Search

Large-scale energy storage plants based on power-to-gas-to-power technologies incorporating high temperature electrolysis, catalytic methanation of H₂ and CO₂ and novel, highly efficient methane-fired Allam reconversion cycles allow for a confined and circular use of CO₂ and thus an emission-free storage of intermittent renewable energy. The Allam power cycle is considered as a beneficial power plant concept, which employs supercritical CO₂ as working fluid as well as an oxy-combustion process to reach high efficiencies of up to 66%. The combination of said process chain could reach a maximum roundtrip efficiency of 54.2 % assuming the presence of sufficient storage capacities for all relevant technical gases. In a technically feasible scenario, paired with a separate air separation unit instead of stationary O₂ storages, roundtrip efficiencies of 49.0 % were determined.. The implementation of said energy storage systems into existing national energy systems will pose a major challenge, since they will require far-reaching infrastructural changes to the respective systems itself, such as extensive installations of renewable generation and electrolysis capacities as well as sufficient subsurface storage capacities for both CO₂ and CH₂. Furthermore, an exemplary energy system forecast for Germany for the year of 2050 is presented to show the viability of the energy storage concept. In case of a fully circular use of CO₂, when electricity is solely generated by renewable energy sources (RES), 736 GW of RES, 234 GW of electrolysis and 62 GW of gas-to-power capacities are required. The total storage volume on the national scale of Germany for both CO₂ and CH₄ was determined to be 7.8 billion Nm³, respectively, leading to a CH₄ storage capacity of 54.5 TWh. The present investigation illustrates the feasibility of large-scale energy storage systems for renewable electricity based on high temperature electrolysis, catalytic methanation and Allam power cycles paired with large subsurface storages for CO₂ and CH₄.

In the past decades, complex hydrides and complex hydrides-based materials have been thoroughly investigated as materials for energy storage, owing to their very high gravimetric and volumetric hydrogen capacities and interesting cation and hydrogen diffusion properties. Concerning hydrogen storage, the main limitations of this class of materials are the high working temperatures and pressures, the low hydrogen absorption and desorption rates and the poor cyclability. In the past years, research in this field has been focused on understanding the hydrogen release and uptake mechanism of the pristine and catalyzed materials and on the characterization of the thermodynamic aspects, in order to rationally choose the composition and the stoichiometry of the systems in terms of hydrogen active phases and catalysts/destabilizing agents. Moreover, new materials have been discovered and characterized in an attempt to find systems with properties suitable for practical on-board and stationary applications. A significant part of this rich and productive activity has been performed by the research groups led by the Experts of the International Energy Agreement Task 32, often in collaborative research projects. The most recent findings of these joint activities and other noteworthy recent results in the field are reported in this paper.

Porous Al scaffolds were synthesised and melt-infiltrated with various eutectic metal borohydride mixtures (0.725LiBH4-0.275KBH4, 0.68NaBH4-0.32KBH4, 0.4NaBH4-0.6 Mg(BH4)2) to simultaneously act as both a confining framework and a reactive destabilising agent for H2 release. The scaffolds were synthesised by sintering a pellet of NaAlH4/2 mol%TiCl3 at 450 °C under dynamic vacuum. During the sintering process the sodium alanate (NaAlH4) decomposed to Al metal. The vacuum applied at elevated temperature promoted the Na metal to vaporise and be extruded from the pellet. The pores of the resulting Al scaffold were created during removal of the H2 and the Na from the body of the NaAlH4/2 mol%TiCl3 pellet. According to the morphological observations carried out by a Scanning Electron Microscope (SEM), melt-infiltrated eutectic mixtures of metal borohydrides were highly dispersed into the porous scaffolds. Temperature Programmed Desorption (TPD) experiments, revealed that the melt-infiltrated samples exhibited faster H2 desorption kinetics in comparison to bulk samples, with onset temperatures (Tdes) lower than the bulk by 150–250 °C. The as-synthesised porous Al scaffolds acted as a reactive containment vessel for these eutectic mixtures that simultaneously nanoconfined and destabilised the mixtures.

