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The inevitable formation of passivating oxide films on the surface of the TiFe intermetallic compound limits its performance as a stationary hydrogen storage material. Extensive experimental efforts have been dedicated to the activation of TiFe, i.e. oxide layer removal prior to utilization for hydrogen storage. However, development of an efficient activation protocol necessitates a fundamental understanding of the composition and structure of the air-exposed surface and its interaction with hydrogen, which currently is absent. Therefore, in this study we explored the growth and nature of the oxide films on the most exposed TiFe surface (110) in depth using static and dynamic first-principles methods. We identified the lowest energy structures for six oxygen coverages up to approximately 1.12 nm of thickness with a global optimization method and studied the temperature effects and structural evolution of the oxide phases in detail via ab-initio molecular dynamics (AIMD). Based on structural similarity and coordination analysis, motifs for TiO2, TiFeO3 as well as Ti(FeO2)x (x = 2, 3 or 5) phases were identified. On evaluating the interaction of the oxidized surface with hydrogen, a minimal energy barrier of 0.172 eV was predicted for H2 dissociation while the H migration from the top of the oxidized surface to the bulk TiFe was limited by several high-lying energy barriers above 1.4 eV. Our mechanistic insights will prove themselves valuable for informed designs towards new activation methods of TiFe and related systems as hydrogen storage materials.

Hydrogen storage properties of K2Mn(NH2)4–8LiH were investigated by considering its de/re-hydrogenation properties and reaction mechanisms. Experimental results show that the dehydrogenated K2Mn(NH2)4–8LiH can be almost re-hydrogenated completely at 230 °C and 50 bar of H2 with a hydrogenation rate more than 1.0 wt%/min. In-situ synchrotron radiation powder X-ray diffraction (SR-PXD) and FTIR investigations reveal that during ball milling K2Mn(NH2)4 reacts with LiH to form LiNH2 and K–Mn-species1 which is probably a K–Mn-containing hydride. The ball milled sample releases hydrogen in a multi-step reaction with the formation of K3MnH5 and K–Mn-species2 as intermediates and Li2NH, Mn3N2 and MnN as final products. The full hydrogenated products are LiH, LiNH2, and K–Mn-species2. The K–Mn-species2 may play a critical role for the fast hydrogeneration. This work indicates that transition metal contained amide-hydride composite holds potentials for hydrogen storage.

Over the last decade's magnesium and magnesium based compounds have been intensively investigated as potential hydrogen storage as well as thermal energy storage materials due to their abundance and availability as well as their extraordinary high gravimetric and volumetric storage densities. This review work provides a broad overview of the most appealing systems and of their hydrogenation/dehydrogenation properties. Special emphasis is placed on reviewing the efforts made by the scientific community in improving the material's thermodynamic and kinetic properties while maintaining a high hydrogen storage capacity.

Although Mg2FeH6 has drawn significant attention for storing hydrogen, its sluggish kinetics during hydrogenation and poor reversibility hinder practical uses. In this work, the replacement of Fe atoms in Mg2FeH6 with Ni atoms is attempted and the material properties are investigated. A detailed study of the de/rehydrogenation kinetics and reaction mechanisms of the Ni-doped Mg2FeH6 is carried out. The effects of Ni-loading contents on kinetic properties and behaviors as well as reversibility and reaction pathways are characterized. In addition, the crystal structure of a new Ni-substituted Mg2FeH6 phase is confirmed.

To find a solution to efficiently exploit renewable energy sources is a key step to achieve complete independence from fossil fuel energy sources. Hydrogen is considered by many as a suitable energy vector for efficiently exploiting intermittent and unevenly distributed renewable energy sources. However, although the production of hydrogen from renewable energy sources is technically feasible, the storage of large quantities of hydrogen is challenging. Comparing to conventional compressed and cryogenic hydrogen storage, the solid-state storage of hydrogen shows many advantages in terms of safety and volumetric energy density. Among the materials available to store hydrogen, metal hydrides and complex metal hydrides have been extensively investigated due to their appealing hydrogen storage properties. Among several potentials candidates, magnesium hydride (MgH2) and lithium borohydride (LiBH4) have been widely recognized as promising solid-state hydrogen storage materials. However, before considering these hydrides ready for real-scale applications, the issue of their high thermodynamic stability and of their poor hydrogenation/dehydrogenation kinetics must be solved. An approach to modify the hydrogen storage properties of these hydrides is nanoconfinement. This review summarizes and discusses recent findings on the use of porous scaffolds as nanostructured tools for improving the thermodynamics and kinetics of MgH2 and LiBH4.

