage density (65.58 g·L⁻¹) and average hydrogen production rate (142 μmol·g⁻¹·min⁻¹) at 550 °C. The performance is maintained with negligible deactivation over repetitive redox cycles. The high performance can be attributed to the ability of Cu and Co to improve the reduction and the reversible phase change during the oxidation stage at moderate temperatures. The performance of the Cu_0.5Co_0.5Fe₂O₄ is comparable to the state-of-the-art Rh-FeO_x containing rare earth metals, which enables its potential in industry application.     

Improving comparability of hydrogen storage capacities of nanoporous materials

We present results of investigations into improving methods by which gas sorption data are collected and reported. The focus is the accurate comparison of hydrogen storage capacities of different nanoporous materials. The aim is to produce a more rigorous approach to the assessment of the hydrogen storage capacities of different nanoporous materials through formulation of meticulous and systematic data collection routines for production of universally reproducible H₂ isotherms over a wide range of pressure and temperature conditions. Effects of a range of experimental variables are examined and recommendations for the optimisation of data collection routines are given.     

Hydrogen generation from LiBH4 solution catalyzed by multiwalled carbon nanotubes supported Co–B nanocatalysts for a portable micro proton exchange membrane fuel cell application

LiBH₄ has high hydrogen storage capacities, and could potentially serve as a superior hydrogen storage material. In the hydrolytic process, however, incomplete hydrolysis caused by the agglomeration of its hydrolytic product and un-reacted LiBH₄ limits its full utilization. Furthermore, application of hydrogen generated from LiBH₄ aqueous solution for proton exchange membrane fuel cell (PEMFC) has not been reported yet. In this paper, CNTs-supported Co–B nanocatalyst was used for hydrogen generation from LiBH₄ solution. 22 wt% LiBH₄ alkaline solution can fully release its stoichiometric amount of hydrogen and supply a 2.3 W portable PEMFC stack to run stably. The overall power density of the PEMFC/LiBH₄ solution system with Co–B/CNTs addition is 1020 Wh L⁻¹. Due to the high gravimetric and volumetric hydrogen capacities, the LiBH₄ solution could be used as a promising liquid hydrogen storage material for hydrogen fuel cells-based devices.     

DFT simulation of hydrogen storage on manganese phosphorous trisulphide (MnPS3)

Manganese phosphorous trisulphide, MnPS₃, is a solid layered material. The hydrogen gravimetric storage capacities of MnPS₃ powder at 80.15, 173.15 and 298.15 K and at moderate pressures has been recently measured in experiments. The origin of the storage capacities of this material is not well understood. The main hypothesis is that hydrogen is stored in the pores of MnPS₃ powder. The pores are modelled as two parallel MnPS₃ layers separated a certain distance. Density Functional Theory simulations of the interaction of H₂ with the surface of a MnPS₃ layer have been carried out, in order to test that hypothesis. The simulations indicate that the adsorption of hydrogen on the surface of a MnPS₃ layer is energetically favourable, but only through the physisorption mechanism. Calculations of the gravimetric capacities of the pores of MnPS₃ powder have also been carried out, obtaining a reasonable agreement with the experimental results. The comparison of the calculated and experimental gravimetric capacities show that the hydrogen storage on MnPS₃ powder is mainly due to compression in the pores and that the contribution of the physisorption process to the storage is very small.     