Binary combinations of borohydrides have been extensivly investigated evidencing the formation of eutectics, bimetallic compounds or solid solutions. In this paper, the investigation has been extended to ternary and quaternary systems in the LiBH4-NaBH4-KBH4-Mg(BH4)2-Ca(BH4)2 system. Possible interactions among borohydrides in equimolar composition has been explored by mechanochemical treatment. The obtained phases were analysed by X-ray diffraction and the thermal behaviour of the mixtures were analysed by HP-DSC and DTA, defining temperature of transitions and decomposition reactions. The release of hydrogen was detected by MS, showing the role of the presence of solid solutions and multi-cation compounds on the hydrogen desorption reactions. The presence of LiBH4 generally promotes the release of H2 at about 200 °C, while KCa(BH4)3 promotes the release in a single-step reaction at higher temperatures.

To improve the packing efficiency in tank scale, hydrides have been compacted into pellet form; however, poor hydrogen permeability through the pellets results in sluggish kinetics. In this work, the hydrogen sorption properties of compacted 2LiBH4single bondMgH2 doped with 30 wt % activated carbon nanofibers (ACNF) are investigated. After doping with ACNF, onset dehydrogenation temperature of compacted 2LiBH4single bondMgH2 decreases from 350 to 300 °C and hydrogen released content enhances from 55 to 87% of the theoretical capacity. The sample containing ACNF releases hydrogen following a two-step mechanism with reversible hydrogen storage capacities up to 4.5 wt % H2 and 41.8 gH2/L, whereas the sample without ACNF shows a single-step decomposition mainly from MgH2 with only 1.8 wt % H2 and 15.4 gH2/L. Significant kinetic improvement observed in the doped system is due to the enhancement of both hydrogen permeability and heat transfer through the pellet.

Mg2FeD6 is successfully synthesised with various degrees of purity using reactive ball milling and annealing under low pressure deuterium conditions to a maximum of 10 bar. The deuteride of the low cost ternary metal hydride Mg2FeH6, is synthesised to enable further characterisation studies such as isotopic exchange behaviour. Both on laboratory and industrial scales, keeping the pressure low reduces the need for expensive compression systems and also minimises the quantity of gas necessary for use; therefore it is important to assess synthesis under these cost effective conditions. This is especially the case when using a specialised gas such as high purity deuterium. The maximum pressure chosen is 10 bar, to comply with the High Pressure Safety Act in Japan. This Safety Act limits the use of any gas including hydrogen and deuterium to 10 bar eliminating the use of traditional synthesis methods for Mg2FeH6 or Mg2FeD6 synthesis at high pressure (120 bar). Ball milling parameters such as milling times, ball to powder ratios as well as sintering times were altered to achieve improved Mg2FeD6 yields under these low pressure conditions.

Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the slow rates for some processes such as hydrogen diffusion through the bulk create challenges for large-scale implementation. The present paper reviews fundamentals of the Mg–H system and looks at the recent advances in the optimisation of magnesium hydride as a hydrogen storage material through the use of catalytic additives, incorporation of defects and an understanding of the rate-limiting processes during absorption and desorption.

Magnesium-based alloys attract significant interest as cost-efficient hydrogen storage materials allowing the combination of high gravimetric storage capacity of hydrogen with fast rates of hydrogen uptake and release and pronounced destabilization of the metal–hydrogen bonding in comparison with binary Mg–H systems. In this review, various groups of magnesium compounds are considered, including (1) RE–Mg–Ni hydrides (RE = La, Pr, Nd); (2) Mg alloys with p-elements (X = Si, Ge, Sn, and Al); and (3) magnesium alloys with d-elements (Ti, Fe, Co, Ni, Cu, Zn, Pd). The hydrogenation–disproportionation–desorption–recombination process in the Mg-based alloys (LaMg12, LaMg11Ni) and unusually high-pressure hydrides synthesized at pressures exceeding 100 MPa (MgNi2H3) and stabilized by Ni–H bonding are also discussed. The paper reviews interrelations between the properties of the Mg-based hydrides and p–T conditions of the metal–hydrogen interactions, chemical composition of the initial alloys, their crystal structures, and microstructural state.

