Synthesis and Hydrogen Storage Properties of a Single-Phase Magnesium Borohydride Mg(BH&lt;SUB&gt;4&lt;/SUB&gt;)&lt;SUB&gt;2&lt;/SUB&gt;

Li, Haiwen; Kikuchi, Kentaro; Sato, Toyoto; Nakamori, Yoshiteru; Ohba, Nobuko; Aoki, Masakazu; Miwa, Kenji; Towata, Shin‐ichi; Orimo, Shin Ichi

doi:10.2320/matertrans.ma200807

Cited by 41 publications

(33 citation statements)

References 36 publications

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“…So far, enthalpy change of 57 kJ mol À1 H 2 was reported for the reactions (a)+(b) (from Mg(BH 4 ) 2 to MgH 2 ), based on the PCT measurement. 9,12) The value is different from that determined from the first-principles calculations, 13) as shown in Table 1. Experimentally, Differential Scanning Calorimetry (DSC) measurement under hydrogen pressures can provide accurate values of enthalpy changes for dehydriding reactions.…”

Section: Introductionmentioning

confidence: 71%

“…2 in the reaction (a). 9,[11][12][13] Further studies on Mg(BH 4 ) 2 are highly required viewpoints both from thermodynamics and dynamics aspects.…”

Section: )mentioning

confidence: 99%

“…[1][2][3][4][5] Recently, studies on syntheses, structural characterizations and dehydriding (decomposition)-rehydriding (recombination) reactions of Mg(BH 4 ) 2 have been intensively carried out. [6][7][8][9][10][11][12] Upon heating, the dehydriding reaction of Mg(BH 4 ) 2 starts at approximately 500 K and 14.4 mass% of hydrogen is released up to 800 K. Both TG (thermogravimetry) and PCT (pressure-composition-temperature) measurements consistently indicate the occurrence of the multistep dehydriding reactions, as follows:…”

Section: Introductionmentioning

confidence: 99%

“…MgB 12 H 12 . 9,11,12) For further development of Mg(BH 4 ) 2 , it is of quite importance to precisely estimate the values of enthalpy changes for the multistep dehydriding reactions mentioned above. So far, enthalpy change of 57 kJ mol À1 H 2 was reported for the reactions (a)+(b) (from Mg(BH 4 ) 2 to MgH 2 ), based on the PCT measurement.…”

Section: Introductionmentioning

confidence: 99%

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Differential Scanning Calorimetry Measurements of Magnesium Borohydride Mg(BH4)2

Yan

Nakamori

et al. 2008

Mater. Trans.

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Multistep dehydriding reactions of magnesium borohydride Mg(BH 4 ) 2 were studied by Differential Scanning Calorimetry (DSC) measurements. The values of the enthalpy changes of the reactions from the measurements are in good agreement with those from first-principles calculations. Kinetically restricted dehydriding reaction of Mg(BH 4 ) 2 , suggested also by the measurements, was briefly discussed.

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Section: Introductionmentioning

confidence: 71%

“…2 in the reaction (a). 9,[11][12][13] Further studies on Mg(BH 4 ) 2 are highly required viewpoints both from thermodynamics and dynamics aspects.…”

Section: )mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Differential Scanning Calorimetry Measurements of Magnesium Borohydride Mg(BH4)2

Yan

Nakamori

et al. 2008

Mater. Trans.

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“…1) In contrast to the compressed hydrogen and the liquefaction hydrogen, hydrogen storage in the solid state is the most promising alternative. [2][3][4][5] In the past decades, the complex hydrides consisting of light elements, e.g., alanates, [6][7][8][9][10] amides, [11][12][13][14][15] borohydrides [16][17][18][19][20] and ammonia borane (AB), [21][22][23] have been attracting extensive attention as the potential hydrogen storage materials due to their high gravimetric and volumetric hydrogen storage densities. In particular, significant efforts have been made in recent years with metal amide-hydride combined systems since Chen et al reported that lithium nitride, Li 3 N could absorb/desorb reversibly 11.4 mass% of hydrogen in 2002.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Storage Properties of the Mg(NH3)6Cl2-LiH Combined System

Liu

Luo

et al. 2011

Mater. Trans.