MOF-5 and activated carbons as adsorbents for gas storage

This paper reports comparatively the capacities of two activated carbons (ACs) and MOF-5 for storing gases. It analyzes, using similar equipments and experimental procedures, the density used to convert gravimetric data to volumetric ones, measuring the density (tap and packing at different pressures). It presents data on porosity, surface area and gas storage (H₂, CH₄ and CO₂) obtained under different temperatures (77 K and RT) and pressures (0.1, 4 and 20 MPa). MOF-5 presents lower volume of narrow micropores than both ACs, making its storage at RT lower, independently of the gas used (H₂, CH₄ and CO₂) and the basis of reporting data (gravimetric or volumetric). For H₂ at 77 K the reliability of the results depends too much on the density used. It is shown that the outstanding volumetric performance of MOF-5, in relation to ACs, is due to the use of an unrealistic high density (crystal density) that, not including the adsorbent inter-particle space, gives an apparently high volumetric gas storage capacity. When a density measured similarly in both types of adsorbents is used (e.g. tap or packing densities) MOF-5 presents, for all gases and conditions studied, lower adsorption capacities on volumetric basis and storage capacities than ACs.     

Different effects of temperature on supramolecular protein and non-protein materials in hydrogen storage

The storage of large quantities of hydrogen at ambient temperature is a key factor in establishing a hydrogen-based economy. One strategy for hydrogen storage is to exploit the interaction between H₂ and a solid material by physisorption of hydrogen on porous materials. However, physisorption materials containing MOF, porous carbons, zeolites, clathrates, and synthesized organic polymers physisorb only about 1 wt% of H₂ at ambient temperature. One approach to solving this problem is to prepare new classes of physisorption materials which exhibits a mechanism different from the reported materials in hydrogen storage. Here we report the synthesis of apo cross-linked ferritin supramolecules by disulfide bonds, and their holo form. Unlike non-protein adsorbents, the hydrogen storage capacity of these protein materials increases as a function of temperature over the range of 20–40 °C. The holo supramolecules enable the adsorption of hydrogen up to 3.51 wt% at 40 °C and 40 bar H₂. In contrast, non-protein physisorption materials such as activated carbon and nano Fe₂O₃ marginally adsorb hydrogen, and, as reported, their ability to adsorb hydrogen decreases with increasing temperature under the same experimental condition. These results demonstrate that protein materials have a unique hydrogen storage mechanism which offers new opportunities in exploration of physisorption materials at ambient temperature.     

Enhanced thermodynamic properties of ZrNiH3 by substitution with transition metals (V,Ti, Fe,Mn and Cr)

First-principles calculations based on Plane-Wave Self-Consistent Field (PWSCF) method, implemented in quantum espresso program, have been performed on ZrNiH₃ substituted with transition metals (V, Ti, Fe, Mn, and Cr). The study aims to investigate the heat of formation in terms of material stability and desorption temperature. It is found that the substitution by transition metals, results in a significant enhancement in the thermodynamic properties accompanied by an increase of the volumetric and gravimetric hydrogen storage capacities. In addition, the obtained values of heat of formation and desorption temperature corroborate with that required by the U.S. Department of Energy (DOE) for stability and volumetric capacity criteria. Moreover, Mn and Fe elements are found to present the lowest substituting content (34%) to obtain optimum hydrogen storage characteristics (enthalpy of formation of - 40 kJ/mol.H₂, decomposition temperature of 300 K and volumetric capacity of 134 g.H₂/l), without affecting the electronic structure and the metallic character of ZrNiH₃.     

Carbon materials for H2 storage

In this work a series of carbons with different structural and textural properties were characterised and evaluated for their application in hydrogen storage. The materials used were different types of commercial carbons: carbon fibers, carbon cloths, nanotubes, superactivated carbons, and synthetic carbons (carbon nanospheres and carbon xerogels). Their textural properties (i.e., surface area, pore size distribution, etc.) were related to their hydrogen adsorption capacities. These H₂ storage capacities were evaluated by various methods (i.e., volumetric and gravimetric) at different temperatures and pressures. The differences between both methods at various operating conditions were evaluated and related to the textural properties of the carbon-based adsorbents. The results showed that temperature has a greater influence on the storage capacity of carbons than pressure. Furthermore, hydrogen storage capacity seems to be proportional to surface area, especially at 77 K. The micropore size distribution and the presence of narrow micropores also notably influence the H₂ storage capacity of carbons. In contrast, morphological or structural characteristics have no influence on gravimetric storage capacity. If synthetic materials are used, the textural properties of carbon materials can be tailored for hydrogen storage. However, a larger pore volume would be needed in order to increase storage capacity. It seems very difficult approach to attain the DOE and EU targets only by physical adsorption on carbon materials. Chemical modification of carbons would seem to be a promising alternative approach in order to increase the capacities.     

