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Abstract: In this work, the tests of a hydrogen storage system intended for vehicular applications, using a metal hydride as storage material, are reported. The system is designed to deliver gas to a fuel cell prototype vehicle. The room temperature hydride is an interstitial alloy, which is selected for its capacity to absorb and desorb hydrogen over an appropriate range of temperature and pressure. The static tests aim to assess whether the requirements for hydrogen release are reliably met by the tank setup. Hypothetical on‐road tests have been designed and applied. Dynamic tests allow moving from energy to power density. Solutions are adopted to face the issues of thermal management at higher‐demanding performances. Several cycles have been performed to find the ideal settings to preserve high average and peak gas flow in a realistic situation. The use of a metal hydride, to replace pressurized gas, results in improved performances, including an extended range at lower loading pressures. Decreasing the pressure in the storage system enables the advantageous possibility to reload the tank several times with commercially available cylinders. Possible future enhancements in the reduction of the total weight of the system are also considered. [ABSTRACT FROM AUTHOR]

Ball milled (30 h) MgH 2 is impregnated on the pores/grooves of activated charcoal scaffold using a programmed heat treatment at 550 °C under 5 bar pure hydrogen ambient. The result obtained by this approach is better and more consistent than the materials prepared by metal infiltration at 650 °C or vacuum heated samples under 550 °C. The activation energy value (88 kJ/mol) obtained in the case of impregnated catalyst free material is far better than the activation energy value of the unconfined material (149 kJ/mol). The impregnated material can absorb hydrogen almost closer to its actual capacity at ∼1 bar under 170 °C. The low temperature desorption characteristics and ab/desorption behaviors are extensively analyzed and described. [ABSTRACT FROM AUTHOR]

With the aim to find suitable hydrogen storage materials for stationary and mobile applications, multi-cation amide-based systems have attracted considerable attention, due to their unique hydrogenation kinetics. In this work, AmZn(NH2)n (with A = Li, K, Na, and Rb) were synthesized via an ammonothermal method. The synthesized phases were mixed via ball milling with LiH to form the systems AmZn(NH2)n-2nLiH (with m = 2, 4 and n = 4, 6), as well as Na2Zn(NH2)4∙0.5NH3-8LiH. The hydrogen storage properties of the obtained materials were investigated via a combination of calorimetric, spectroscopic, and diffraction methods. As a result of the performed analyses, Rb2Zn(NH2)4-8LiH appears as the most appealing system. This composite, after de-hydrogenation, can be fully rehydrogenated within 30 s at a temperature between 190 °C and 200 °C under a pressure of 50 bar of hydrogen. [ABSTRACT FROM AUTHOR]

In this paper, a gas-to-power (GtoP) system for power outages is digitally modeled and experimentally developed. The design includes a solid-state hydrogen storage system composed of TiFeMn as a hydride forming alloy (6.7 kg of alloy in five tanks) and an air-cooled fuel cell (maximum power: 1.6 kW). The hydrogen storage system is charged under room temperature and 40 bar of hydrogen pressure, reaching about 110 g of hydrogen capacity. In an emergency use case of the system, hydrogen is supplied to the fuel cell, and the waste heat coming from the exhaust air of the fuel cell is used for the endothermic dehydrogenation reaction of the metal hydride. This GtoP system demonstrates fast, stable, and reliable responses, providing from 149 W to 596 W under different constant as well as dynamic conditions. A comprehensive and novel simulation approach based on a network model is also applied. The developed model is validated under static and dynamic power load scenarios, demonstrating excellent agreement with the experimental results. [ABSTRACT FROM AUTHOR]

Abstract: Several mixtures of LiBH4 and Mg(BH4)2 borohydrides in different stoichiometric ratios (1:0, 2:1, 1:1, 1:2, 0:1), prepared by high energy ball milling, have been investigated with X-ray powder diffraction and thermal programmed desorption (TPD) volumetric analysis to test the dehydrogenation kinetics in correlation with the physical mixture composition. Afterwards mixed and unmixed borohydrides were dispersed on high specific surface area ball milled graphite by means of the solvent infiltration technique. BET and statistical thickness methods were used to characterize the support surface properties, and SEM micrographs gave a better understanding of the preparation techniques. It has been observed by TPD volumetric measurements that the confinement of the reactive borohydrides on the nanoporous supports leads to a lower dehydrogenation temperature compared to unsupported borohydrides. Moreover, a further decrease of the dehydrogenation temperature has been observed by increasing the specific surface area of the support and the pores volume and by using the prepared mixtures instead of pure materials. The dehydrogenation process seems to be favoured by the heterogeneous nucleation on the graphite surface of decomposition products or intermediate phases from melted liquid borohydrides. [Copyright &y& Elsevier]