Magnesium hydride has been studied extensively for applications as a hydrogen storage material owing to the favourable cost and high gravimetric and volumetric hydrogen densities. However, its high enthalpy of decomposition necessitates high working temperatures for hydrogen desorption while the slow rates for some processes such as hydrogen diffusion through the bulk create challenges for large-scale implementation. The present paper reviews fundamentals of the Mg–H system and looks at the recent advances in the optimisation of magnesium hydride as a hydrogen storage material through the use of catalytic additives, incorporation of defects and an understanding of the rate-limiting processes during absorption and desorption.

Combinations of complex metal borohydrides ball milled with the transition metal complex hydride, Mg2FeH6, are analysed and compared. Initially, the Reactive Hydride Composite (RHC) of Mg2+ cation mixtures of Mg2FeH6 and γ-Mg(BH4)2 is combined in a range of molar ratios and heated to a maximum of 450 °C. For the molar ratio of 6 Mg2FeH6 + Mg(BH4)2, simultaneous desorption of the two hydrides occurred, which resulted in a single event of hydrogen release. This single step desorption occurred at temperatures between those of Mg2FeH6 and γ-Mg(BH4)2. Keeping this anionic ratio constant, the desorption behavior of four other borohydrides, Li-, Na-, K-, and Ca-borohydrides was studied by using materials ball milled with Mg2FeH6 applying the same milling parameters. The mixtures containing Mg-, Li-, and Ca-borohydrides also released hydrogen in a single event. The Mass Spectrometry (MS) results show a double step reaction within a narrow temperature range for both the Na- and K-borohydride mixtures. This phenomenon, observed for the RHC systems at the same anionic ratio with all five light metal borohydride mixtures, can be described as simultaneous hydrogen desorption within a narrow temperature range centered around 300 °C.

Nanoconfinement of 2LiBH-MgH-TiCl in resorcinol-formaldehyde carbon aerogel scaffold (RF-CAS) for reversible hydrogen storage applications is proposed. RF-CAS is encapsulated with approximately 1.6 wt. % TiCl by solution impregnation technique, and it is further nanoconfined with bulk 2LiBH-MgH via melt infiltration. Faster dehydrogenation kinetics is obtained after TiCl impregnation, for example, nanoconfined 2LiBH-MgH-TiCl requires ∼1 and 4.5 h, respectively, to release 95% of the total hydrogen content during the 1st and 2nd cycles, while nanoconfined 2LiBH -MgH (∼2.5 and 7 h, respectively) and bulk material (∼23 and 22 h, respectively) take considerably longer. Moreover, 95-98.6% of the theoretical H storage capacity (3.6-3.75 wt. % H) is reproduced after four hydrogen release and uptake cycles of the nanoconfined 2LiBH-MgH-TiCl. The reversibility of this hydrogen storage material is confirmed by the formation of LiBH and MgH after rehydrogenation using FTIR and SR-PXD techniques, respectively.

Die Speicherung intermittierend zur Verfügung stehender erneuerbarer Energien (Wind, Sonne) über die Wasserstoff-route stellt eine Möglichkeit dar, diese Energie im MWh Maßstab bedarfsgerecht zur Verfügung zu stellen. Hierzu be-darf es effizienter und kostengünstig Elektrolyseure oder auch direkter photoelektrischer oder -katalytischer Verfahren zur Wasserstofferzeugung. Insbesondere aber muss dieser Wasserstoff vor der Rückverstromung oder stofflichen Nut-zung energieeffizient und kostengünstig zwischengespeichert werden. Der vorliegende Beitrag diskutiert den Stand der Technik bei der Speicherung von Wasserstoff in Metallhydriden und zeigt Vor- und Nachteile dieser Technologie ge-genüber der Druck- und Flüssigwasserstoffspeicherung auf.

The Ca(BH4)2-MgH2 composite system represents a promising candidate for mobile hydrogen storage due to a 10.5 wt % theoretical hydrogen storage capacity and an estimated equilibrium temperature lower than 160 °C. For this system, the reversibility was achieved without further addition of additives. In this study, the decomposition path of the Ca(BH4)2 + MgH2 composite system is investigated in detail by in situ synchrotron radiation powder X-ray diffraction and differential scanning calorimetry combined with thermogravimetry. The sorption properties are analyzed by volumetric measurements. 11B{1H} solid state magic angle spinning-nuclear magnetic resonance was employed for the characterization of the final amorphous or nanocrystalline boron-based decomposition products. This study shows that the intermediate formation of Ca4Mg3H14 upon dehydrogenation of the Ca(BH4)2-MgH2 composite system is not a necessary step, and its presence can be adjusted modifying the preparation procedure. Moreover, the d-value mismatch calculated for the {111}CaB6/{1011}Mg plane pair is the lowest among the other plane pairs considered in the system. The mismatch in the third direction between CaB6 and Mg is also extremely good. These findings propose Mg as a supporter of the heterogeneous nucleation of CaB6 during decomposition of the Ca(BH4)2 + MgH2 composite system.