Enhanced volumetric hydrogen density in sodium alanate by compaction

Powder compaction is a potential process for the enhancement of the volumetric and gravimetric capacities of hydrogen storage systems based on metal hydrides. This paper presents the hydrogen absorption and desorption behaviour of compacts of sodium alanate material prepared under different levels of compaction pressure. It is shown that even at high compaction levels and low initial porosities, hydrogen absorption and desorption kinetics can proceed comparatively fast in compacted material. Furthermore, experimental hydrogen weight capacities of compacted material are higher than the experimental values obtained in case of loose powder. It is demonstrated that the kinetic behaviour of the compacted material during cycling is directly associated to the volumetric expansion of the compact, which is quantitatively measured and analyzed during both hydrogen absorption and desorption processes. The cycling behaviour and dimensional changes of compacted sodium alanate material are a key consideration point if it is used as hydrogen storage materials in practical tank systems.     

High pressure cryo-storage of hydrogen by adsorption at 77 K and up to 50 MPa

In this paper, we focused on hydrogen adsorption on large surface area solids, combining optimal extreme conditions i.e. very high pressure and low temperature for gas storage process purpose. Therefore, a new volumetric device is elaborated to obtain excess adsorption isotherms at 77 K up to 500 bar. Two activated carbons with different micro-porosities are analysed in the view of hydrogen storage investigation. Also, the results are compared to zeolite adsorption properties. Based on these results, the total mass and volumetric storage capacity are calculated using the bulk density relationship. Thereby, we obtained high storage in situ capacities equal to 5.2 wt% and 54.5 kgH₂/m³. Further, we also considered practical application aspects related to hydrogen storage process in highly porous packed materials.     

Automotive storage of hydrogen in alane

Although alane (AlH₃) has many interesting properties as a hydrogen storage material, it cannot be regenerated on-board a vehicle. One way of overcoming this limitation is to formulate an alane slurry that can be easily loaded into a fuel tank and removed for off-board regeneration. In this paper, we analyze the performance of an on-board hydrogen storage system that uses alane slurry as the hydrogen carrier. A model for the on-board storage system was developed to analyze the AlH₃ decomposition kinetics, heat transfer requirements, stability, startup energy and time, H₂ buffer requirements, storage efficiency, and hydrogen storage capacities. The results from the model indicate that reactor temperatures higher than 200 °C are needed to decompose alane at reasonable liquid hourly space velocities, i.e., > 60 h⁻¹. At the system level, a gravimetric capacity of 4.2 wt% usable hydrogen and a volumetric capacity of 50 g H₂/L may be achievable with a 70% solids slurry. Under optimum conditions, 80% of the H₂ stored in the slurry may be available for the fuel cell engine. The model indicates that H₂ loss is limited by the decomposition kinetics rather than by the rate of heat transfer from the ambient to the slurry tank.     

Bounding material properties for automotive storage of hydrogen in metal hydrides for low-temperature fuel cells

Metal hydride material properties required for on-board hydrogen storage for use with automotive polymer electrolyte fuel cell systems are discussed. Thermodynamic relationships between enthalpy and entropy of sorption are determined such that the storage system can be thermally integrated with the fuel cell system and be refueled at reasonable H₂ supply pressures of 50–200 atm. Simple criteria are developed for specifying minimum discharge kinetic rates needed to satisfy hydrogen demand on automotive duty cycles. Simple criteria are also developed for specifying minimum charge kinetic rates needed to refuel metal hydride tanks in reasonable time. Accessible intrinsic capacity and bulk density of the metal hydride are determined for the storage system to achieve system level targets for gravimetric and volumetric capacities. Based on these analyses, it is recommended that the storage media properties be measured on samples prepared by mixing the metal hydride with a high thermal conductivity material, and compacted to 600 kg m⁻³ bulk density. The compact should have a minimum effective thermal conductivity of 8.5 W m⁻¹ K⁻¹.     

