Unexpected dehydrogenation behavior of LiBH4/Mg(BH4)2 mixture associated with the in situ formation of dual-cation borohydride

Fang, Zhan Zhao; Kang, Xiangdong; Wang, Ping; Li, Haiwen; Orimo, Shin Ichi

doi:10.1016/j.jallcom.2009.10.149

Cited by 58 publications

(39 citation statements)

References 33 publications

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“…The slightly lowered dehydrogenation temperature of Mg(BH 4 ) 2 in the combined systems may be due to its interaction with the intermediates of MgH 2 and Al formed at the first stage and/or the LiBH 4 formed during ball-milling. It was reported by Bardaji et al [19] and Fang et al [20], the dehydrogenation property of Mg(BH 4 ) 2 could be improved by the combination of LiBH 4 . Moreover, MgH 2 was also reported to improve the hydrogen storage properties of LiBH 4 by reaction [12,21].…”

Section: Dehydrogenation Process Of the Mg(bh 4 ) 2 -Xlialh 4 Systemsmentioning

confidence: 80%

“…However, enhanced dehydrogenation of this ball-milled/ combined Mg(BH 4 ) 2 -LiBH 4 system, compared with the pristine Mg(BH 4 ) 2 , was only noted at an early stage of dehydrogenation between 170e240 C in another article [20]. In addition, an un-known phase was formed during milling in that work [20]. The difference may be due to the different ballmilling parameters used by the two groups.…”

Section: Introductionmentioning

confidence: 85%

“…Bardaji et al [19] reported that the dehydrogenation performance of the combined system of Mg(BH 4 ) 2 -LiBH 4 prepared by ball-milling was much better than that of either Mg(BH 4 ) 2 or LiBH 4 in the temperature range of 170e320 C. They further pointed out that the milling process was mainly physical mixing of the two compounds, as no new phase was found in the mixture. However, enhanced dehydrogenation of this ball-milled/ combined Mg(BH 4 ) 2 -LiBH 4 system, compared with the pristine Mg(BH 4 ) 2 , was only noted at an early stage of dehydrogenation between 170e240 C in another article [20]. In addition, an un-known phase was formed during milling in that work [20].…”

Section: Introductionmentioning

confidence: 86%

See 2 more Smart Citations

Multi-hydride systems with enhanced hydrogen storage properties derived from Mg(BH4)2 and LiAlH4

Yang

Gao

Liu

et al. 2012

International Journal of Hydrogen Energy

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Section: Dehydrogenation Process Of the Mg(bh 4 ) 2 -Xlialh 4 Systemsmentioning

confidence: 80%

Section: Introductionmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 86%

See 1 more Smart Citation

Multi-hydride systems with enhanced hydrogen storage properties derived from Mg(BH4)2 and LiAlH4

Yang

Gao

Liu

et al. 2012

International Journal of Hydrogen Energy

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“…Recently, both theoretical 2,3,4,5 and experimental 6,7,8 studies have been performed to understand mixing of two metal borohydrides. Li et al 9 mixed LiBH 4 with Zn, Zr or Al based borohydrides, and showed that the decomposition temperature of LiBH 4 could be decreased on mixing with other metal borohydrides.…”

Section: Introductionmentioning

confidence: 99%

First-principles prediction of phase stability and crystal structures in Li-Zn and Na-Zn mixed-metal borohydrides

Aidhy

Wolverton

2011

Phys. Rev. B

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We use a combination of first principles density functional theory (DFT) calculations and the recently developed Prototype Electrostatic Ground State (PEGS) method to predict low energy crystal structures and study phase stability of Li-Zn and Na-Zn mixed-metal borohydride compounds, i.e., NaZn(BH 4 ) 3 , NaZn 2 (BH 4 ) 5 , LiZn(BH 4 ) 3 and LiZn 2 (BH 4 ) 5 .We find the following: (i) DFT+PEGS successfully predicts low-energy structures in these mixed-metal borohydride systems. (ii) DFT calculations show negative mixing energies in both the Li-Zn and Na-Zn borohydride systems, consistent with the observation of mixed-metal ordering in these systems. (iii) Our DFT calculations of the recently reported experimental crystal structures of NaZn 2 (BH 4 ) 5 and NaZn(BH 4 ) 3 show that the former has a negative mixing energy, while the latter has a positive mixing energy, (iv) Using the PEGS approach, we predict a new crystal structure of NaZn(BH 4 ) 3 with negative mixing energy and find that the experimental structure of NaZn 2 (BH 4 ) 5 and the PEGS obtained structure of NaZn(BH 4 ) 3 lie on the ground state convex hull. (v) In the Li-Zn borohydride system, we have used the PEGS+DFT approach to predict a stable crystal structure of new, previously unobserved stoichiometry, LiZn(BH 4 ) 3 . As a consequence of this predicted low-energy compound,

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“…In the 1st cycle (Figure 5b, 1st cycle), the polymorphic transition of LiBH 4 is observed as a broad peak at T peak = 111 • C, followed by the melting of the eutectic at T peak = 176 • C. Upon cooling the crystallization of the eutectic is not clearly detected, possibly because some Mg(BH 4 ) 2 has already reacted, enriching the LiBH 4 fraction in the composition of the borohydride mixture [16][17][18]. In fact, the DSC peak due to the LiBH 4 phase transformation appears more intense on cooling with respect to that observed on heating.…”

Section: Mg 2 Nih 4 -Libh 4 -Mg(bh 4 ) 2 Eutectic Compositionmentioning

confidence: 99%

Reactive Hydride Composite of Mg2NiH4 with Borohydrides Eutectic Mixtures

et al. 2018

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Abstract:The development of materials showing hydrogen sorption reactions close to room temperature and ambient pressure will promote the use of hydrogen as energy carrier for mobile and stationary large-scale applications. In the present study, in order to reduce the thermodynamic stability of MgH 2 , Ni has been added to form Mg 2 NiH 4 , which has been mixed with various borohydrides to further tune hydrogen release reactions. De-hydrogenation/re-hydrogenation properties of Mg 2 NiH 4 -LiBH 4 -M(BH 4 ) x (M = Na, K, Mg, Ca) systems have been investigated. Mixtures of borohydrides have been selected to form eutectics, which provide a liquid phase at low temperatures, from 110 • C up to 216 • C. The presence of a liquid borohydride phase decreases the temperature of hydrogen release of Mg 2 NiH 4 but only slight differences have been detected by changing the borohydrides in the eutectic mixture.

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Unexpected dehydrogenation behavior of LiBH4/Mg(BH4)2 mixture associated with the in situ formation of dual-cation borohydride

Cited by 58 publications

References 33 publications

Multi-hydride systems with enhanced hydrogen storage properties derived from Mg(BH4)2 and LiAlH4

Multi-hydride systems with enhanced hydrogen storage properties derived from Mg(BH4)2 and LiAlH4

First-principles prediction of phase stability and crystal structures in Li-Zn and Na-Zn mixed-metal borohydrides

Reactive Hydride Composite of Mg2NiH4 with Borohydrides Eutectic Mixtures

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