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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]

The thermochemical energy storage properties of calcium hydride (CaH 2) destabilised with either silicon (Si) or Ca x Si y compounds at various molar ratios, were thoroughly studied by a combination of experimental and computer assisted thermodynamic calculations. Particularly, the destabilisation effect of Si on CaH 2 at five different molar ratios (1:1, 1:2, 2:1, 3:4, 5:3 CaH 2 to Si) was extensively investigated. Theoretical calculations predicted a multi-step thermal decomposition reaction between CaH 2 and Si forming Ca x Si y at varying temperatures, which was confirmed by in-situ synchrotron X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis and mass-spectroscopic measurements. The most suitable destabilisation reactions between CaH 2 and Si or Ca x Si y that meet the criteria of a thermal energy storage system for the next-generation of concentrated solar power (CSP) plants were identified. The CaH 2 and CaSi system (in a 2:3 molar ratio of CaH 2 to CaSi) showed desirable operating conditions with a decomposition temperature of 747 ± 33 °C at a hydrogen pressure of 1 bar. Pressure composition isothermal measurements were conducted on this system to determine its practical enthalpy of decomposition to form Ca 5 Si 3. The calculated value (107.3 kJ mol−1 H 2) was lower compared to the experimentally determined value (154 ± 4 kJ mol−1 H 2). This mismatch was mainly due to the formation of CaO and a CaSi solid solution in addition to the desired Ca 5 Si 3 phase. ga1 • Calcium hydride has been thermodynamically destabilised with silicon. • A multistep decomposition pathway was determined by theoretical calculations. • The experimental thermal decomposition pathway and thermodynamics were established. • The Ca–Si system is a viable thermal energy storage material. [ABSTRACT FROM AUTHOR]

CaH 2 is a metal hydride with a high energy density that decomposes around 1100 °C at 1 bar of H 2 pressure. Due to this high decomposition temperature, it is difficult to utilise this material as a thermal battery for the next generation of concentrated solar power plants, where the currently targeted operational temperature is between 600 and 800 °C. In this study, CaH 2 has been mixed with calcium halide salts (CaCl 2 , CaBr 2 and CaI 2) and annealed at 450 °C under 100 bar of H 2 pressure to form CaHCl, CaHBr and CaHI. These hydride-halide salts incur a thermodynamic destabilisation of their hydrogen release, compared to CaH 2 , so that they can operate between 600 and 800 °C within practical operating pressures (1–10 bar H 2) for thermochemical energy storage. The as-synthesised metal hydrides were studied by in-situ synchrotron X-ray diffraction, temperature programmed desorption and pseudo pressure composition isothermal analysis. Each of the calcium hydride-halide salts decomposed to form calcium metal and a calcium halide salt after hydrogen release. In comparison to pure CaH 2, their decomposition reactions were faster when heated up to 850 °C, and the experimental values of the desorbed hydrogen gas were very close to the theoretical ones. All samples after their decomposition showed signs of sintering, which hindered their rehydrogenation reaction. • CaH 2 was thermodynamically destabilised when mixed with calcium halide salts. • The new compounds exhibited faster reaction kinetics compared to CaH 2. • All three compounds exhibited equilibrium pressures between 1 and 10 bar at 650 °C. [ABSTRACT FROM AUTHOR]