The present investigation focuses on a new synthesis route of NaBH4 starting from the 2NaH + MgB2 system subjected to mechanochemical activation under reactive hydrogen atmosphere. The milling process was carried out under two different hydrogen pressures (1 and 120 bar) with two different rotation speeds (300 and 550 rpm). The reaction products were characterized by ex-situ solid state magic angle spinning (MAS) nuclear magnetic resonance (NMR), ex-situ X-ray powder diffraction (XRPD) and Infrared Spectroscopy (IR). From the results of these analyses, it can be concluded that milling in all the considered conditions led to the formation of NaBH4 (cubic-Fm-3m). In particular, a reaction yield of 5 and 14 wt% is obtained after 20 h of milling at 120 bar of H2 for the tests performed at 300 rpm and 550 rpm, respectively. The presence of MgH2 is also detected among the final products on the as milled powders. The influence of the milling conditions and the evaluation of the parameters related the mechanochemical process are here discussed.

Light metal tetrahydroborates are regarded as promising materials for solid state hydrogen storage. Due to both a high gravimetric hydrogen capacity of 11.5 wt % and an ideal dehydrogenation enthalpy of 32 kJ mol-1 H2, Ca(BH4)2 is considered to be one of the most interesting compounds in this class of materials. In this work, a comprehensive investigation of the effect of different selected additives (TiF4, NbF5, Ti-isopropoxide, and CaF2) on the reversible hydrogenation reaction of calcium borohydride is presented combining different investigation techniques. The chemical state of the Nb- and Ti-based additives is studied by X-ray absorption spectroscopy (e.g., XANES). Transmission electron microscopy (TEM) coupled with selected area electron diffraction (SAED) and energy-dispersive X-ray spectroscopy (EDX) was used to show the local structure, size, and distribution of the additive/catalyst. 11B{1H} solid state magic angle spinning-nuclear magnetic resonance (MAS NMR) was carried out to detect possible amorphous phases. The formation of TiB2 and NbB2 nanoparticles was observed after milling or upon sorption reactions of the Nb- and Ti-based Ca(BH4)2 doped systems. The formation of transition-metal boride nanoparticles is proposed to support the heterogeneous nucleation of CaB6. The {111}CaB6/{1011}NbB2, {111}CaB6/{1010}NbB2, as well as {111}CaB6/{1011}TiB2 plane pairs have the potential to be the matching planes because the d-value mismatch is well below the d-critical mismatch value (6%). Transition-metal boride nanoparticles act as heterogeneous nucleation sites for CaB6, refine the microstructure thus improving the sorption kinetics, and, as a consequence, lead to the reversible formation of Ca(BH4)2.

The structure of an unknown crystalline phase observed during the hydrogen absorption reaction of the powder mixtures 2NaH + MgB2 at high pressure has been studied by ab-initio structure determination from powder diffraction. The sequence of un-overlapped peaks extracted from the X-ray powder diffraction pattern could be indexed with a primitive cubic cell with lattice parameter a = 7.319 Å. The diffraction patterns of the peaks are matched with the Pa-3 space group. The stoichiometry of the hydrogen absorption reaction suggests the presence of a high-boron content phase in the compound under investigation. Assuming this phase to be composed only by boron atoms and therefore having a density similar to that found for boron polymorphs, the solution with a space group of Pa-3 leads to reasonable B–B interatomic distances.

Sodium alanate is being experimentally tested in scaled-up quantities. For this purpose, several tanks have been designed and constructed. The tank functionality during absorption and desorption of hydrogen was demonstrated in a scale of 8 kg of alanate, with a peak technical absorption time below 10 min. The absorption and desorption data show good reproducibility. Neutron radiography was used in another tank to show the powder’s physical behavior during sorption, showing conservation of the macroscopic structure during cycling.

