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This document provides an overview of the development of hydrogen as a clean energy solution and the challenges of hydrogen storage. It explores the use of metal hydrides as a potential solution for hydrogen storage and investigates various hydrogen-rich materials for different applications. The document covers topics such as hydrogen release and uptake, electrolytes, physical properties, and metallic alloys. It also discusses the use of metallic hydrides for hydrogen purification and compression. The document acknowledges the contributors and sponsors of the International Symposium on Metal-Hydrogen Systems and invites readers to explore the contributed articles in the special edition for more information. [Extracted from the article]

Calcium hydride has shown great potential as a hydrogen storage material and as a thermochemical energy storage material. To date, its high operating temperature (above 800 °C) has not only hindered its opportunity for technological application but also prevented detailed determination of its thermodynamics of hydrogen sorption. In addition, calcium metal suffers from high volatility, high corrosivity from Ca (and CaH 2), slow kinetics of hydrogen sorption, and the solubility of Ca in CaH 2. In this work, a literature review of the wide-ranging thermodynamic properties of CaH 2 is provided along with a detailed experimental investigation into the thermodynamic properties of molten and solid CaH 2. The thermodynamic values of hydrogen release from both molten and solid CaH 2 were determined as Δ H des (molten CaH 2) = 216 ± 10 kJ mol−1.H 2 , Δ S des (molten CaH 2) = 177 ± 9 J K−1 mol−1.H 2, which equates to a 1 bar hydrogen equilibrium temperature for molten CaH 2 of 947 ± 65 °C. Similarly, in the solid-state: Δ H des (solid CaH 2) = 172 ± 12 kJ mol−1.H 2 , Δ S des (solid CaH 2) = 144 ± 10 J K−1 mol−1.H 2. Moreover, the activation energy of hydrogen release from CaH 2 was also calculated using DSC analysis as E a = 203 ± 12 kJ mol−1. This study provides the first thermodynamics for the Ca–H system in over 60 years, providing more accurate data on this emerging energy storage material. • The thermodynamics for hydrogen desorption of calcium hydride were determined. • This is the first study in over 60 years to determine the thermal properties. • The kinetics of hydrogen release were measured using the Kissinger method. • The melting point of CaH 2 was measured under a hydrogen atmosphere. • A literature review of previous thermodynamic studies on CaH 2 is included. [ABSTRACT FROM AUTHOR]

Two highly ordered porous Al scaffolds were synthesized by applying a soft template assisted electrodeposition method, using an ionic liquid as the electrolyte. Polystyrene (PS) spheres with an average diameter of 399 ± 2 nm or 89 ± 20 nm were deposited on a polished Cu electrode using a dip-coater. An imidazolium-based ionic liquid mixed with aluminium chloride [EMIm]/AlCl3 (40/60 mol%) was used as the electrolyte for the Al electrodeposition. The PS spheres that were used as a soft template were removed after the Al electrodeposition method by chemically dissolving them in tetrahydrofuran (THF). Lithium borohydride (LiBH4) was then melt-infiltrated into the porous Al scaffold. Morphological observations of the dip-coated Cu electrodes with the PS spheres, the as-synthesized porous Al scaffolds and the LiBH4 melt-infiltrated samples were carried out using Scanning Electron Microscopy (SEM). The scaffolds exhibited a highly ordered porous Al structure with an open network of pores and an average pore size of 355 ± 25 and 56 ± 20 nm respectively. The porous Al acts as a reactive scaffold which interacts with LiBH4 at elevated temperature. Temperature Programmed Desorption (TPD) experiments revealed that the melt-infiltrated LiBH4 samples exhibited faster H2 desorption kinetics in comparison to the bulk material. In particular, the 56 ± 20 nm Al scaffold showed a H2 desorption onset temperature (Tdes) at 100◦C which is 250◦C lower than for bulk LiBH4. This temperature drop can be attributed to the size reduction of LiBH4 down to the nanoscale, together with the high contact surface area with the Al scaffold. [ABSTRACT FROM AUTHOR]

Rare earth (RE) borohydrides have received considerable attention during the past ten years as possible hydrogen storage materials due to their relatively high gravimetric hydrogen density. This review illustrates the rich chemistry, structural diversity and thermal properties of borohydrides containing RE elements. In addition, it highlights the decomposition and rehydrogenation properties of composites containing RE-borohydrides, light-weight metal borohydrides such as LiBH4 and additives such as LiH. [ABSTRACT FROM AUTHOR]