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 0.85 Mn 0.05 was selected as H 2 -carrier for a storage plant of about 50 kg of H 2. In this work, a batch of 5 kg of TiFe 0.85 Mn 0.05 alloy was synthesized at industrial level and characterized to determine the structure and phase abundance. The H 2 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 1.0H 2 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 H 2 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. [Display omitted] • TiFe 0.85 Mn 0.05 alloy was prepared at industrial level and deeply characterized. • Industrial preparation strongly affects the hydrogen sorption properties. • TiFe 0.85 Mn 0.05 shows suitable properties for a large-scale storage system. • TiFe 0.85 Mn 0.05 is activated in mild conditions, stable over cycling and poisoning. [ABSTRACT FROM AUTHOR]

In this work, the possibility of creating a polymer-based adaptive scaffold for improving the hydrogen storage properties of the system 2LiH+MgB2+7.5(3TiCl3·AlCl3) was studied. Because of its chemical stability toward the hydrogen storage material, poly(4-methyl-1-pentene) or in-short TPXTM was chosen as the candidate for the scaffolding structure. The composite system was obtained after ball milling of 2LiH+MgB2+7.5(3TiCl3·AlCl3) and a solution of TPXTM in cyclohexane. The investigations carried out over the span of ten hydrogenation/de-hydrogenation cycles indicate that the material containing TPXTM possesses a higher degree of hydrogen storage stability. [ABSTRACT FROM AUTHOR]

Several different milling parameters (additive content, rotation velocity, ball-to-powder ratio, degree of filling, and time) affect the hydrogen absorption and desorption properties of a reactive hydride composite (RHC). In this paper, these effects were thoroughly tested and analyzed. The milling process investigated in such detail was performed on the 2LiH-MgB2 system doped with TiCl3. Applying an upgraded empirical model, the transfer of energy to the material during the milling process was determined. In this way, it is possible to compare the obtained experimental results with those from processes at different scales. In addition, the different milling parameters were evaluated independently according to their individual effect on the transferred energy. Their influence on the reaction kinetics and hydrogen capacity was discussed and the results were correlated to characteristics like particle and crystallite size, specific surface area, presence of nucleation sites and contaminants. Finally, an optimal value for the transferred energy was determined, above which the powder characteristics do not change and therefore the RHC system properties do not further improve. [ABSTRACT FROM AUTHOR]

Reaction kinetic behaviour and cycling stability of the 2LiBH4–MgH2 reactive hydride composite (Li-RHC) are experimentally determined and analysed as a basis for the design and development of hydrogen storage tanks. In addition to the determination and discussion about the properties; different measurement methods are applied and compared. The activation energies for both hydrogenation and dehydrogenation are determined by the Kissinger method and via the fitting of solid-state reaction kinetic models to isothermal volumetric measurements. Furthermore, the hydrogen absorption–desorption cycling stability is assessed by titration measurements. Finally, the kinetic behaviour and the reversible hydrogen storage capacity of the Li-RHC are discussed. [ABSTRACT FROM AUTHOR]

Thermodynamic and heat transfer properties of the 2LiBH4-MgH2 composite (Li-RHC) system are experimentally determined and studied as a basis for the design and development of hydrogen storage tanks. Besides the determination and discussion of the properties, different measurement methods are applied and compared to each other. Regarding thermodynamics, reaction enthalpy and entropy are determined by pressure-concentration-isotherms and coupled manometric-calorimetric measurements. For thermal diffusivity calculation, the specific heat capacity is measured by high-pressure differential scanning calorimetry and the effective thermal conductivity is determined by the transient plane source technique and in situ thermocell. Based on the results obtained from the thermodynamics and the assessment of the heat transfer properties, the reaction mechanism of the Li-RHC and the issues related to the scale-up for larger hydrogen storage systems are discussed in detail. [ABSTRACT FROM AUTHOR]

