Dehydriding Process and Hydrogen–Deuterium Exchange of LiBH4–Mg2FeD6 Composites

Li, Guanqiao; Matsuo, Motoaki; Aoki, Katsutoshi; Ikeshoji, Tamio; Orimo, Shin Ichi

doi:10.3390/en8065459

Cited by 6 publications

(6 citation statements)

References 24 publications

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“…Ghaani et al reported a composite reaction similar to that shown in Equation (2) in the LiBH4-rich composition [13,19]. Our results demonstrate that the reaction between LiBH4 and Mg2FeH6 was stoichiometric and did not degrade when excess LiBH4 or Mg2FeH6 was present.…”

Section: Discussionsupporting

confidence: 79%

“…Therefore, in a previous study, we have tried to bring down the dehydrogenation temperature of LiBH 4 by combining it with a transition-metal-based complex hydride, Mg 2 FeH 6 . We ball-milled the two complex hydrides over a large composition range: (1 − x)LiBH 4 + xMg 2 FeH 6 (0.25 ≤ x ≤ 0.9) [12][13][14][15]. The dehydrogenation properties were investigated using a dynamic measurement: thermogravimetry-mass spectrometry (TG-MS).…”

Section: Introductionmentioning

confidence: 99%

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Thermodynamic Properties and Reversible Hydrogenation of LiBH4–Mg2FeH6 Composite Materials

Matsuo

Takagi

et al. 2017

Inorganics

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Abstract:In previous studies, complex hydrides LiBH 4 and Mg 2 FeH 6 have been reported to undergo simultaneous dehydrogenation when ball-milled as composite materials (1 − x)LiBH 4 + xMg 2 FeH 6 . The simultaneous hydrogen release led to a decrease of the dehydrogenation temperature by as much as 150 K when compared to that of LiBH 4 . It also led to the modified dehydrogenation properties of Mg 2 FeH 6 . The simultaneous dehydrogenation behavior between stoichiometric ratios of LiBH 4 and Mg 2 FeH 6 is not yet understood. Therefore, in the present work, we used the molar ratio x = 0.25, 0.5, and 0.75, and studied the isothermal dehydrogenation processes via pressure-composition-isothermal (PCT) measurements. The results indicated that the same stoichiometric reaction occurred in all of these composite materials, and x = 0.5 was the molar ratio between LiBH 4 and Mg 2 FeH 6 in the reaction. Due to the optimal composition ratio, the composite material exhibited enhanced rehydrogenation and reversibility properties: the temperature and pressure of 673 K and 20 MPa of H 2 , respectively, for the full rehydrogenation of x = 0.5 composite, were much lower than those required for the partial rehydrogenation of LiBH 4 . Moreover, the x = 0.5 composite could be reversibly hydrogenated for more than four cycles without degradation of its H 2 capacity.

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Section: Discussionsupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Thermodynamic Properties and Reversible Hydrogenation of LiBH4–Mg2FeH6 Composite Materials

Matsuo

Takagi

et al. 2017

Inorganics

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“…Interestingly, this mixes the elevated gravimetric hydrogen density of LiBH4 (13.9%) [13] with its impressive volumetric counterpart of Mg2FeH6 (150 g L −1 ) [5]. Other studies on related compounds have also shown similarly great levels of promise [14][15][16][17]. In a study by Li et Al.…”

Section: Namementioning

confidence: 88%

In Situ Synchrotron X-ray Diffraction Studies of Hydrogen-Desorption Properties of 2LiBH4–Mg2FeH6 Composite

2021

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Adding a secondary complex metal hydride can either kinetically or thermodynamically facilitate dehydrogenation reactions. Adding Mg2FeH6 to LiBH4 is energetically favoured, since FeB and MgB2 are formed as stable intermediate compounds during dehydrogenation reactions. Such “hydride destabilisation” enhances H2-release thermodynamics from H2-storage materials. Samples of the LiBH4 and Mg2FeH6 with a 2:1 molar ratio were mixed and decomposed under three different conditions (dynamic decomposition under vacuum, dynamic decomposition under a hydrogen atmosphere, and isothermal decomposition). In situ synchrotron X-ray diffraction results revealed the influence of decomposition conditions on the selected reaction path. Dynamic decomposition of Mg2FeH6–LiBH4 under vacuum, or isothermal decomposition at low temperatures, was found to induce pure decomposition of LiBH4, whilst mixed decomposition of LiBH4 + Mg and formation of MgB2 were achieved via high-temperature isothermal dehydrogenation.

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“…Another likely explanation for mutual desorption behavior is the hydrogen exchange of each of the components prior to desorption similar to the system LiBH 4 -Mg 2 FeD 6 . 24 Hydrogen exchange has been shown in the MgH 2 þ LiBH 4 system therefore increasing the desorption temperature of MgH 2 . 25 In simultaneous hydrogen release from all of the RHCs occurred within a narrow temperature release with a single or near single transition.…”

mentioning

confidence: 99%

Simultaneous desorption behavior of M borohydrides and Mg2FeH6 reactive hydride composites (M = Mg, then Li, Na, K, Ca)

Chaudhary

Matsuo

et al. 2015

Applied Physics Letters

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Original Chaudhary, A.-L.; Li, G.; Matsuo, M.; Orimo, S.; Deledda, S., Soerby, M.H.; Hauback, B.C.; Pistidda, C.; Klassen, T.; Dornheim, M.: Simultaneous desorption behavior of M borohydrides and Mg2FeH6 reactive hydride composites (M = Mg, then Li, Na, K, Ca)In: Applied Physics Letters (2015) AIP Combinations of complex metal borohydrides ball milled with the transition metal complex hydride, Mg 2 FeH 6 , are analysed and compared. Initially, the Reactive Hydride Composite (RHC) of Mg 2þ cation mixtures of Mg 2 FeH 6 and c-Mg(BH 4 ) 2 is combined in a range of molar ratios and heated to a maximum of 450 C. For the molar ratio of 6 Mg 2 FeH 6 þ Mg(BH 4 ) 2 , simultaneous desorption of the two hydrides occurred, which resulted in a single event of hydrogen release. This single step desorption occurred at temperatures between those of Mg 2 FeH 6 and c-Mg(BH 4 ) 2 . Keeping this anionic ratio constant, the desorption behavior of four other borohydrides, Li-, Na-, K-, and Ca-borohydrides was studied by using materials ball milled with Mg 2 FeH 6 applying the same milling parameters. The mixtures containing Mg-, Li-, and Ca-borohydrides also released hydrogen in a single event. The Mass Spectrometry (MS) results show a double step reaction within a narrow temperature range for both the Na-and K-borohydride mixtures. This phenomenon, observed for the RHC systems at the same anionic ratio with all five light metal borohydride mixtures, can be described as simultaneous hydrogen desorption within a narrow temperature range centered around 300 C. V C 2015 AIP Publishing LLC. [http://dx.

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Dehydriding Process and Hydrogen–Deuterium Exchange of LiBH4–Mg2FeD6 Composites

Cited by 6 publications

References 24 publications

Thermodynamic Properties and Reversible Hydrogenation of LiBH4–Mg2FeH6 Composite Materials

Thermodynamic Properties and Reversible Hydrogenation of LiBH4–Mg2FeH6 Composite Materials

In Situ Synchrotron X-ray Diffraction Studies of Hydrogen-Desorption Properties of 2LiBH4–Mg2FeH6 Composite

Simultaneous desorption behavior of M borohydrides and Mg2FeH6 reactive hydride composites (M = Mg, then Li, Na, K, Ca)

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