Composite cooperative enhancement on the hydrogen desorption kinetics of LiBH4 by co-doping with NbCl5 and hexagonal BN

Tu, Guo-Ping; Xiao, Xuezhang; Jiang, Yiqun; Qin, Teng; Li, Shouquan; Ge, Hongwei; Wang, Qidong; Chen, Lixin

doi:10.1016/j.ijhydene.2015.06.168

Cited by 21 publications

(7 citation statements)

References 43 publications

(36 reference statements)

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“…The next known category of catalyst is halides, which mainly include chloride and fluorides, which were also successfully employed to enhance sorption kinetics of magnesium hydride as well as alanates. With the hope of having similar benefits, several halides were employed as additive with borohydrides [284][285][286][287][288][289][290][291][292][293][294][295][296][297][298][299][300][301][302][303]. It was suggested [284] that transition metal halides reduce the decomposition temperature of LiBH 4 , however, at the same time the formation of unstable transition metal borohydrides lead to the release of diborane gas due to immediate decomposition, which causes the loss of reversibility.…”

Section: Catalysts For Borohydridesmentioning

confidence: 99%

Catalytic Tuning of Sorption Kinetics of Lightweight Hydrides: A Review of the Materials and Mechanism

2018

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Hydrogen storage materials have been a subject of intensive research during the last 4 decades. Several developments have been achieved in regard of finding suitable materials as per the US-DOE targets. While the lightweight metal hydrides and complex hydrides meet the targeted hydrogen capacity, these possess difficulties of hard thermodynamics and sluggish kinetics of hydrogen sorption. A number of methods have been explored to tune the thermodynamic and kinetic properties of these materials. The thermodynamic constraints could be resolved using an intermediate step of alloying or by making reactive composites with other hydrogen storage materials, whereas the sluggish kinetics could be improved using several approaches such as downsizing and the use of catalysts. The catalyst addition reduces the activation barrier and enhances the sorption rate of hydrogen absorption/desorption. In this review, the catalytic modifications of lightweight hydrogen storage materials are reported and the mechanism towards the improvement is discussed.

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Section: Catalysts For Borohydridesmentioning

confidence: 99%

Catalytic Tuning of Sorption Kinetics of Lightweight Hydrides: A Review of the Materials and Mechanism

2018

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“…In our previous works, ball-milled nanocrystal h-BN was composited with LiBH 4 as a catalyst to improve the hydrogen storage properties of LiBH 4 . − It has been found that adding a small amount of h-BN could enhance the dehydrogenation kinetics of LiBH 4 , and the cyclic de/rehydrogenation of LiBH 4 would be improved by adding more h-BN . It has been revealed that both B and N atoms of h-BN play important roles in this system.…”

Section: Introductionmentioning

confidence: 99%

Achieving High Dehydrogenation Kinetics and Reversibility of LiBH₄ by Adding Nanoporous h-BN to Destabilize LiH

et al. 2018

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Lithium borohydride (LiBH 4 ) is a potential high-capacity hydrogen storage material but is limited by its high thermal stability and poor reversibility. Nanostructured hexagonal boron nitrides (h-BNs) with thin-layer (TL-BN) and nanoporous (NP-BN) structures have been prepared by treating h-BN in a hydrolysis process of LiBH 4 and then mixing with LiBH 4 by ball-milling to investigate their catalyzing effect on dehydrogenation and rehydrogenation. Nanostructured h-BN, in particular NP-BN, with an average pore size of 40 nm, significantly promotes the dehydrogenation kinetics, dehydrogenation capacity, and reversibility of LiBH 4 . For a LiBH 4 + NP-BN (mole ratio 1:0.3) composite, the dehydrogenation capacity reaches 13.9 wt % for LiBH 4 at 400 °C, which is very close to its theoretical one. The cycling capacity could remain stable at ∼7.6 wt % with rapid kinetics after de/rehydrogenation cycles under 10 MPa of hydrogen at 400 °C. The improved de/hydrogenation performance of LiBH 4 depends on the nanoconfinement structure of LiBH 4 in NP-BN. After dehydrogenation, a lithium-intercalated h-BN(LixBN) nanocrystal was formed by the reaction of h-BN and LiH. This LixBN nanocrystal confined the dehydrogenation products of the amorphous structure during dehydrogenation. Thus, this nanocrystal-confine-amorphous structure destabilizing LiH and benefiting the rehydrogenation and reversible capacity of the composite.