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

The Mg(NH2)2–2LiH composite has been regarded as a promising on-board hydrogen storage material, due to its favorable thermodynamics and high H2 gravimetric capacity. In this paper, a new route to synthesize the Mg(NH2)2–2LiH composite, starting from hydrogenated Li2Mg(NH)2, is presented. Li2Mg(NH)2 is obtained from the decomposition of a mixture of a magnesium waste alloy (AZ91) and LiH, after a multi-step treatment. The as-prepared Mg(NH2)2–2LiH with Mg coming from AZ91 shows improved hydrogen storage properties, as compared with that synthesized from pure magnesium powder, with a lower dehydrogenation peak temperature of about 15 °C. The reaction pathways during the conversion of the AZ91 alloy to Mg(NH2)2–2LiH are investigated by ex situ and in situ XRD techniques. The obtained results confirm that this new approach is an effective way to recycle magnesium waste alloys into lightweight hydrogen storage materials. In addition, this new technology is easy to scale up and reduces the cost of Mg(NH2)2–2LiH, which has important significance for its practical applications.

Sustainability 14(3), 1672 (2022). doi:10.3390/su14031672, 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, A$_m$Zn(NH$_2$)$_n$ (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 A$_m$Zn(NH2)$_n$-2nLiH (with m = 2, 4 and n = 4, 6), as well as Na$_2$Zn(NH$_2$)$_4$∙0.5NH$_3$-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, Rb$_2$Zn(NH$_2$)$_4$-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., Published by MDPI, Basel

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, Industrial and public interest in hydrogen technologies has risen strongly recently, as hydrogen is the ideal means for medium to long term energy storage, transport and usage in combination with renewable and green energy supply. In a future energy system, the production, storage and usage of green hydrogen is a key technology. Hydrogen is and will in future be even more used for industrial production processes as a reduction agent or for the production of synthetic hydrocarbons, especially in the chemical industry and in refineries. Under certain conditions material based systems for hydrogen storage and compression offer advantages over the classical systems based on gaseous or liquid hydrogen. This includes in particular lower maintenance costs, higher reliability and safety. Hydrogen storage is possible at pressures and temperatures much closer to ambient conditions. Hydrogen compression is possible without any moving parts and only by using waste heat. In this paper, we summarize the newest developments of hydrogen carriers for storage and compression and in addition, give an overview of the different research activities in this field

Large-scale energy storage plants based on power-to-gas-to-power (PtG–GtP) technologies incorporating high temperature electrolysis, catalytic methanation for the provision of synthetic natural gas (SNG) and novel, highly efficient SNG-fired Allam reconversion cycles allow for a confined and circular use of CO2/CH4 and thus an emission-free storage of intermittent renewable energy. This study features a thorough technology assessment for large-scale PtG–GtP storage plants based on highly efficient sCO2 power cycles combined with subsurface CO2 storage. The Allam cycle employs supercritical CO2 as working fluid as well as an oxy-combustion process to reach high efficiencies of up to 66%. The entire PtG–GtP process chain assessed in this study is expected to reach maximum roundtrip efficiencies of 54.2% (with dedicated and sufficient O2 storage) or 49.0% (with a dedicated air separation unit). The implementation of said energy storage systems into existing national energy grids will pose a major challenge, since they will require far-reaching infrastructural changes to the respective systems, such as extensive installations of renewable generation and electrolysis capacities as well as sufficient subsurface storage capacities for both CO2 and CH4. Therefore, this study incorporates an assessment of the present subsurface storage potential for CO2 and CH4 in Germany. Furthermore, a basic forecast study for the German energy system with an assumed mass deployment of the proposed SNG-based PtG–GtP energy storage system for the year 2050 is conducted. In case of a fully circular use of CO2/CH4, when electricity is solely generated by renewable energy sources, 736 GW of renewables, 234 GW of electrolysis and 62 GW of gas-to-power capacities are required in the best case scenario in 2050. The total storage volume on the national scale of Germany for both CO2 and CH4 was determined to be 7.8 billion N m3, respectively, leading to a CH4 storage capacity of 54.5 TW h. The presented investigations illustrate 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.