Lithium aluminium hydride (LiAlH 4 ) has long been identified as a viable hydrogen storage material, due to its high attainable theoretical gravimetric hydrogen capacity of 7.9 wt%. The main impediment to its viability for technical application is its limitation for regeneration. Recently, solvent-mediated regeneration has been achieved at room temperature using dimethyl-ether, Me 2 O, although the reaction pathway has not been determined. This in situ multinuclear NMR spectroscopy study ( 27 Al and 7 Li) has confirmed that the Me 2 O-mediated, direct synthesis of LiAlH 4 occurs by a one-step process in which LiAlH 4 · x Me 2 O is formed, and does not involve Li 3 AlH 6 or any other intermediates. Hydrogenation has been shown to occur below ambient temperatures (at 0 °C) for the first time, and the importance of solvate adducts formed during the process is demonstrated. [ABSTRACT FROM AUTHOR]

Metal hydrides have received much attention due to the flourishing concept of a hydrogen economy. In addition, recent studies of metal hydride materials have shown that technological implementation of these compounds not only lies in the storage of hydrogen, but for a range of multi-functional applications; including, smart optical windows, energy storage materials in fuel cells for both stationary and mobile devices, and as thermal energy storage materials for concentrating solar thermal plants. This review concentrates on the molecular structures, thermodynamic properties and other physical properties of the complexes of [NiH 4 ] 4− , [FeH 6 ] 4− , [CoH 5 ] 4− and [RuH 6 ] 4− . The synthesized derivatives of these compounds have also been reviewed to give a full overview on the advancement of these systems and will allow for a fresh prospective for future studies to fully understand the physical and chemical nature of these complex transition metal hydrides. [ABSTRACT FROM AUTHOR]

A novel species of metal amidoborane ammoniate, [Al(NH2BH3)63-][Al(NH3)63+] has been successfully synthesized in up to 95% via the one-step reaction of AlH3·OEt2 with liquid NH3BH3·nNH3 (n = 1~6) at 0 °C. This solution based reaction method provides an alternative pathway to the traditional mechano-chemical ball milling methods, avoiding possible decomposition. MAS 27Al NMR spectroscopy confirms the formulation of the compound as an Al(NH2BH3)63- complex anion and an Al(NH3)63+ cation. Initial dehydrogenation studies of this aluminum based M-N-B-H compound demonstrate that hydrogen is released at temperatures as low as 65 °C, totaling ~8.6 equivalents of H2 (10.3 wt %) upon heating to 105 °C. This method of synthesis offers a promising route towards the large scale production of metal amidoborane ammoniate moieties. [ABSTRACT FROM AUTHOR]

• The SrH 2 and 2Al system was studied for thermochemical energy storage applications. • Thermodynamic destablization was observed compared to pure strontium hydride. • The system reversibly stores H 2 at a temperature of 846 °C at 1 bar H 2 pressure. • After 50 cycles mild degradation in H 2 storage capacity was observed. • The material could be a thermal energy storage material upon further modification. [Display omitted] Thermal batteries are ideal for storing renewable energies or excess electricity from the grid. The most efficient thermal batteries utilize reversible thermochemical reactions where the heat produced during discharge drives a heat engine. Metal hydrides can be used as the thermal energy storage (TES) material in these batteries, since when heated, hydrogen is released in an endothermic process, charging the battery. When this hydrogen is reintroduced to the metal the metal hydride is reformed during the exothermic reaction (discharge). The optimal thermal battery would have a high operating temperature, low operating pressure and low material cost. SrH 2 could meet these demands except its operating temperature is above 1000 °C. Adding aluminum to strontium hydride causes thermal destablization allowing an operating temperature of 1 bar hydrogen at 846 ± 36 °C, providing ideal properties as a TES material. The SrH 2 -2Al system reacts in two stages with the second step exhibiting only a 32% reduction in capacity over 50 cycles. Pressure-composition isotherm analysis of the second step determined the thermodynamics of H 2 desorption to be Δ H des = 132 ± 2 kJ/mol H 2 and Δ S des = 118 ± 2 J/K/mol H 2. Further studies by scanning electron microscopy have determined changes in morphology over cyclic activity, while simultaneous thermal analysis and powder X-ray diffraction have identified the reaction pathways of the process. A cost analysis of the system has shown that a reduction in materials cost would enhance technological application of this material. [ABSTRACT FROM AUTHOR]