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Metal ammine complexes (MACs) were recently regarded as one of promising materials for reversible hydrogen storage due to their high hydrogen content. In this work, a first attempt is conducted to elucidate the hydrogen storage reversibility by combining Mg(NH 3 ) 6 Cl 2 with LiH. It is found that hydrogen is gradually evolved from the combined system during ball milling. After 24 h of milling, approximate 3.5 mass% of hydrogen, equivalent to 6 mol of H 2 molecules, is released from the Mg(NH 3 ) 6 Cl 2 -18LiH mixture. Additional 3.4 mass% of hydrogen is further desorbed from the combined system milled for 24 h with a two-step reaction in heating process. Totally $ 12 mol of H 2 molecules are librated from the Mg(NH 3 ) 6 Cl 2 -18LiH mixture along with the formation and consumption of Mg(NH 2 ) 2 and LiNH 2 in the ball milling and subsequent heating process. The resultant products consist of Li 2 Mg(NH) 2 , Li 2 NH, LiH and LiCl after dehydrogenation at 310 C. Further hydrogenation experiment indicates that $ 6 mol of H 2 molecules are reversibly stored in the Mg(NH 3 ) 6 Cl 2 -12LiH mixture.

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Desolvation and Dehydrogenation of Solvated Magnesium Salts of Dodecahydrododecaborate: Relationship between Structure and Thermal Decomposition

Chen

Liu

Alexander

et al. 2014

Chemistry A European J

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Attempts to synthesize solvent‐free MgB12H12 by heating various solvated forms (H2O, NH3, and CH3OH) of the salt failed because of the competition between desolvation and dehydrogenation. This competition has been studied by thermogravimetric analysis (TGA) and temperature‐programmed desorption (TPD). Products were characterized by IR, solution‐ and solid‐state NMR spectroscopy, elemental analysis, and single‐crystal or powder X‐ray diffraction analysis. For hydrated salts, thermal decomposition proceeded in three stages, loss of water to form first hexahydrated then trihydrated, and finally loss of water and hydrogen to form polyhydroxylated complexes. For partially ammoniated salts, two stages of thermal decomposition were observed as ammonia and hydrogen were released with weight loss first of 14 % and then 5.5 %. Thermal decomposition of methanolated salts proceeded through a single step with a total weight loss of 32 % with the release of methanol, methane, and hydrogen. All the gaseous products of thermal decomposition were characterized by using mass spectrometry. Residual solid materials were characterized by solid‐state 11B magic‐angle spinning (MAS) NMR spectroscopy and X‐ray powder diffraction analysis by which the molecular structures of hexahydrated and trihydrated complexes were solved. Both hydrogen and dihydrogen bonds were observed in structures of [Mg(H2O)6B12H12]⋅6 H2O and [Mg(CH3OH)6B12H12]⋅6 CH3OH, which were determined by single‐crystal X‐ray diffraction analysis. The structural factors influencing thermal decomposition behavior are identified and discussed. The dependence of dehydrogenation on the formation of dihydrogen bonds may be an important consideration in the design of solid‐state hydrogen storage materials.

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Synthesis and Hydrogen Storage Properties of a Single-Phase Magnesium Borohydride Mg(BH<SUB>4</SUB>)<SUB>2</SUB>

Cited by 41 publications

References 36 publications

Differential Scanning Calorimetry Measurements of Magnesium Borohydride Mg(BH<SUB>4</SUB>)<SUB>2</SUB>

Differential Scanning Calorimetry Measurements of Magnesium Borohydride Mg(BH<SUB>4</SUB>)<SUB>2</SUB>

Hydrogen Storage Properties of the Mg(NH<SUB>3</SUB>)<SUB>6</SUB>Cl<SUB>2</SUB>-LiH Combined System

Desolvation and Dehydrogenation of Solvated Magnesium Salts of Dodecahydrododecaborate: Relationship between Structure and Thermal Decomposition

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