The influence of different titanium additives on hydrogen sorption in LiH–MgB2 system has been investigated. For all the composites LiH–MgB2–X (X = TiF4, TiO2, TiN, and TiC), prepared by ball-milling in molar ratios 2:1:0.1, five hydrogen uptake/release cycles were performed. In-situ synchrotron radiation powder X-ray diffraction (SR-PXD) and attenuated total reflection infrared spectroscopy (ATR-IR) have been used to characterize crystal phases developed during the hydrogen absorption–desorption cycles. All the composites with the titanium additives displayed an improvement of reaction kinetics, especially during hydrogen desorption. The LiH–MgB2–TiO2 system reached a storage of about 7.6 wt % H2 in ∼1.8 h for absorption and ∼2.7 h for desorption. Using in-situ SR-PXD measurements, magnesium was detected as an intermediate phase during hydrogen desorption for all composites. In the composite with TiF4 addition the formation of new phases (TiB2 and LiF) were observed. Characteristic diffraction peaks of TiO2, TiN and TiC additives were always present during hydrogen absorption–desorption. For all as-milled composites, ATR-IR spectra did not show any signals for borohydrides, while for all hydrogenated composites B–H stretching (2450–2150 cm−1) and B–H bending (1350–1000 cm−1) bands were exactly the same as for commercial LiBH4.

The influence of additives on the reaction kinetics and microstructure refinement in LiBH4–MgH2 composites is investigated in detail. Indications of the rate-limiting processes during the reactions are obtained by comparison of the measured reaction kinetics with simulations with one specific rate-limiting process. The kinetics of the sorption reactions are derived from volumetric measurements as well as from in situ X-ray diffraction measurements. During desorption, the hydrogen is released at a constant rate, which is possibly correlated with the one-dimensional growth of MgB2 platelets. In contrast, the kinetic curves of the absorption reactions exhibit the typical shape of contracting-volume controlled kinetics. The microscopical interpretation of kinetic measurements are supported by transmission electron microscopy images confirming the formation of additive-nanostructures in the grain boundaries upon cycling. The present investigations underline the importance of the additives as nucleation substrates and the influence of microstructure on the reaction kinetics.

Im Rahmen des EU-Projekts STORHY ist der Prototyp eines Metallhydridspeichers auf Natriumalanatbasis für automobile Anwendungen entwickelt worden. Besonderes Merkmal ist die Größe im Vergleich zu bisher vorhandenen Laborreaktoren. Mit Hilfe einer modell-gestützten Simulation wird sein Beladungsverhalten für verschiedene Betriebsbedingungen berechnet. Anhand der Ergebnisse werden die Wirksamkeit der Kühlung und ihr Optimierungspotenzial diskutiert.

The kinetics of the reversible reaction of hydrogen gas with magnesium forming MgH2 is enhanced significantly by the addition of transition metals oxide catalysts and by using nanostructured powders. Hydrogen absorption and desorption properties of such systems were studied by differential scanning calorimetry (DSC) under hydrogen atmosphere, from which the heat of hydride formation and decomposition is determined. Apart from Mg and stoichiometric MgH2, we find an additional, slightly destabilized phase, which is formed prior to MgH2 upon hydrogenation. The amount of this phase depends on the degree of nanostructuring and the used additive. X-ray diffraction measurements confirm the compared to MgH2 slightly different lattice parameters of the intermediate phase. The results correspond to recent neutron diffraction measurements, by which a new MgH2d phase was found. We propose that this destabilized phase acts as a gateway for de-hydrogenation of MgH2.

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 MgH 2 , 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 MgH 2 are presented.