Green chemistry 24(10), 4153 - 4163 (2022). doi:10.1039/D1GC04709D, To reduce the carbon footprint associated with the production of hydrogen storage materials and to reduce their cost, we pursue the possibility of obtaining high-quality hydride-based materials from industrial metals waste. In particular, in this manuscript, we propose a method for obtaining high-quality NaAlH$_4$, starting from the Al-based automotive recycled alloy DIN-GDAlSi10Mg(Cu). The hydrogen storage properties of the material obtained by ball milling NaH and DIN-GDAlSi10Mg(Cu) under a hydrogen atmosphere were comprehensively explored via a broad range of experimental techniques, e.g. volumetric analysis, ex situ X-ray diffraction (XRD), in situ synchrotron radiation powder X-ray diffraction (SR-PXD), scanning electron microscopy (SEM), and differential thermal analysis (DTA). These investigations show that NaAlH$_4$ was successfully synthesized and that its properties are comparable with those of high-purity commercial NaAlH$_4$., Published by RSC, Cambridge

In recent years, many solid-state hydride-based materials have been considered as hydrogen storage systems for mobile and stationary applications. Due to a gravimetric hydrogen capacity of 5.6 wt% and a dehydrogenation enthalpy of 38.9 kJ/mol H2, Mg(NH2)2 + 2LiH is considered a potential hydrogen storage material for solid-state storage systems to be coupled with PEM fuel cell devices. One of the main challenges is the reduction of dehydrogenation temperature since this system requires high dehydrogenation temperatures (~ 200 °C). The addition of KH to this system significantly decreases the dehydrogenation onset temperature to 130 °C. On the one hand, the addition of KH stabilizes the hydrogen storage capacity. On the other hand, the capacity is reduced by 50% (from 4.1 to 2%) after the first 25 cycles. In this work, the particle sizes of the overall hydride matrix and the potassium-containing species are investigated during hydrogen cycling. Relation between particle size evolution of the additive and hydrogen storage kinetics is described by using an advanced synchrotron-based technique: Anomalous small-angle X-ray scattering, which was applied for the first time at the potassium K-edge for amide-hydride hydrogen storage systems. The outcomes from this investigation show that, the nanometric potassium-containing phases might be located at the reaction interfaces, limiting the particle coarsening. Average diameters of potassium-containing nanoparticles double after 25 cycles (from 10 to 20 nm). Therefore, reaction kinetics at subsequent cycles degrade. The deterioration of the reaction kinetics can be minimized by selecting lower absorption temperatures, which mitigates the particle size growth, resulting in two times faster reaction kinetics.

In recent years, the use of selected additives for improving the kinetic behavior of the system 2LiH + MgB2 (Li‐RHC) has been investigated. As a result, it has been reported that some additives (e.g., 3TiCl3∙AlCl3), by reacting with the Li‐RHC components, form nanostructured phases (e.g., AlTi3) possessing peculiar microstructural properties capable of enhancing the system’s kinetic behavior. The effect of in‐house‐produced AlTi3 nanoparticles on the hydrogenation/dehydrogenation kinetics of the 2LiH + MgB2 (Li‐RHC) system is explored in this work, with the aim of reaching high hydrogen storage performance. Experimental results show that the AlTi3 nanoparticles significantly improve the reaction rate of the Li‐RHC system, mainly for the dehydrogenation process. The observed improvement is most likely due to the similar structural properties between AlTi3 and MgB2 phases which provide an energetically favored path for the nucleation of MgB2. In comparison with the pristine material, the Li‐RHC doped with AlTi3 nanoparticles has about a nine times faster dehydrogenation rate. The results obtained from the kinetic modeling indicate a change in the Li‐RHC hydrogenation reaction mechanism in the presence of AlTi3 nanoparticles.

