• Energy Research

AbstractMetal‐organic frameworks (MOFs) are very promising host materials for nanoscale guest materials. However, some MOFs such as MIL‐53 are known to undergo phase transitions which can complicate the guest particle size control. In this study, Pd nanoparticles embedded in Al‐MIL‐53 were synthesised via (a) electrodeposition and (b) gas‐phase reduction. A thorough structural investigation revealed that each synthesis method most likely favoured a different phase of Al‐MIL‐53, presenting the possibility of MOF phase selection as a technique for size control of embedded nanoparticles. For the first time, we hereby report the use of pair distribution function analysis to successfully investigate the structure and morphology of guest particles embedded in a MOF host.

Abstract The thermochemical energy storage properties of calcium hydride (CaH2) destabilised with either silicon (Si) or CaxSiy 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 CaH2 at five different molar ratios (1:1, 1:2, 2:1, 3:4, 5:3 CaH2 to Si) was extensively investigated. Theoretical calculations predicted a multi-step thermal decomposition reaction between CaH2 and Si forming CaxSiy 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 CaH2 and Si or CaxSiy that meet the criteria of a thermal energy storage system for the next-generation of concentrated solar power (CSP) plants were identified. The CaH2 and CaSi system (in a 2:3 molar ratio of CaH2 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 Ca5Si3. The calculated value (107.3 kJ mol−1 H2) was lower compared to the experimentally determined value (154 ± 4 kJ mol−1 H2). This mismatch was mainly due to the formation of CaO and a CaSi solid solution in addition to the desired Ca5Si3 phase.

Abstract 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.

Nanoconfinement of 2LiBH4-NaAlH4 into a mesoporous carbon aerogel scaffold with a pore size, BET surface area and total pore volume of Dmax = 30 nm, SBET = 689 m2/g and Vtot = 1.21 mL/g, respectively is investigated. Nanoconfinement of 2LiBH4-NaAlH4 facilitates a reduction in the temperature of the hydrogen release by 132 °C, compared to that of bulk 2LiBH4-NaAlH4 and the onset of hydrogen release is below 100 °C. The reversible hydrogen storage capacity is also significantly improved for the nanoconfined sample, maintaining 83% of the initial hydrogen content after three cycles compared to 47% for that of the bulk sample. During nanoconfinement, LiBH4 and NaAlH4 reacts to form LiAlH4 and NaBH4 and the final dehydrogenation products, obtained at 481 °C are LiH, LiAl, AlB2 and Al. After rehydrogenation of the nanoconfined sample at T = 400 °C and p(H2) = 126 bar, amorphous NaBH4 is recovered along with unreacted LiH, AlB2 and Al and suggests that NaBH4 is the main compound that can reversibly release and uptake hydrogen.

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