Solid state hydrogen storage in alanates and alanate-based compounds: A review

The safest way to store hydrogen is in solid form, physically entrapped in molecular form in highly porous materials, or chemically bound in atomic form in hydrides. Among the different families of these compounds, alkaline and alkaline earth metals alumino-hydrides (alanates) have been regarded as promising storing media and have been extensively studied since 1997, when Bogdanovic and Schwickardi reported that Ti-doped sodium alanate could be reversibly dehydrogenated under moderate conditions. In this review, the preparative methods; the crystal structure; the physico-chemical and hydrogen absorption-desorption properties of the alanates of Li, Na, K, Ca, Mg, Y, Eu, and Sr; and of some of the most interesting multi-cation alanates will be summarized and discussed. The most promising alanate-based reactive hydride composite (RHC) systems developed in the last few years will also be described and commented on concerning their hydrogen absorption and desorption performance

Solid state hydrogen storage in alanates and alanate-based compounds: a review

The safest way to store hydrogen is in solid form, physically entrapped in molecular form in highly porous materials, or chemically bound in atomic form in hydrides. Among the different families of these compounds, alkaline and alkaline earth metals alumino-hydrides (alanates) have been regarded as promising storing media and have been extensively studied since 1997, when Bogdanovic and Schwickardi reported that Ti-doped sodium alanate could be reversibly dehydrogenated under moderate conditions. In this review, the preparative methods; the crystal structure; the physico-chemical and hydrogen absorption-desorption properties of the alanates of Li, Na, K, Ca, Mg, Y, Eu, and Sr; and of some of the most interesting multi-cation alanates will be summarized and discussed. The most promising alanate-based reactive hydride composite (RHC) systems developed in the last few years will also be described and commented on concerning their hydrogen absorption and desorption performanc

Recent progress and new perspectives on metal amide and imide systems for solid-state hydrogen storage

Hydrogen storage in the solid state represents one of the most attractive and challenging ways to supply hydrogen to a proton exchange membrane (PEM) fuel cell. Although in the last 15 years a large variety of material systems have been identified as possible candidates for storing hydrogen, further efforts have to be made in the development of systems which meet the strict targets of the Fuel Cells and Hydrogen Joint Undertaking (FCH JU) and U.S. Department of Energy (DOE). Recent projections indicate that a system possessing: (i) an ideal enthalpy in the range of 20-50 kJ/mol H2, to use the heat produced by PEM fuel cell for providing the energy necessary for desorption; (ii) a gravimetric hydrogen density of 5 wt. % H2 and (iii) fast sorption kinetics below 110 °C is strongly recommended. Among the known hydrogen storage materials, amide and imide-based mixtures represent the most promising class of compounds for on-board applications; however, some barriers still have to be overcome before considering this class of material mature for real applications. In this review, the most relevant progresses made in the recent years as well as the kinetic and thermodynamic properties, experimentally measured for the most promising systems, are reported and properly discussed

Development and experimental validation of kinetic models for the hydrogenation/dehydrogenation of Mg/Al based metal waste for energy storage

With the increased use of renewable energy sources, the need to store large amounts of energy will become increasingly important in the near future. A cost efficient possibility is to use the reaction of recycled Mg waste with hydrogen as thermo-chemical energy storage. Owing to the high reaction enthalpy, the moderate pressure and appropriate temperature conditions, the broad abundance and the recyclability, the Mg/Al alloy is perfectly suitable for this purpose. As further development of a previous work, in which the performance of recycled Mg/Al waste was presented, a kinetic model for hydro- and dehydrogenation is derived in this study. Temperature and pressure dependencies are determined, as well as the rate limiting step of the reaction. First experiments are carried out in an autoclave with a scaled-up powder mass, which is also used to validate the model by simulating the geometry with the scaled-up experiments at different conditions

Using the emission of muonic x-rays as a spectroscopic tool for the investigation of the local chemistry of elements