In this work, the mechanical milling of a FeTiMn alloy for hydrogen storage purposes was performed in an industrial milling device. The TiFe hydride is interesting from the technological standpoint because of the abundance and the low cost of its constituent elements Ti and Fe, as well as its high volumetric hydrogen capacity. However, TiFe is difficult to activate, usually requiring a thermal treatment above 400 °C. A TiFeMn alloy milled for just 10 min in a 100 L industrial milling device showed excellent hydrogen storage properties without any thermal treatment. The as-milled TiFeMn alloy did not need any activation procedure and showed fast kinetic behavior and good cycling stability. Microstructural and morphological characterization of the as-received and as-milled TiFeMn alloys revealed that the material presents reduced particle and crystallite sizes, even after such short time of milling. The refined microstructure of the as-milled TiFeMn is deemed to account for the improved hydrogen absorption-desorption properties. • First industrial-sized milling treatment procedure for TiFe alloys reported. • Milled alloy does not need thermal activation. • Milled alloy shows superior H 2 sorption behavior vs. thermally treated alloy. • Procedure is easily scalable to larger mills. [ABSTRACT FROM AUTHOR]

Hydrogen is an efficient energy carrier that can be produced from renewable sources, enabling the transition towards CO 2 -free energy. Hydrogen can be stored for a long period in the solid-state, with suitable alloys. Ti-rich TiFe 0.90 compound exhibits a mild activation process for the first hydrogenation, and Ti(Fe,Mn) 0.90 substituted alloys can lead to the fine tuning of equilibrium pressure as a function of the final application. In this study, the crystal structure of TiFe (0.90- x) Mn x alloys (x = 0, 0.05 and 0.10) and their deuterides has been determined by in-situ neutron diffraction, while recording Pressure-Composition Isotherms at room temperature. The investigation aims at analysing the influence of Mn for Fe substitution in Ti-rich Ti(Fe,Mn) 0.90 alloys on structural properties during reversible deuterium loading, which is still unsolved and seldom explored. After activation, samples have been transferred into custom-made stainless-steel and aluminium alloy cells used for in-situ neutron diffraction experiments during deuterium loading at ILL and ISIS neutron facilities, respectively. The study enables remarkable understanding on hydrogen storage, basic structural knowledge, and support to the industrial application of TiFe-type alloys for integrated hydrogen tank in energy storage systems by determining the volume expansion during deuteration. Furthermore, the study demonstrates that different contents of Mn do not significantly change the volumetric expansion during phase transitions, affecting only the deuterium content for the γ phase and the cell evolution for the β phase. The study confirms that the deuterated structures of the γ phase upon absorption, β and α phase upon desorption, correspond to S.G. Cmmm , P 222 1 and Pm -3 m , respectively. [Display omitted] • Effect of Mn content on structural and hydrogenation properties in TiFe determined. • Mn-substituted TiFe deuterates structures determined by in situ neutron diffraction. • Mn does not significantly change volumetric expansion during phase transitions. • Mn substitution affects deuterium content for γ and cell evolution for β phase. • Mn substitution favours a stable deuterium occupancy over 2 a and 2 d sites. [ABSTRACT FROM AUTHOR]

Mesoporous carbon frameworks were synthesized using the soft-template method. Ca(BH4)2 was incorporated into activated mesoporous carbon by the incipient wetness method. The activation of mesoporous carbon was necessary to optimize the surface area and pore size. Thermal programmed absorption measurements showed that the confinement of this borohydride into carbon nanoscaffolds improved its reversible capacity (relative to the reactive portion) and performance of hydrogen storage compared to unsupported borohydride. Hydrogen release from the supported hydride started at a temperature as low as 100 °C and the dehydrogenation rate was fast compared to the bulk borohydride. In addition, the hydrogen pressure necessary to regenerate the borohydride from the dehydrogenation products was reduced. [ABSTRACT FROM AUTHOR]

This work proposes an effective thermal activation method with low technical effort for industrially produced titanium-iron-manganese powders (TiFeMn) for hydrogen storage. In this context, the influence of temperature and particle size of TiFeMn on the activation process is systematically studied. The results obtained from this investigation suggest that the activation of the TiFeMn material at temperatures as low as 50 °C is already possible, with a combination of "Dynamic" and "Static" routines, and that an increase to 90 °C strongly reduces the incubation time for activation, i.e. the incubation time of the sample with the two routines at 90 °C is about 0.84 h, while ∼ 277 h is required for the sample treated at 50 °C in both "Dynamic" and "Static" sequences. Selecting TiFeMn particles of larger size also leads to significant improvements in the activation performance of the investigated material. The proposed activation routine makes it possible to overcome the oxide layer existing on the compound surface, which acts as a diffusion barrier for the hydrogen atoms. This activation method induces further cracks and defects in the powder granules, generating new surfaces for hydrogen absorption with greater frequency, and thus leading to faster sorption kinetics in the subsequent absorption-desorption cycles. [Display omitted] • An effective, low technical effort, thermal activation method for TiFe alloy is proposed. • Systematic analysis of the effect of temperature and particle size on the activation. • The diffusion barrier, due to the oxide layer on the surface, is overcome. • Creation of cracks and defects in the powder leads to improved initial kinetics. [ABSTRACT FROM AUTHOR]