Rechargeable solid-state magnesium batteries are considered for high energy density storage and usage in mobile applications as well as to store energy from intermittent energy sources, triggering intense research for suitable electrode and electrolyte materials. Recently, magnesium borohydride, Mg(BH$_{4}$)$_{2}$, was found to be an effective precursor for solid-state Mg-ion conductors. During the mechanochemical synthesis of these Mg-ion conductors, amorphous Mg(BH$_{4}$)$_{2}$ is typically formed and it was postulated that this amorphous phase promotes the conductivity. Here, electrochemical impedance spectroscopy of as-received γ-Mg(BH$_{4}$)$_{2}$ and ball milled, amorphous Mg(BH$_{4}$)$_{2}$ confirmed that the conductivity of the latter is ~2 orders of magnitude higher than in as-received γ-Mg(BH$_{4}$)$_{2}$ at 353 K. Pair distribution function (PDF) analysis of the local structure shows striking similarities up to a length scale of 5.1 Å, suggesting similar conduction pathways in both the crystalline and amorphous sample. Up to 12.27 Å the PDF indicates that a 3D net of interpenetrating channels might still be present in the amorphous phase although less ordered compared to the as-received γ-phase. However, quasi elastic neutron scattering experiments (QENS) were used to study the rotational mobility of the [BH$_{4}$] units, revealing a much larger fraction of activated [BH$_{4}$] rotations in amorphous Mg(BH$_{4}$)$_{2}$. These findings suggest that the conduction process in amorphous Mg(BH$_{4}$)$_{2}$ is supported by stronger rotational mobility, which is proposed to be the so-called “paddle-wheel” mechanism.

Artículo escrito por un elevado número de autores, solo se referencian el que aparece en primer lugar, el nombre del grupo de colaboración, si le hubiere, y los autores pertenecientes a la UAM, Hydrides based on magnesium and intermetallic compounds provide a viable solution to the challenge of energy storage from renewable sources, thanks to their ability to absorb and desorb hydrogen in a reversible way with a proper tuning of pressure and temperature conditions. Therefore, they are expected to play an important role in the clean energy transition and in the deployment of hydrogen as an efficient energy vector. This review, by experts of Task 40 'Energy Storage and Conversion based on Hydrogen' of the Hydrogen Technology Collaboration Programme of the International Energy Agency, reports on the latest activities of the working group 'Magnesium- and Intermetallic alloys-based Hydrides for Energy Storage'. The following topics are covered by the review: multiscale modelling of hydrides and hydrogen sorption mechanisms; synthesis and processing techniques; catalysts for hydrogen sorption in Mg; Mg-based nanostructures and new compounds; hydrides based on intermetallic TiFe alloys, high entropy alloys, Laves phases, and Pd-containing alloys. Finally, an outlook is presented on current worldwide investments and future research directions for hydrogen-based energy storage

Communications materials 3(1), 101 (2022). doi:10.1038/s43246-022-00324-5, Intermetallic alloys such as FeTi have attracted ever-growing attention as a safe and efficient hydrogen storage medium. However, the utilization of high-purity metals for the synthesis of such materials poses considerable concerns over the environmental sustainability of their large-scale production. Here, we report an approach for synthesizing FeTi from industrial scraps of iron (steels C45 and 316 L) and titanium (Ti alloy Grade 2) to reduce the carbon footprint associated with FeTi alloy synthesis, without compromising their hydrogen storage properties. At 50 °C and a pressure of 0 to 100 bar, the alloys obtained by using C45-Ti Grade 2 and 316L-Ti Grade 2 can absorb a maximum amount of hydrogen of 1.61 wt.% and 1.50 wt.%, respectively. Moreover, depending on the type of steel utilized, the thermodynamic properties can be modified. Our findings pave a pathway for developing high-performance, environmentally-sustainable FeTi alloys for hydrogen storage purposes using industrial metal wastes., Published by Springer Nature, London

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, The research for the lab-scale compressor is part of the activities of SCCER HaE, which is financially supported by Innosuisse - Swiss Innovation Agency . The authors thank the Alexander von Humboldt Foundation in the frame of the post-doctoral fellowship of Dr. J. Puszkiel (No. 1187279 STP ) as well as the European Union for their funding of projects STORHY (contract Nr. SES6-CT-2004-502667 , FP6-2002-Energy-1, 6.1.3.2.2), NESSHY (contract Nr. 518271 , FP6-2004-Energy-3, 6.1.3.2.2) and the EU Horizon 2020 /RISE project HYDRIDE4MOBILITY. Financial support from the S02 and KP8 S05), the European Union's Seventh Framework Programme ( FP7/2007e2013 ) for the Fuel Cells and Hydrogen Joint Technology Initiative under grant agreement no. 256653 (SSH2S), from the European Fuel Cells and Hydrogen Joint Undertaking in the framework of BOR4STORE (Grant agreement no. 303428 ), from the Australian Research Council for grants LP120101848 , LP150100730 , and LE0989180 , The Innovation Fund Denmark (project HyFill-Fast), DST within Hydrogen South Africa/HySA programme (projects KP3 National Research Foundation/NRF of South Africa , incentive funding grant number 109092 and the Research Council of Norway (project 285147 ) is thankfully acknowledged