Simulations of volumetric hydrogen storage capacities of nanoporous carbons: Effect of dispersion interactions as a function of pressure,temperature and pore width

Simulations of the hydrogen storage capacities of activated carbons require an accurate treatment of the interaction of a hydrogen molecule physisorbed on the graphitic-like surfaces of nanoporous carbons, which is dominated by the dispersion interactions. These interactions are described accurately by high level quantum chemistry methods such as the Coupled cluster method with single and double excitations and a non-iterative correction for triple excitations (CCSD(T)), but those methods are computationally very expensive for large systems and massive simulations. Density functional theory (DFT) based methods that include dispersion interactions are less accurate, but computationally less expensive. Calculations of the volumetric hydrogen storage capacities of nanoporous carbons, simulated as benzene and graphene slit-shaped pores, have been carried out, using a quantum-thermodynamic model of the physisorption of H₂ on surfaces and the interaction potential energy curves of H₂ physisorbed on benzene and graphene obtained using the CCSD(T) and second order Møller-Plesset (MP2) methods and the 14 most popular DFT-based methods that include the dispersion interactions at different levels of complexity. The effect of the dispersion interactions on the DFT-based volumetric capacities as a function of the pressure, temperature and pore width is evaluated. The error of the volumetric capacities obtained with the quantum-thermodynamic model and each method is also calculated and analyzed.     

Catalytic hydrolysis of hydrazine borane for chemical hydrogen storage: Highly efficient and fast hydrogen generation system at room temperature

There has been rapidly growing interest for materials suitable to store hydrogen in solid state for transportation of hydrogen that requires materials with high volumetric and gravimetric storage capacity. B-N compounds such as ammonia-triborane, ammonia-borane and amine-borane adducts are well suited for this purpose due to their light weight, high gravimetric hydrogen storage capacity and inclination for bearing protic (N-H) and hydridic (B-H) hydrogens. In addition to them, more recent study [26] has showed that hydrazine borane with a gravimetric hydrogen storage capacity of 15.4% wt needs to be considered as another B-N compound that can be used for the storage of hydrogen. Herein we report for the first time, metal catalyzed hydrolysis of hydrazine borane (N₂H₄BH₃, HB) under air at room temperature. Among the catalyst systems tested, rhodium(III) chloride was found to provide the highest catalytic activity in this reaction. In the presence of rhodium(III) chloride, the aqueous solution of hydrazine borane undergoes fast hydrolysis to release nearly 3.0 equivalent of H₂ at room temperature with previously unprecedented H₂ generation rate TOF = 12000 h⁻¹. More importantly, it was found that in the catalytic hydrolysis of hydrazine borane the reaction between hydrazine borane and water proceeds almost in stoichiometric proportion indicating that the efficient hydrogen generation can be achieved even from the highly concentrated solution of hydrazine borane or in the solid state when water added to the solid hydrazine borane. This finding is crucial especially for on-board application of the existing system. The work reported here also includes (i) finding the solubility of hydrazine borane plus its stability against self-hydrolysis in water, (ii) the definition of reaction stoichiometry and the identification of reaction products for the catalytic hydrolysis of hydrazine borane, (iii) the collection of wealthy kinetic data to demonstrate the effect of substrate and catalyst concentrations on the hydrogen generation rate and to determine the rate law for the catalytic hydrolysis of hydrazine borane, (iv) the investigation of the effect of temperature on the rate of hydrogen generation and determination of activation parameters (E_a, ΔH^#, and ΔS^#) for the catalytic hydrolysis of hydrazine borane.