First-principles calculations were employed to investigate hypothetical complex hydrides (M,M')4FeH8 (M = Na, Li; M' = Mg, Zn, Y, Al). Besides complex anion [FeH6]4-, these materials contain two H- anions, which raise the total anionic charge state from tetravalent to hexavalent, and thereby significantly increasing the number of combinations of countercations. We have determined that similar to complex hydrides (M,M')2FeH6 containing only [FeH6]4-, the thermodynamic stability is tuned by the average cation electronegativity. Thus, the chemical flexibility provided by incorporating H- enhances the tunability of thermodynamic stability, which will be beneficial in obtaining optimal stability for hydrogen storage materials. [ABSTRACT FROM AUTHOR]

Abstract: Aluminum hydride (alane; AlH3) has been identified as a leading hydrogen storage material by the US Department of Energy. With a high gravimetric hydrogen capacity of 10.1 wt.%, and a hydrogen density of 1.48 g/cm3, AlH3 decomposes cleanly to its elements above 60 °C with no side reactions. This study explores in detail the thermodynamic and spectroscopic properties of AlH3; in particular the α, α′ and γ polymorphs, of which α′-AlH3 is reported for the first time, free from traces of other polymorphs or side products. Thermal analysis of α-, α′-, and γ-AlH3 has been conducted, using DSC and TGA methods, and the results obtained compared with each other and with literature data. All three polymorphs were investigated by 1H MAS-NMR spectroscopy for the first time, and their 27Al MAS-NMR spectra were also measured and compared with literature values. AlH3·nEt2O has also been studied by 1H and 27Al MAS-NMR spectroscopy and DSC and TGA methods, and an accurate decomposition pathway has been established for this adduct. [Copyright &y& Elsevier]

Hydrogen and ammonia are both potential energy carriers being considered for large scale energy transport. Sodium borohydride (NaBH 4) has been widely applied as a potential solid-state hydrogen storage material. It can produce hydrogen gas and sodium metaborate (NaBO 2) after hydrolysis with water at room temperature. The regeneration of NaBH 4 from NaBO 2 could significantly reduce the cost of NaBH 4 and enable its wide-spread industrial use. In this work, we demonstrate a simple method for regenerating NaBH 4 from NaBO 2 ·4H 2 O using Mg 2 N 3 , which combines NaBH 4 production with NH 3 gas production in a single step at room temperature. NaBH 4 is successfully synthesized from NaBO 2 ·4H 2 O using the Mg 3 N 2 reducing agent via ball milling under a hydrogen atmosphere. NaBH 4 is formed at a 76.6% yield by planetary ball milling at 600 rpm under 40 bar hydrogen for 12 h. NH 3 gas is also formed, which can be easily separated from the solid products. Therefore, this one-step process could produce two different types of carbon-free hydrogen carriers suitable for energy export from renewable sources. • One step process to store hydrogen in NaBH 4 and NH 3. • Lower cost for NaBH 4 regeneration. • Mg 3 N 2 can be considered as a promising reductant for simultaneous synthesis of NaBH 4 and NH 3. • The hydrogen pressure have a effect on the ball milling. [ABSTRACT FROM AUTHOR]

Metal hydrides are regarded as one of the most attractive options for thermal energy storage (TES) materials for concentrated solar thermal applications. Improved thermal performance of such systems is vitally determined by the effectiveness of heat exchange between the metal hydride and the heat transfer fluid (HTF). This paper presents a numerical study supported by experimental validation on a magnesium hydride reactor fitted with a helical coil heat exchanger for enhanced thermal performance. The model incorporates hydrogen absorption kinetics of ball-milled magnesium hydride, with titanium boride and expanded natural graphite additives obtained by Sievert's apparatus measurements and considers thermal diffusion within the reactor to the heat transfer fluid for a realistic representation of its operation. A detailed parametric analysis is carried out, and the outcomes are discussed, examining the ramifications of hydrogen supply pressure and its flow rate. The study identifies that the enhancement of thermal conductivity in magnesium hydride has an insignificant impact on current reactor performance. • 3-D validation of MgH 2 reactor with a helical coil heat exchanger was performed. • Reaction kinetics was found out by using Sievert's apparatus. • Effect of operating parameters on MH reactor performance was studied. • Addition of 20% ENG into MH reactor, under the study, proved ineffective. [ABSTRACT FROM AUTHOR]

