Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

Sadikin, Yolanda; Stare, Katarina; Schouwink, Pascal; Ley, Morten B.; Meden, Anton; Černý, Radovan

doi:10.1016/j.jssc.2014.12.018

Cited by 28 publications

(21 citation statements)

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“…Solvent-based methods can provide a solvent-free monometallic borohydride, often by using a metal borohydride solvate as an intermediate, such as M(BH 4 ) x , M = Mg, Mn, Y, Eu, Gd [27][28][29][30][31]. This approach has also led to the first tri-metallic borohydrides [32][33][34].…”

Section: )Cl 2 ]mentioning

confidence: 99%

Complex and liquid hydrides for energy storage

et al. 2016

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The research on complex hydrides for hydrogen storage was initiated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH 4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized, and the knowledge regarding the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant portion of the research groups active in the field of complex hydrides is collaborators in the International Energy Agreement Task 32. This paper reports about the important issues in the field of complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and is an excellent summary of the recent achievements.

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Section: )Cl 2 ]mentioning

confidence: 99%

Complex and liquid hydrides for energy storage

et al. 2016

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“…The various Ca(BH4)2 polymorphs are, for instance, similar to TiO2 polymorphs (Ti 4+ being isoelectronic to Ca 2+ ) [47]. A series of 20 RE-borohydrides with perovskite-like structures have been reported [38,[48][49][50][51][52][53]. Seven of the compounds exhibit face-centered cubic double-perovskite-type structures (space group Fm3 ).…”

Section: Bi-and Trimetallic Re-borohydridesmentioning

confidence: 99%

“…Non-stoichiometric chloride-containing borohydrides, NaY(BH 4 ) 2−x Cl 2+x , LiYb(BH 4 ) 4−x Cl x and Yb(BH 4 ) 2−x Cl x , where chloride anions partly substitute BH 4 -have also been reported [29,31,38].…”

Section: Halide-containing Re-borohydridesmentioning

confidence: 99%

Rare Earth Borohydrides—Crystal Structures and Thermal Properties

et al. 2017

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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 LiBH 4 and additives such as LiH.

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“…[ 11 ] We suspected that the incorporation of both complex anions in the same structure could provide means of stabilizing compounds with high symmetry, favoring cationic mobility at RT. Herein, we apply this concept to anion-mixed metal boranes containing mobile species of relevance and present a novel class of solid electrolytes with the compounds Na 3 BH 4 B 12 H 12 and (Li 0.7 Na 0.3 ) 3 BH 4 B 12 H 12 , capable of conducting either Na + or both Na + and Li + ions.…”

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Superionic Conduction of Sodium and Lithium in Anion‐Mixed Hydroborates Na₃BH₄B₁₂H₁₂ and (Li_0.7Na_0.3)₃BH₄B₁₂H₁₂

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et al. 2015

Advanced Energy Materials

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invested to stabilize superionic conduction in such materials at room temperature (RT).We have previously reported stable Cs-and Rb-borohydrides containing the closo -borane anion [B 12 H 12 ] 2− on the A -site of an inversed perovskite structure, [ 11 ] whose RT polymorph had already been reported for Cs [ 12 ] and forming during the decomposition of bi-and trimetallic borohydrides. [ 11 ] We suspected that the incorporation of both complex anions in the same structure could provide means of stabilizing compounds with high symmetry, favoring cationic mobility at RT. Herein, we apply this concept to anion-mixed metal boranes containing mobile species of relevance and present a novel class of solid electrolytes with the compounds Na 3 BH 4 B 12 H 12 and (Li 0.7 Na 0.3 ) 3 BH 4 B 12 H 12 , capable of conducting either Na + or both Na + and Li + ions. Unlike order-disorder-governed dodeca-and decaboranes the cationic mobility is not entropically activated in Na 3 BH 4 B 12 H 12 and (Li 0.7 Na 0.3 ) 3 BH 4 B 12 H 12 , thus requiring no HT phase transition. The conduction pathways in Na 3 BH 4 B 12 H 12 are 2D where Na 2 B 12 H 12 -like slabs are in fact nonconducting, reaching RT conductivity values close to the order of 10 −3 S cm −1 and hence superior to many sulfi de glasses, NASICON and rivaling even β-alumina. [ 13,14 ] (Li 0.7 Na 0.3 ) 3 BH 4 B 12 H 12 , on the other hand, forms 1D channels for mixed cation conduction. The chemical reaction forming the compound at 500 K is accompanied by a dramatic increase in ionic conductivity attaining values higher than 10 −1 S cm −1 in the thermal stability region. Conductivity decreases upon cooling owed to full reversibility of the reaction. Such temperatures are nevertheless within reasonable limits for large-scale facilities, which operate at over 573 K in the case of Na-S power grids, for instance.The Figure S1). Ball milling is also attracting attention in battery research due to its fl exibility and the ease with which it is brought to the industrial scale. It has recently been used to prepare promising Na-based materials. [ 13,15 ] We also recently employed it to scan a wide variety of perovskite-type metal-borohydride systems. [ 12,16 ] Here it is used to "activate" the powders, whereby no reaction takes place even at high energies. (Li 0.7 Na 0.3 ) 3 BH 4 B 12 H 12 forms at 498 K (reaction onset) and dissociates to the precursors upon cooling. Meanwhile, the Na-rich Na 3 BH 4 B 12 H 12 forms above 638 K, and once formed it maintains the same structure in a wide temperature range of 100-653 K. Differential scanning calorimetry was used to follow the thermal events for the evolution of Na 3 BH 4 B 12 H 12 It has been recognized that battery grids are one of the more realistic contenders for future large-scale energy storage. [ 1 ] A paradigm shift is taking place in battery research that is focusing on inexpensive and abundant chemical species as alternative to compensate for the dwindling resources of lithium in terms of charge carrier (electrolyte) [ 2 ] as we...

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Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

Cited by 28 publications

References 50 publications

Complex and liquid hydrides for energy storage

Complex and liquid hydrides for energy storage

Rare Earth Borohydrides—Crystal Structures and Thermal Properties

Superionic Conduction of Sodium and Lithium in Anion‐Mixed Hydroborates Na₃BH₄B₁₂H₁₂ and (Li_0.7Na_0.3)₃BH₄B₁₂H₁₂

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Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

Cited by 28 publications

References 50 publications

Complex and liquid hydrides for energy storage

Complex and liquid hydrides for energy storage

Rare Earth Borohydrides—Crystal Structures and Thermal Properties

Superionic Conduction of Sodium and Lithium in Anion‐Mixed Hydroborates Na3BH4B12H12 and (Li0.7Na0.3)3BH4B12H12

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Superionic Conduction of Sodium and Lithium in Anion‐Mixed Hydroborates Na₃BH₄B₁₂H₁₂ and (Li_0.7Na_0.3)₃BH₄B₁₂H₁₂