There are several techniques providing quantitative elemental analysis, but very few capable of identifying both the concentration and chemical state of elements. This study presents a systematic investigation of the properties of the X-rays emitted after the atomic capture of negatively charged muons. The probability rates of the muonic transitions possess sensitivity to the electronic structure of materials, thus making the muonic X-ray Emission Spectroscopy complementary to the X-ray Absorption and Emission techniques for the study of the chemistry of elements, and able of unparalleled analysis in case of elements bearing low atomic numbers. This qualitative method is applied to the characterization of light elements-based, energy-relevant materials involved in the reaction of hydrogen desorption from the reactive hydride composite Ca(BH4)2-Mg2NiH4. The origin of the influence of the band-structure on the muonic atom is discussed and the observed effects are attributed to the contribution of the electronic structure to the screening and to the momentum distribution in the muon cascade

A new mutually destabilized reactive hydride system: LiBH4–Mg2NiH4

In this work, the hydrogen sorption properties of the LiBH4–Mg2NiH4 composite system with the molar ratio 2:2.5 were thoroughly investigated as a function of the applied temperature and hydrogen pressure. To the best of our knowledge, it has been possible to prove experimentally the mutual destabilization between LiBH4 and Mg2NiH4. A detailed account of the kinetic and thermodynamic features of the dehydrogenation process is reported here

Ca(BH4)2–Mg2NiH4: on the pathway to a Ca(BH4)2 system with a reversible hydrogen cycle

The hydride composite Ca(BH4)2–Mg2NiH4 transfers all boron to MgNi2.5B2 upon dehydrogenation, avoiding boron sinks. The rehydrogenation to Ca(BH4)2 was confirmed

Kinetics and hydrogen storage performance of Li-Mg-N-H systems doped with Al and AlCl3

Recent investigations showed the formation of new amide-chloride phases between LiNH2 and AlCl3 after milling and/or heating under hydrogen pressure. These phases exhibited a key role in the improvement of the hydrogen storage properties of the LiNH2-LiH composite. In the present work, we studied the effects of Al and AlCl3 additives on the hydrogen storage behavior of the Li-Mg-N-H system. The dehydrogenation kinetics and the reaction pathway of Al and AlCl3 modified LiNH2-MgH2 composite were investigated through a combination of kinetic measurements and structural analyses. During the first cycle, the addition of Al catalytically accelerates the hydrogen release at 200 °C. In the subsequent cycles, the formation of a new phase of unknown nature is probably responsible for both increased equilibrium hydrogen pressure and decreased dehydrogenation rate. In contrast, AlCl3 additive reacts with LiNH2-MgH2 through the milling and continues during heating under hydrogen pressure. Addition of AlCl3 leads to the formation of two cubic structures identified in the Li-Al-N-H-Cl system, which improves dehydrogenation rate by modifying the thermodynamic stability of the material. This study evidences positive effect of cation and/or anion substitution on hydrogen storage properties of the Li-Mg-N-H system.This study has been partially supported by bilateral collaboration Project MINCyT-MA

KNH2 - KH: a metal amide - hydride solid solution

We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2 - ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.Fil: Santoru, Antonio. Helmholtz-zentrum Geesthacht; Alemania. Università di Torino; ItaliaFil: Pistidda, Claudio. Helmholtz-zentrum Geesthacht; AlemaniaFil: Sørby, Magnus H.. Institute for Energy Technology. Physics Department; NoruegaFil: Chierotti, Michele R.. Università di Torino; ItaliaFil: Garroni, Sebastian. University of Sassari; ItaliaFil: Pinatel, Eugenio. Università di Torino; ItaliaFil: Karimi, Fahim. Helmholtz-zentrum Geesthacht; AlemaniaFil: Cao, Hujun. Helmholtz-zentrum Geesthacht; AlemaniaFil: Bergemann, Nils. Helmholtz-zentrum Geesthacht; AlemaniaFil: Le, Thi T.. Helmholtz-zentrum Geesthacht; AlemaniaFil: Puszkiel, Julián Atilio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; ArgentinaFil: Gobetto, Roberto. Università di Torino; ItaliaFil: Baricco, Marcello. Università di Torino; ItaliaFil: Hauback, Bjorn C.. Institute for Energy Technology. Physics Department; NoruegaFil: Klassen, Thomas. Helmholtz-zentrum Geesthacht; AlemaniaFil: Dornheim, Martín. Helmholtz-zentrum Geesthacht; Alemani