Abstract: Hydrogenation properties and mechanical stability of pellets made starting from compressed ball-milled MgH2 powders mixed with catalysts (Nb2O5 and graphite) and a binding agent (aluminium powder) have been investigated. Structural characterization with X-ray diffraction and gas–solid reaction kinetic and thermodynamic tests with a Sievert''s apparatus have been done on the samples up to 50 hydrogen absorption/desorption (a/d) cycles. The best cycling behaviour and mechanical strength stability have been observed for pellets of catalysed MgH2 powders added with 5 wt% aluminium annealed in vacuum at 450°C before starting the a/d cycles. This mechanical stability to cycles has been attributed to the formation of a solid solution of aluminium in magnesium. [Copyright &y& Elsevier]

The goal of the EU Horizon 2020 RISE project 778307 "Hydrogen fuelled utility vehicles and their support systems utilising metal hydrides" (HYDRIDE4MOBILITY), is in addressing critical issues towards a commercial implementation of hydrogen powered forklifts using metal hydride (MH) based hydrogen storage and PEM fuel cells, together with the systems for their refuelling at industrial customers facilities. For these applications, high specific weight of the metallic hydrides has an added value, as it allows counterbalancing of a vehicle with no extra cost. Improving the rates of H 2 charge/discharge in MH on the materials and system level, simplification of the design and reducing the system cost, together with improvement of the efficiency of system "MH store-FC", is in the focus of this work as a joint effort of consortium uniting academic teams and industrial partners from two EU and associated countries Member States (Norway, Germany, Croatia), and two partner countries (South Africa and Indonesia). The work within the project is focused on the validation of various efficient and cost-competitive solutions including (i) advanced MH materials for hydrogen storage and compression, (ii) advanced MH containers characterised by improved charge-discharge dynamic performance and ability to be mass produced, (iii) integrated hydrogen storage and compression/refuelling systems which are developed and tested together with PEM fuel cells during the collaborative efforts of the consortium. This article gives an overview of HYDRIDE4MOBILITY project focused on the results generated during its first phase (2017–2019). • Advanced metal hydrides for H storage and compression were proposed. • MH containers with improved H charge-discharge dynamic performance. • Integrated with PEM fuel cell hydrogen energy system was developed. • EU Horizon 2020 RISE project 778307 project HYDRIDE4MOBILITY. • Hydrogen powered forklift uses MH based H storage and PEM fuel cell. [ABSTRACT FROM AUTHOR]

• Dependency of hydrogenation properties over extended Ti and Mn compositional range. • Ti and Mn substitutions enlarge TiFe cell volume and linearly reduce equilibrium pressure and hysteresis. • Samples at the Ti-rich side have enhanced storage reversible capacities. • Formation of secondary phases allows first hydrogenation in milder conditions. • Sample s6: best compositional trade-off (high capacity, 1.63 wt%, easy activation, good kinetics). [Display omitted] TiFe intermetallic compound has been extensively studied, owing to its low cost, good volumetric hydrogen density, and easy tailoring of hydrogenation thermodynamics by elemental substitution. All these positive aspects make this material promising for large-scale applications of solid-state hydrogen storage. On the other hand, activation and kinetic issues should be amended and the role of elemental substitution should be further understood. This work investigates the thermodynamic changes induced by the variation of Ti content along the homogeneity range of the TiFe phase (Ti:Fe ratio from 1:1–1:0.9) and of the substitution of Mn for Fe between 0 and 5 at%. In all considered alloys, the major phase is TiFe-type together with minor amounts of TiFe 2 or β-Ti-type and Ti 4 Fe 2 O-type at the Ti-poor and rich side of the TiFe phase domain, respectively. Thermodynamic data agree with the available literature but offer here a comprehensive picture of hydrogenation properties over an extended Ti and Mn compositional range. Moreover, it is demonstrated that Ti-rich alloys display enhanced storage capacities, as long as a limited amount of β-Ti is formed. Both Mn and Ti substitutions increase the cell parameter by possibly substituting Fe, lowering the plateau pressures and decreasing the hysteresis of the isotherms. A full picture of the dependence of hydrogen storage properties as a function of the composition will be discussed, together with some observed correlations. [ABSTRACT FROM AUTHOR]