In recent years, the use of selected additives for improving the kinetic behavior of the system 2LiH + MgB2 (Li-RHC) has been investigated. As a result, it has been reported that some additives (e.g., 3TiCl3·AlCl3), by reacting with the Li-RHC components, form nanostructured phases (e.g., AlTi3) possessing peculiar microstructural properties capable of enhancing the system’s kinetic behavior. The effect of in-house-produced AlTi3 nanoparticles on the hydrogenation/dehydrogenation kinetics of the 2LiH + MgB2 (Li-RHC) system is explored in this work, with the aim of reaching high hydrogen storage performance. Experimental results show that the AlTi3 nanoparticles significantly improve the reaction rate of the Li-RHC system, mainly for the dehydrogenation process. The observed improvement is most likely due to the similar structural properties between AlTi3 and MgB2 phases which provide an energetically favored path for the nucleation of MgB2. In comparison with the pristine material, the Li-RHC doped with AlTi3 nanoparticles has about a nine times faster dehydrogenation rate. The results obtained from the kinetic modeling indicate a change in the Li-RHC hydrogenation reaction mechanism in the presence of AlTi3 nanoparticles.

Reversible solid-state hydrogen storage is one of the key technologies toward pollutant-free and sustainable energy conversion. The composite system LiBH4-MgH2 can reversibly store hydrogen with a gravimetric capacity of 13 wt%. However, its dehydrogenation/hydrogenation kinetics is extremely sluggish (~40 h) which hinders its usage for commercial applications. In this work, the kinetics of this composite system is significantly enhanced (~96%) by adding a small amount of NbF5. The catalytic effect of NbF5 on the dehydrogenation/hydrogenation process of LiBH4-MgH2 is systematically investigated using a broad range of experimental techniques such as in situ synchrotron radiation X-ray powder diffraction (in situ SR-XPD), X-ray absorption spectroscopy (XAS), anomalous small angle X-ray scattering (ASAXS), and ultra/small-angle neutron scattering (USANS/SANS). The obtained results are utilized to develop a model that explains the catalytic function of NbF5 in hydrogen release and uptake in the LiBH4-MgH2 composite system., The authors thank the great support from the BT5-Instrument staff at NIST center for Neutron Research. In particular, the authors are thankful to Dr David Mildner and Dr Steve Kline for the fruitful discussions and help for the USANS data evaluation and interpretation. The authors thank also CONICET (Consejo Nacional de Invetigaciones Científicas y Técnicas), ANPCyT – (Agencia Nacional de Promoción Científica y Tecnológica), for financial support to carry out this work. We would also like to thank the Metals Physics Division at Helmoltz-Zentrum Hereon for providing the TEM devices. The research leading to these results has received funding from Alexander von Humboldt Foundation, Fellowship number: ARG-1187279-GF-P. This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 712949 (TECNIOspring PLUS) and the Government of Catalonia's Agency for Business Competitiveness (ACCIÓ).

Apparatus comprising a metal hydride store for operating an exothermic hydrogen consumer. Starting coupled fuel cell systems + metal hydride based hydrogen storage systems, especially (but not only) at low temperatures down to -30 ° C. Also, other chemically-based hydrogen storage systems (eg, LOHCs, ammonia, methanol, or formic acid) need a cold-start capability given by this invention.

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 2LiBH4 MgH2 doped with 30 wt % activated carbon nanofibers (ACNF) are investigated. After doping with ACNF, onset dehydrogenation temperature of compacted 2LiBH4 MgH2 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.

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.

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.

FeTi-based hydrides have recently re-attracted attention as stationary hydrogen storage materials due to favorable reversibility, good sorption kinetics and relatively low costs compared to alternative intermetallic hydrides. Employing the OpenCalphad software, the thermodynamics of the (FeTi)$_{1-x}$H$_{x}$ (0 $\leq x \leq$ 1) system were assessed as a key basis for modeling hydrogenation of FeTi-based alloys. New thermodynamic data were acquired from our experimental pressure-composition-isotherm (PCI) curves, as well as first-principles calculations utilizing density functional theory (DFT). The thermodynamic phase models were carefully selected based on critical analysis of literature information and \emph{ab-initio} investigations. Key thermodynamic properties such as dissociation pressure, formation enthalpies and phase diagrams were calculated in good agreement to our performed experiments and literature-reported data. This work provides an initial perspective, which can be extended to account for higher-order thermodynamic assessments and subsequently enables the design of novel FeTi-based hydrides. In addition, the assessed thermodynamic data can serve as key inputs for kinetic models and hydride microstructure simulations., Comment: 15 pages, 7 figures

