Rare Earth Borohydrides—Crystal Structures and Thermal Properties

Frommen, Christoph; Sørby, Magnus H.; Heere, Michael; Humphries, Terry D.; Olsen, Jørn Eirik; Hauback, Bjørn C.

doi:10.3390/en10122115

Cited by 42 publications

(38 citation statements)

References 74 publications

(202 reference statements)

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“…These RE borohydrides can be obtained by milling of LiBH 4 and RE halides, mainly the LiBH 4 -RECl 3 or LiBH 4 -RECl 3 -LiH mixtures, where LiCl is formed as a by-product. In some cases, the milling induces partial halide substitution in the RE borohydride [101,102]. Afterward, for the case of the three synthesis procedures, the as-synthesized RE hydride and LiBH 4 powders are mixed using ball milling, obtaining new destabilized composites with promising properties.…”

Section: Destabilization Of Libh 4 By Rare Earth (Re) Metal Hydridesmentioning

confidence: 99%

“…In this study, only the rehydrogenation of the 6LiBH 4 -RECl 3 (RE = La, Er) systems was explored. For the milled 6LiBH 4 -RECl 3 mixture where RE = La, Ce, Pr and Nd, dehydrogenation starts below 200 • C and proceeds up to 350 • C, involving complex interactions as the temperature increases, inducing Cl-substitution in LiBH 4 , undergoing partial decomposition of RE borohydride, and leading to lower dehydrogenation temperatures than pure LiBH 4 as a result of the interaction between LiBH 4 and RE hydrides [102]. No emission of diborane or other borane species was detected.…”

Section: Destabilization Of Libh 4 By Rare Earth (Re) Metal Hydridesmentioning

confidence: 99%

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Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches

et al. 2019

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Hydrogen technology has become essential to fulfill our mobile and stationary energy needs in a global low–carbon energy system. The non-renewability of fossil fuels and the increasing environmental problems caused by our fossil fuel–running economy have led to our efforts towards the application of hydrogen as an energy vector. However, the development of volumetric and gravimetric efficient hydrogen storage media is still to be addressed. LiBH4 is one of the most interesting media to store hydrogen as a compound due to its large gravimetric (18.5 wt.%) and volumetric (121 kgH2/m3) hydrogen densities. In this review, we focus on some of the main explored approaches to tune the thermodynamics and kinetics of LiBH4: (I) LiBH4 + MgH2 destabilized system, (II) metal and metal hydride added LiBH4, (III) destabilization of LiBH4 by rare-earth metal hydrides, and (IV) the nanoconfinement of LiBH4 and destabilized LiBH4 hydride systems. Thorough discussions about the reaction pathways, destabilizing and catalytic effects of metals and metal hydrides, novel synthesis processes of rare earth destabilizing agents, and all the essential aspects of nanoconfinement are led.

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Section: Destabilization Of Libh 4 By Rare Earth (Re) Metal Hydridesmentioning

confidence: 99%

Section: Destabilization Of Libh 4 By Rare Earth (Re) Metal Hydridesmentioning

confidence: 99%

Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches

et al. 2019

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“…Here, we explore for the first time the magnetic properties of a large series of lanthanide borohydrides [Ln(BH 4 ) 3 with direct Ln ··· HBH ··· Ln bridges present in their structure], and of selected MLn(BH 4 ) 4 systems [with structurally isolated Ln 3+ ions embedded in complex Ln(BH 4 ) 4 – anions]. These systems were explored so far mostly in terms of their hydrogen storage properties and thermal decomposition profiles , . More complex systems, e.g.…”

Section: Introductionmentioning

confidence: 99%

Borohydride as Magnetic Superexchange Pathway in Late Lanthanide Borohydrides

et al. 2019

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The magnetic characteristics of a series of borohydride‐based systems, including binary α‐/β‐Ln(BH4)3 phases (Ln = Gd, Tb, Dy, Ho, Er, and Tm) with direct Ln–HBH–Ln bridges and selected mixed‐metal systems, LiYb(BH4)4, NaYb(BH4)4, KHo(BH4)4, RbTm(BH4)4, with isolated Ln3+ ions embedded in [Ln(BH4)4]– anions are described for the first time using SQUID magnetometry and DFT+U calculations. Crystal field effects as well as the nature and strength of magnetic superexchange interactions via BH4– ligands are established based on a ligand field theory approach. We find Auzel's scalar crystal field strength parameter (Nv, the weighted quadratic mean of the ligand field parameters Bkq) for these systems to be substantial, in particular for α‐Ho(BH4)3, indicating a significant covalent component in the Ho···H bonding. The BH4– anion is capable of mediating both weakly ferro‐ or antiferromagnetic superexchange. Quantum mechanical DFT+U calculations, even when including spin‐orbit coupling effects, do not reliably describe the sign and the size of the magnetic superexchange constants in these systems.

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“…Sieverts-type measurements reveal a three-step desorption-absorption cycle with release of 4.2, 3.7 and 3.5 wt % H 2 for the first, second and third cycle. This work adds a new example to the growing interest in utilisation of rare earth metals and their unique properties [30,31].…”

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confidence: 98%

Functional Materials Based on Metal Hydrides

Zhu

Buckley

2018

Inorganics

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Storage of renewable energy remains a key obstacle for the implementation of a carbon free energy system. There is an urgent need to develop a variety of energy storage systems with varying performance, covering both long-term/large-scale and high gravimetric and volumetric densities for stationary and mobile applications. Novel materials with extraordinary properties have the potential to form the basis for technological paradigm shifts. Here, we present metal hydrides as a diverse class of materials with fascinating structures, compositions and properties. These materials can potentially form the basis for novel energy storage technologies as batteries and for hydrogen storage.

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Rare Earth Borohydrides—Crystal Structures and Thermal Properties

Cited by 42 publications

References 74 publications

Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches

Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches

Borohydride as Magnetic Superexchange Pathway in Late Lanthanide Borohydrides

Functional Materials Based on Metal Hydrides

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