MgH 2 -based hydrogen storage materials are promising candidates for solid-state hydrogen storage allowing efficient thermal management in energy systems integrating metal hydride hydrogen store with a solid oxide fuel cell (SOFC) providing dissipated heat at temperatures between 400 and 600 °C. Recently, we have shown that graphite-modified composite of TiH 2 and MgH 2 prepared by high-energy reactive ball milling in hydrogen (HRBM), demonstrates a high reversible gravimetric H storage capacity exceeding 5 wt % H, fast hydrogenation/dehydrogenation kinetics and excellent cycle stability. In present study, 0.9 MgH 2 + 0.1 TiH 2 +5 wt %C nanocomposite with a maximum hydrogen storage capacity of 6.3 wt% H was prepared by HRBM preceded by a short homogenizing pre-milling in inert gas. 300 g of the composite was loaded into a storage tank accommodating an air-heated stainless steel metal hydride (MH) container equipped with transversal internal (copper) and external (aluminium) fins. Tests of the tank were carried out in a temperature range from 150 °C (H 2 absorption) to 370 °C (H 2 desorption) and showed its ability to deliver up to 185 NL H 2 corresponding to a reversible H storage capacity of the MH material of appr. 5 wt% H. No significant deterioration of the reversible H storage capacity was observed during 20 heating/cooling H 2 discharge/charge cycles. It was found that H 2 desorption performance can be tailored by selecting appropriate thermal management conditions and an optimal operational regime has been proposed. • Upscaled synthesis of MgH 2 –TiH 2 –graphite H storage nanocomposite performed. • The nanocomposite (300 g; storage capacity 6.3 wt %H) used to build H 2 storage tank. • Fast H 2 charge of the tank proceeds at T ≥ 150 °C and P(H 2) = 5–10 bar. • At T = 370–390 °C the tank is able to provide 185 NL H 2 (5 wt% H) with P(H 2) = 2 bar. • H 2 discharge performance is very sensitive to the thermal management conditions. [ABSTRACT FROM AUTHOR]

Abstract Metal hydrides are known as a potential efficient, low-risk option for high-density hydrogen storage since the late 1970s. In this paper, the present status and the future perspectives of the use of metal hydrides for hydrogen storage are discussed. Since the early 1990s, interstitial metal hydrides are known as base materials for Ni – metal hydride rechargeable batteries. For hydrogen storage, metal hydride systems have been developed in the 2010s [1] for use in emergency or backup power units, i. e. for stationary applications. With the development and completion of the first submarines of the U212 A series by HDW (now Thyssen Krupp Marine Systems) in 2003 and its export class U214 in 2004, the use of metal hydrides for hydrogen storage in mobile applications has been established, with new application fields coming into focus. In the last decades, a huge number of new intermetallic and partially covalent hydrogen absorbing compounds has been identified and partly more, partly less extensively characterized. In addition, based on the thermodynamic properties of metal hydrides, this class of materials gives the opportunity to develop a new hydrogen compression technology. They allow the direct conversion from thermal energy into the compression of hydrogen gas without the need of any moving parts. Such compressors have been developed and are nowadays commercially available for pressures up to 200 bar. Metal hydride based compressors for higher pressures are under development. Moreover, storage systems consisting of the combination of metal hydrides and high-pressure vessels have been proposed as a realistic solution for on-board hydrogen storage on fuel cell vehicles. In the frame of the "Hydrogen Storage Systems for Mobile and Stationary Applications" Group in the International Energy Agency (IEA) Hydrogen Task 32 "Hydrogen-based energy storage", different compounds have been and will be scaled-up in the near future and tested in the range of 500 g to several hundred kg for use in hydrogen storage applications. Highlights • Latest developments in the application of hydride technology. • Investigations on both stationary and mobile applications. • Special attention to metal hydride compressors. • Heat storage and H 2 compression especially noted in the Outlook. [ABSTRACT FROM AUTHOR]