Advanced engineering materials 23(11), 2100620 (2021). doi:10.1002/adem.202100620, The hydrogen storage performance of reactive hydride composite Mg(NH$_2$)$_2$+2LiH can be significantly improved by the addition of LiBH$_4$ and the subsequent formation of an amide���borohydride compound Li$_4$(BH$_4$)(NH$_2$)$_3$ during hydrogen release. Herein, an investigation into the structure and anion motions of Li$_4$(BH$_4$)(NH$_2$)$_3$ using synchrotron radiation powder X-ray diffraction (SR-PXD; 295���573 K) and quasielastic neutron scattering (QENS; 297���514 K) is described. The highest temperature studied with QENS (514 K) is above the melting point of Li$_4$(BH$_4$)(NH$_2$)$_3$. The neutron measurements confirm a long-range diffusive motion of hydrogen-containing species with the diffusion coefficient �������10$^{���6}$ cm$^2$ s$^{���1}$. Interestingly, this value is comparable to that of Li$^+$ diffusion inferred from conductivity measurements. SR-PXD confirms the recrystallization of Li$_4$(BH$_4$)(NH$_2$)$_3$ from the melt into the ��-phase upon cooling. At temperatures below 514 K, localized rotational motions are observed that are attributed to (BH$_4$)��� tetrahedra units mainly undergoing rotations around the ����$_3$ axes. The activation energy for this thermally activated process is found to be ����$_a$=15.5��0.9 and 17.4��0.9 kJ mol$^{���1}$ respectively for the two instrumental resolutions utilized in the QENS measurements, corresponding to observation times of 55 and 14 ps., Published by Deutsche Gesellschaft fu��r Materialkunde, Frankfurt, M.

Reversible solid-state hydrogen storage in metal hydrides is a key technology for pollution-free energy conversion systems. Herein, the LiBH2–MgH2 composite system with and without ScCl3 additive is investigated using synchrotron- and neutron-radiation-based probing methods that can be applied to characterize such lightweight metal–hydrogen systems from nanoscopic levels up to macroscopic scale. Combining the results of neutron- and photon-based methods allows a complementary insight into reaction paths and mechanisms, complex interactions between the hydride matrix and additive, hydrogen distribution, material transport, structural changes, and phase separation in the hydride matrix. The gained knowledge is of great importance for development and optimization of such novel metal-hydride-based hydrogen storage systems with respect to future applications.

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&middot, 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&middot, 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.

The Mg(NH2)2-2LiH composite has been regarded as a promising on-board hydrogen storage material, due to its favorable thermodynamics and high H2 gravimetric capacity. In this paper, a new route to synthesize the Mg(NH2)2-2LiH composite, starting from hydrogenated Li2Mg(NH)2, is presented. The Li2Mg(NH)2 is obtained from the decomposition of a mixture of magnesium waste alloy (AZ91) and LiH, after a multi-step treatment. The as-prepared Mg(NH2)2-2LiH with Mg coming from AZ91 shows improved hydrogen storage properties, as compared with that synthesized from pure magnesium powder, with a lower dehydrogenation peak temperature of about 15 °C. The reaction pathways during the conversion of the AZ91 alloy to Mg(NH2)2 2LiH are investigated by ex situ and in situ XRD techniques. The obtained results confirm that this new approach is an effective way to recycle magnesium waste alloys into light weight hydrogen storage material. In addition, this new technology is easy to scale up and reduce the cost of Mg(NH2)2-2LiH, that has important significance for its practical applications. &nbsp

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(BH4)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(BH4)2 is typically formed and it was postulated that this amorphous phase promotes the conductivity. Here, electrochemical impedance spectroscopy of as-received γ-Mg(BH4)2 and ball milled, amorphous Mg(BH4)2 confirmed that the conductivity of the latter is ~2 orders of magnitude higher than in as-received γ-Mg(BH4)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 [BH4] units, revealing a much larger fraction of activated [BH4] rotations in amorphous Mg(BH4)2. These findings suggest that the conduction process in amorphous Mg(BH4)2 is supported by stronger rotational mobility, which is proposed to be the so-called “paddle-wheel” mechanism.

