Structural Changes Observed during the Reversible Hydrogenation of Mg(BH<sub>4</sub>)<sub>2</sub> with Ni-Based Additives

Saldan, Ivan; Hino, Satoshi; Humphries, Terry D.; Zavorotynska, Olena; Chong, Marina; Jensen, Craig M.; Deledda, Stefano; Hauback, Bjørn C.

doi:10.1021/jp5066677

Cited by 49 publications

(62 citation statements)

References 36 publications

(77 reference statements)

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“…The addition of several TM-compounds has indeed resulted in improved hydrogen storage properties of stable borohydrides and related composites, including decrease in Tdec [35,41], in some cases remarkably by as much as 200 °C [36]. Enhancement of the desorption and absorption reactions kinetics [26,42], improved hydrogen purity, reversibility [37] and borohydride synthesis from the decomposition products [39] has also been documented.…”

Section: Introductionmentioning

confidence: 96%

“…In our previous works [26,42] we have shown that Ni-and Co-based additives have an effect on the kinetics of hydrogen desorption and absorption in γ-Mg(BH4)2 [13]. Ex-situ X-ray absorption spectroscopy (XAS) studies have shown that the additives were chemically modified to compounds similar to Ni-and Co-borides after first decomposition of Mg(BH4)2.…”

Section: Introductionmentioning

confidence: 99%

“…A few studies have addressed the mechanisms of the additives' "catalytic" activity [26,34,42,43]. It has been shown that the additives undergo chemical transformations and form alkali-or alkaline-earth metal halides [34], finely dispersed metal clusters or/and boride-like structures [26,42,43].…”

Section: Introductionmentioning

confidence: 99%

“…It has been shown that the additives undergo chemical transformations and form alkali-or alkaline-earth metal halides [34], finely dispersed metal clusters or/and boride-like structures [26,42,43]. The latter can be stable upon cycling [26,42] or change the metal-B coordination numbers reversibly [43].…”

Section: Introductionmentioning

confidence: 99%

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Combined X-ray and Raman Studies on the Effect of Cobalt Additives on the Decomposition of Magnesium Borohydride

et al. 2015

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Magnesium borohydride (Mg(BH4)2) is one of the most promising hydrogen storage materials. Its kinetics of hydrogen desorption, reversibility, and complex reaction pathways during decomposition and rehydrogenation, however, present a challenge, which has been often addressed by using transition metal compounds as additives. In this work the decomposition of Mg(BH4)2 ball-milled with CoCl2 and CoF2 additives, was studied by means of a combination of several in-situ techniques. Synchrotron X-ray diffraction and Raman spectroscopy were used to follow the phase transitions and decomposition of Mg(BH4)2. By comparison with pure milled Mg(BH4)2, the temperature for the γ → ε phase transition in the samples with CoF2 or CoCl2 additives was reduced by 10-45 °C. In-situ Raman measurements showed the formation of a decomposition phase with vibrations at in the sample with CoF2. Simultaneous X-ray absorption measurements at the Co K-edge revealed that the additives chemically transformed to other species. CoF2 slowly reacted upon heating till ~290 °C, whereas CoCl2 transformed drastically at ~180 °C.

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Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Combined X-ray and Raman Studies on the Effect of Cobalt Additives on the Decomposition of Magnesium Borohydride

et al. 2015

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“…Consequently, the dehydrogenation temperature is reduced to 360 • C. However, the hydrogen capacity of the system is still low, i.e., 4.5 wt %. The effect of additives on the reversibility of Mg(BH 4 ) 2 has been an object of intensive investigation [101,[183][184][185][186][187][188]. The result of the doping seems to be a sensible acceleration of hydrogenation and dehydrogenation processes.…”