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“…Zhou (Zhou et al 2017) prepared a 2LiBH 4 -LiAlH 4 composite nanoconfined in an RFC aerogel, and found that both the thermodynamic and kinetic properties were enhanced. Some catalysts such as CaH 2 (Jiang et al, 2012), NbF 5 (Mao et al, 2013), TiF 3 (Mao et al, 2010) and NbCl 5 (Tu et al, 2015) destabilize LiBH 4 to decompose H 2 under moderate conditions. Ming mixed LiBH 4 with several additives using the ball-milling method (Au and Jurgensen, 2006).…”

Section: Introductionmentioning

confidence: 99%

Effect of Different Amounts of TiF3 on the Reversible Hydrogen Storage Properties of 2LiBH4–Li3AlH6 Composite

Zhang

Chen

2021

Front. Chem.

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Hydrogen is a potential green alternative to conventional energy carriers such as oil and coal. Compared with the storage of hydrogen in gaseous or liquid phases, the chemical storage of hydrogen in solid complex hydrides is safer and more effective. In this study, the complex hydride composite 2LiBH4–Li3AlH6 with different amounts of TiF3 was prepared by simple ball-milling and its hydrogen storage properties were investigated. Temperature programmed desorption and differential scanning calorimetry were used to characterize the de/rehydrogenation performance, and X-ray diffraction and scanning electron microscopy (SEM) were used to explore the phase structure and surface topography of the materials. The dehydrogenation temperature decreased by 48°C in 2LiBH4–Li3AlH6 with 15 wt% TiF3 composites compared to the composite without additives while the reaction kinetics was accelerated by 20%. In addition, the influence of hydrogen back pressure on the 2LiBH4–Li3AlH6 with 5 wt% TiF3 composite was also investigated. The results show that hydrogen back pressure between 2.5 and 3.5 bar can improve the reversible performance of the composite to some extent. With a back pressure of 3.5 bar, the second dehydrogenation capacity increased to 4.6 wt% from the 3.3 wt% in the 2LiBH4–Li3AlH6 composite without hydrogen back pressure. However, the dehydrogenation kinetics was hindered. About 150 h, which is 100 times the time required without back pressure, was needed to release 8.7 wt% of hydrogen at 3.5 bar hydrogen back pressure. The SEM results show that aluminum was aggregated after the second cycle of dehydrogenation at the hydrogen back pressure of 3 bar, resulting in the partial reversibility of the 5 wt% TiF3-added 2LiBH4–Li3AlH6 composite.

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Composite cooperative enhancement on the hydrogen desorption kinetics of LiBH4 by co-doping with NbCl5 and hexagonal BN

Cited by 21 publications

References 43 publications

Catalytic Tuning of Sorption Kinetics of Lightweight Hydrides: A Review of the Materials and Mechanism

Catalytic Tuning of Sorption Kinetics of Lightweight Hydrides: A Review of the Materials and Mechanism

Achieving High Dehydrogenation Kinetics and Reversibility of LiBH₄ by Adding Nanoporous h-BN to Destabilize LiH

Effect of Different Amounts of TiF3 on the Reversible Hydrogen Storage Properties of 2LiBH4–Li3AlH6 Composite

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Composite cooperative enhancement on the hydrogen desorption kinetics of LiBH4 by co-doping with NbCl5 and hexagonal BN

Cited by 21 publications

References 43 publications

Catalytic Tuning of Sorption Kinetics of Lightweight Hydrides: A Review of the Materials and Mechanism

Catalytic Tuning of Sorption Kinetics of Lightweight Hydrides: A Review of the Materials and Mechanism

Achieving High Dehydrogenation Kinetics and Reversibility of LiBH4 by Adding Nanoporous h-BN to Destabilize LiH

Effect of Different Amounts of TiF3 on the Reversible Hydrogen Storage Properties of 2LiBH4–Li3AlH6 Composite

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Achieving High Dehydrogenation Kinetics and Reversibility of LiBH₄ by Adding Nanoporous h-BN to Destabilize LiH