The subject of this paper concerns the development of a vehicular hydrogen tank system, using a commercial interstitial metal hydride as storage material. The design of the tank was intended to feed a fuel cell in a light prototype vehicle, and the chosen hydride material, Hydralloy C5 by GfE, was expected to be able to absorb and desorb hydrogen in a range of pressure suitable for this purpose. A systematic analysis of the material in laboratory scale allows an extrapolation of the thermodynamic and reaction kinetics data. The following development of the modular tank was done according to the requirements of the prototype vehicle propulsion system and led to promising intermediate results. The modular approach granted flexibility in the design, allowing both to reach carefully the design goals and to learn the limiting factors in the sorption process. Proper heat management and suitable equipment remain key factors in order to achieve the best performances.

The investigations based on kinetic improvement and reaction mechanisms during melt infiltration, dehydrogenation, and rehydrogenation of nanoconfined 2LiBH4-MgH2-0.13TiCl4 in carbon aerogel scaffold (CAS) are proposed. It is found that TiCl4 and LiBH4 are successfully nanoconfined in CAS, while MgH2 proceeds partially. In the same temperature (25-500ºC) and time (0?5 h at constant temperature) ranges nanoconfined 2LiBH4-MgH2-0.13TiCl4 dehydrogenates completely 99% of theoretical H2 storage capacity, while that of nanoconfined 2LiBH4?MgH2 is only 94%. Nanoconfined 2LiBH4-MgH2-0.13TiCl4 performs three-step dehydrogenation at 140, 240, and 380ºC. Onset (the first-step) dehydrogenation temperature (140ºC), significantly lower than those of nanoconfined sample of 2LiBH4-MgH2 and 2LiBH4-MgH2-TiCl3 (DT = 140 and 110ºC, respectively) is in agreement with the decomposition of eutectic LiBH4-Mg(BH4)2 and lithium?titanium borohydride. For the second and third steps (240 and 380ºC),decompositions of LiBH4 destabilized by LiCl solvation and MgH2 are accomplished, respectively. In conclusion, dehydrogenation products are B, Mg, LiH, and TiH. Reversibility of nanoconfined 2LiBH4-MgH2-0.13TiCl4 sample is confirmed by the recovery of LiBH4 after rehydrogenation together with the formation of [B12H12] derivatives. The superior kinetics during the 2nd, 3rd, and 4th cycles of nanoconfined2LiBH4-MgH2-0.13TiCl4 to the nanoconfined 2LiBH4-MgH2 can be due to the formations of Ti-MgH2 alloys (Mg0.25Ti0.75H2 and Mg6TiH2) during the 1st rehydrogenation. Fil: Gosalawit Utke, Rapee. Institute of Materials Research; Alemania. Suranaree University of Technology; Tailandia Fil: Milanese, Chiara. University of Pavia; Italia Fil: Javadian, Payam. University of Aarhus; Dinamarca Fil: Girella, Alessandro. University of Pavia; Italia Fil: Laipple, Daniel. Institute of Materials Research; Alemania Fil: Puszkiel, Julián Atilio. Institute of Materials Research; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Cattaneo, Alice S.. University of Aarhus; Dinamarca Fil: Ferrara, Chiara. University of Aarhus; Dinamarca Fil: Wittayakhun, Jatuporn. Suranaree University of Technology; Tailandia Fil: Skibsted, Jørgen. University of Aarhus; Dinamarca Fil: Jensen, Torben R.. University of Aarhus; Dinamarca Fil: Marini, Amedeo. University of Pavia; Italia Fil: Klassen, Thomas. Institute of Materials Research; Alemania Fil: Dornheim, Martin. Institute of Materials Research; Alemania