Section: Nabhmentioning

confidence: 99%

Tetrahydroborates: Development and Potential as Hydrogen Storage Medium

et al. 2017

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Abstract:The use of fossil fuels as an energy supply becomes increasingly problematic from the point of view of both environmental emissions and energy sustainability. As an alternative, hydrogen is widely regarded as a key element for a potential energy solution. However, differently from fossil fuels such as oil, gas, and coal, the production of hydrogen requires energy. Alternative and intermittent renewable energy sources such as solar power, wind power, etc., present multiple advantages for the production of hydrogen. On the one hand, the renewable sources contribute to a remarkable reduction of pollutants released to the air and on the other hand, they significantly enhance the sustainability of energy supply. In addition, the storage of energy in form of hydrogen has a huge potential to balance an effective and synergetic utilization of renewable energy sources. In this regard, hydrogen storage technology is a key technology towards the practical application of hydrogen as "energy carrier". Among the methods available to store hydrogen, solid-state storage is the most attractive alternative from both the safety and the volumetric energy density points of view. Because of their appealing hydrogen content, complex hydrides and complex hydride-based systems have attracted considerable attention as potential energy vectors for mobile and stationary applications. In this review, the progresses made over the last century on the synthesis and development of tetrahydroborates and tetrahydroborate-based systems for hydrogen storage purposes are summarized.

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Graphene‐Tailored Thermodynamics and Kinetics to Fabricate Metal Borohydride Nanoparticles with High Purity and Enhanced Reversibility

Zhang

Xia

Zhang

et al. 2018

Advanced Energy Materials

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Due to their ultrahigh theoretical capacity, metal borohydrides are considered to be one of the most promising candidate hydrogen storage materials. Their application still suffers, however, from high operating temperature, sluggish kinetics, and poor reversibility. Designing nanostructures is an effective way of addressing these issues, but seeking suitable approaches remains a big challenge. Here, a space‐confined solid‐gas reaction to synthesize Mg(BH4)2 nanoparticles supported on grapheme is reported, which serves as the structural support for the dispersed Mg(BH4)2 nanoparticles. More notably, density functional theory calculations reveal that graphene could weaken both the MgH bonds of MgH2 and BB bonds of B2H6, which could thermodynamically and kinetically facilitate the chemical transformation to synthesize Mg(BH4)2 with high purity. Because of the synergistic effects of both the significant reduction in particle size and the catalytic effect of graphene, an onset dehydrogenation temperature of ≈154 °C is observed for Mg(BH4)2 nanoparticles, and a complete dehydrogenation could be achieved at a temperature as low as 225 °C, with the formation of MgB2 as the by‐product. This work provides a new perspective to tailoring the thermodynamics and kinetics of chemical reactions toward the favorable synthesis of functional inorganic materials.

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Structural Changes Observed during the Reversible Hydrogenation of Mg(BH₄)₂ with Ni-Based Additives

Abstract: The decomposition and rehydrogenation of γ-Mg (BH 4 )

Cited by 49 publications

References 36 publications

Combined X-ray and Raman Studies on the Effect of Cobalt Additives on the Decomposition of Magnesium Borohydride

Combined X-ray and Raman Studies on the Effect of Cobalt Additives on the Decomposition of Magnesium Borohydride

Tetrahydroborates: Development and Potential as Hydrogen Storage Medium

Graphene‐Tailored Thermodynamics and Kinetics to Fabricate Metal Borohydride Nanoparticles with High Purity and Enhanced Reversibility

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Structural Changes Observed during the Reversible Hydrogenation of Mg(BH4)2 with Ni-Based Additives

Abstract: The decomposition and rehydrogenation of γ-Mg (BH 4 )

Cited by 49 publications

References 36 publications

Combined X-ray and Raman Studies on the Effect of Cobalt Additives on the Decomposition of Magnesium Borohydride

Combined X-ray and Raman Studies on the Effect of Cobalt Additives on the Decomposition of Magnesium Borohydride

Tetrahydroborates: Development and Potential as Hydrogen Storage Medium

Graphene‐Tailored Thermodynamics and Kinetics to Fabricate Metal Borohydride Nanoparticles with High Purity and Enhanced Reversibility

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Structural Changes Observed during the Reversible Hydrogenation of Mg(BH₄)₂ with Ni-Based Additives