Abstract Porous Al scaffolds were synthesised and melt-infiltrated with various eutectic metal borohydride mixtures (0.725LiBH 4 -0.275KBH 4, 0.68NaBH 4 -0.32KBH 4, 0.4NaBH 4 -0.6 Mg(BH 4) 2) to simultaneously act as both a confining framework and a reactive destabilising agent for H 2 release. The scaffolds were synthesised by sintering a pellet of NaAlH 4 /2 mol%TiCl 3 at 450 °C under dynamic vacuum. During the sintering process the sodium alanate (NaAlH 4) 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 H 2 and the Na from the body of the NaAlH 4 /2 mol%TiCl 3 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 H 2 desorption kinetics in comparison to bulk samples, with onset temperatures (T des) 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. Highlights • Porous scaffolds were fabricated by sintering a NaAlH 4 /2 mol%TiCl 3 pellet at 450 °C. • The pores formed an open network with thin interconnecting walls. • The porous Al scaffolds destabilised the infiltrated eutectic mixtures. • All melt-infiltrated samples started desorbing H 2 150–250 °C lower than the bulk. • The melt-infiltrated samples showed faster reaction kinetics to the bulk. [ABSTRACT FROM AUTHOR]

In solid-state hydrogen storage in light metal hydrides, nanoconfinement and the use of catalysts represent promising solutions to overcoming limitations such as poor reversibility and slow kinetics. In this work, the morphology and hydrogen desorption kinetics of NaAlH 4 melt-infiltrated into a previously developed Ti-based doped porous Al scaffold is analysed. Small-angle X-ray scattering and scanning electron microscopy analysis of low NaAlH 4 loading in the porous Al scaffold has revealed that mesopores and small macropores are filled first, leaving the larger macropores/voids empty. Temperature-programmed desorption experiments have shown that NaAlH 4 -infiltrated porous Al scaffolds show a higher relative H 2 release, with respect to NaAlH 4 + TiCl 3 , in the temperature range 148–220 °C, with the temperature of H 2 desorption trending to bulk NaAlH 4 with increasing scaffold loading. The Ti-based catalytic effect is reproduced when the dopant is present in the scaffold. Further work is required to increase the mesoporous volume in order to enhance the nanoconfinement effect. [ABSTRACT FROM AUTHOR]

A novel approach for confining LiBH 4 within a porous aluminium scaffold was applied in order to enhance its hydrogen storage properties, relative to conventional techniques for confining complex hydrides. The porous aluminium scaffold was fabricated by sintering NaAlH 4, which was in the form of a dense pellet, under dynamic vacuum. The final product was a porous aluminium scaffold with the Na and H 2 having been removed from the initial pellet. This technique contributed to achieving highly dispersed LiBH 4 particles that were also destabilised by the presence of the aluminium scaffold. In this study, the effectiveness of this novel fabrication method of confined/destabilised LiBH 4 was extensively investigated, which aimed to simultaneously improve the hydrogen release at lower temperature and the kinetics of the system. These properties were compared with the properties of other confined LiBH 4 samples found in the literature. As-synthesised samples were characterised using Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD) and Nitrogen Adsorption measurements. The hydrogen storage capacity of all samples was analysed using temperature programmed desorption in order to provide a comprehensive survey of their hydrogen desorption properties. The porous aluminium scaffold has a wide pore size distribution with most of the porosity due to pores larger than 50 nm. Despite this the onset hydrogen desorption temperature (T des ) of the LiBH 4 infiltrated into the porous aluminium scaffold was 200 °C lower than that of bulk LiBH 4 and 100 °C lower than that of nanosized LiBH 4 . Partial cycling could be achieved below the melting point of LiBH 4 but the kinetics of hydrogen release decreased with cycle number. [ABSTRACT FROM AUTHOR]