CO2 capture and conversion are a key research field for the transition towards an economy only based on renewable energy sources. In this regard, hydride materials are a potential option for CO2 methanation since they can provide hydrogen and act as a catalytic species. In this work, Mg2NiH4 complex hydride is synthesized by in situ monitoring of mechanical milling under a hydrogen atmosphere from a 2MgH2:Ni stoichiometric mixture. Temperature and pressure evolution is monitored, and the material is characterized, during milling in situ, thus providing a good insight into the synthesis process. The cubic polymorph of Mg2NiH4 (S.G. Fm3m) starts to be formed in the early beginning of the mechanical treatment due to the mechanical stress induced by the milling process. Then, after 25 hours of milling, Mg2NiH4 with a monoclinic (S.G. C12/c1) structure appears. The formation of the monoclinic polymorph is most likely related to the stress release that follows the continuous refinement of the material's microstructure. At the end of the milling process, after 60 hours, the as-milled material is composed of 90.8 wt% cubic Mg2NiH4, 5.7 wt% monoclinic Mg2NiH4, and 3.5 wt% remnant Ni. The as-milled Mg2NiH4 shows high reactivity for CO2 conversion into CH4. Under static conditions at 400 °C for 5 hours, the interactions between as-milled Mg2NiH4 and CO2 result in total CO2 consumption and in the formation of the catalytic system Ni-MgNi2-Mg2Ni/MgO. Experimental evidence and thermodynamic equilibrium calculations suggest that the global methanation mechanism takes place through the adsorption of C and the direct solid gasification towards CH4 formation. Fil: Grasso, María Laura. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada CAB. Departamento Fisicoquímica de Materiales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Puszkiel, Julián Atilio. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada CAB. Departamento Fisicoquímica de Materiales; Argentina. Helmholtz-Zentrum Geesthacht GmbH; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Gennari, Fabiana Cristina. Comisión Nacional de Energía Atómica. Gerencia de Área de Aplicaciones de la Tecnología Nuclear. Gerencia de Investigación Aplicada CAB. Departamento Fisicoquímica de Materiales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Santoru, Antonio. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Dornheim, Martin. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Pistidda, Claudio. Helmholtz-Zentrum Geesthacht GmbH; Alemania

A high- pressure cell for neutron experiments was developed at Helmholtz-Zentrum Geesthacht (HZG). This cell is designed for the investigation of hydrogen storage materials at pressures up to 700 bar and temperatures up to 500°C. The idea is to have a prototype cell for different neutron scattering methods (diffraction, time- of-flight spectroscopy and small-angle neutron scattering). In this work, we discuss the development and the current state of the high- pressure cell. Furthermore, the deployment of the cell for in situ small-angle neutron scattering measurements on 6Mg(NH2 )2 + 9LiH + LiBH4 (6:9:1) at the instrument SANS-1 at Heinz Maier-Leibnitz Zentrum (MLZ) is demonstrated.

The system Mg(NH2)2 + 2LiH is considered as an interesting solid-state hydrogen storage material owing to its low thermodynamic stability of ca. 40 kJ/mol H2 and high gravimetric hydrogen capacity of 5.6 wt.%. However, high kinetic barriers lead to slow absorption/desorption rates even at relatively high temperatures (>180 °C). In this work, we investigate the effects of the addition of K-modified LixTiyOz on the absorption/ desorption behaviour of the Mg(NH2)2 + 2LiH system. In comparison with the pristine Mg(NH2)2 + 2LiH, the system containing a tiny amount of nanostructured K-modified LixTiyOz shows enhanced absorption/ desorption behaviour. The doped material presents a sensibly reduced (∼30 °C) desorption onset temperature, notably shorter hydrogen absorption/desorption times and reversible hydrogen capacity of about 3 wt.% H2 upon cycling. Studies on the absorption/desorption processes and micro/nanostructural characterizations of the Mg(NH2)2 + 2LiH + K-modified LixTiyOz system hint to the fact that the presence of in situ formed nanostructure K2TiO3 is the main responsible for the observed improved kinetic behaviour., This work was funded by the CAS-HZG collaborative project ''RevHy'' – ''Study on the synthesis, structures and performances of complex hydrides systems for Reversible high capacity Hydrogen storage at low temperatures''. The authors thank CONICET (Consejo Nacional de Invetigaciones Científicas y Técnicas) and Alexander von Humboldt Foundation in the frame of the post-doctoral fellowship of Dr. J. Puszkiel (Fellowship number: ARG−1187279-GF-P). This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 712949 (TECNIOspring PLUS) and the Government of Catalonia's Agency for Business Competitiveness (ACCIÓ).

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.

In this work, the hydrogen absorption and desorption properties of the system K2[Zn(NH2)4]-8LiH are investigated in detail via in situ synchrotron radiation powder X-ray diffraction (SR-PXD), Fourier transform infrared spectroscopy (FT-IR), and volumetric methods. Upon milling, K2[Zn(NH2)4] and 8LiH react to form 4LiNH2-4LiH-K2ZnH4, and then 4LiNH2-4LiH-K2ZnH4 releases H2 in multiple steps. The final products of the desorption reaction are KH, LiZn13, and Li2NH. During rehydrogenation, KH reacts with LiZn13 under 50 bar of hydrogen producing K3ZnH5. This phase appears to enhance the hydrogenation process which after its formation at ca. 220 °C takes place in only 30 s. The system 4LiNH2-4LiH-K2ZnH4 is shown to be reversible under the applied conditions of vacuum at 400 °C for desorption and 50 bar of H2 at 300 °C for absorption.

The 6Mg(NH2)2-9LiH-LiBH4 composite system has a maximum reversible hydrogen content of 4.2 wt% and a predicted dehydrogenation temperature of about 64 °C at 1 bar of H2. However, the existence of severe kinetic barriers precludes the occurrence of de/re-hydrogenation processes at such a low temperature (H. Cao, G. Wu, Y. Zhang, Z. Xiong, J. Qiu and P. Chen, J. Mater. Chem. A, 2014, 2, 15816-15822). In this work, Li3N and YCl3 have been chosen as co-additives for this system. These additives increase the hydrogen storage capacity and hasten the de/re-hydrogenation kinetics: a hydrogen uptake of 4.2 wt% of H2 was achieved in only 8 min under isothermal conditions at 180 °C and 85 bar of H2 pressure. The re-hydrogenation temperature, necessary for a complete absorption process, can be lowered below 90 °C by increasing the H2 pressure above 185 bar. Moreover, the results indicate that the hydrogenation capacity and absorption kinetics can be maintained roughly constant over several cycles. Low operating temperatures, together with fast absorption kinetics and good reversibility, make this system a promising on-board hydrogen storage material. The reasons for the improved de/re-hydrogenation properties are thoroughly investigated and discussed. Fil: Cao, Hujun. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Zhang, Weijin. Chinese Academy of Sciences; República de China Fil: Pistidda, Claudio. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Puszkiel, Julián Atilio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Milanese, Chiara. Università di Padova; Italia Fil: Santoru, Antonio. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Karimi, Fahim. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Castro Riglos, Maria Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Gizer, Gökhan. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Welter, Edmund. Deutsches Elektronen-Synchrotron a Research Centre of the Helmholtz Association; Alemania Fil: Bednarcik, Jozef. Deutsches Elektronen-Synchrotron a Research Centre of the Helmholtz Association; Alemania Fil: Etter, Martin. Deutsches Elektronen-Synchrotron a Research Centre of the Helmholtz Association; Alemania Fil: Chen, Ping. Chinese Academy of Sciences; República de China Fil: Klassen, Thomas. Helmholtz-Zentrum Geesthacht GmbH; Alemania Fil: Dornheim, Martin. Helmholtz-Zentrum Geesthacht GmbH; Alemania