Hydrogen release and structural transformations in LiNH2–MgH2 systems

Pottmaier, Daphiny; Dolci, Francesco; Orlova, M. P.; Vaughan, Gavin; Fichtner, Maximilian; Lohstroh, Wiebke; Baricco, Marcello

doi:10.1016/j.jallcom.2010.10.166

Cited by 14 publications

(6 citation statements)

References 28 publications

(49 reference statements)

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“…These results are similar to dehydrogenation-rehydrogenation studies on ball-milled mixtures of magnesium hydride and lithium nitride. Here, the same hydrides, nitrides, and imides are found after hydrogenation with varying phase contents, depending on reaction conditions. − Analogous DSC and X-ray diffraction experiments for the deuterated compounds yield very similar results.…”

Section: Results and Discussionsupporting

confidence: 58%

Hydrogenation Reaction Pathways in the Systems Li₃N–H₂, Li₃N–Mg–H₂, and Li₃N–MgH₂–H₂ by in Situ X-ray Diffraction, in Situ Neutron Diffraction, and in Situ Thermal Analysis

2016

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The phase diagram Li−Mg−N−H offers ample opportunities for potential hydrogen storage systems. Three systems based on lithium nitride, Li 3 N, were investigated by time-resolved in situ methods (thermal analysis, Xray and neutron diffraction) at temperatures up to 703 K and hydrogen gas pressures up to 9.4 MPa. Pure lithium nitride reacts in a one-step reaction to lithium amide according to Li 3 N + 2H 2 → LiNH 2 + 2LiH at 1.0 MPa hydrogen pressure. Equimolar mixtures of lithium nitride with magnesium hydride, both at 1.5 and 9.4 MPa hydrogen gas pressure, react in the same way up to 543 K, i.e., magnesium hydride does not participate in the reaction. At higher temperatures, lithium magnesium nitride is formed according to the endothermic reaction LiNH 2 + MgH 2 → LiMgN + 2H 2 at moderate (≤1.5 MPa) and via the exothermic reaction Li 3 N + MgH 2 → LiMgN + 2LiH at higher hydrogen gas pressures (5.0 MPa). Mixed imide Li 2 Mg(NH) 2 is formed when an excess of Li 3 N is used in the reaction. The hydrogenation of mixtures of lithium nitride with magnesium starts with the formation Li 2 NH and Li 4 NH, followed by the mixed imide Li 2 Mg(NH) 2 at higher temperatures and finally the formation of Mg 3 N 2 and LiH. Deuterides react accordingly.

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Section: Results and Discussionsupporting

confidence: 58%

Hydrogenation Reaction Pathways in the Systems Li₃N–H₂, Li₃N–Mg–H₂, and Li₃N–MgH₂–H₂ by in Situ X-ray Diffraction, in Situ Neutron Diffraction, and in Situ Thermal Analysis

2016

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“…Following this work, the Li-Mg-N-H system has been widely studied by many groups [7][8][9][10][11][12][13][14], with efforts now concentrated on its improvement as a hydrogen store and, in particular, low temperature hydrogen cycling.…”

Section: Introductionmentioning

confidence: 99%

Effect of the calcium halides, CaCl2 and CaBr2, on hydrogen desorption in the Li–Mg–N–H system

Bill¹,

Reed²,

Book³

et al. 2015

Journal of Alloys and Compounds

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a b s t r a c tCalcium-halide-doped lithium amide-magnesium hydride samples were prepared both by hand-grinding and ball-milling 2LiNH 2 -MgH 2 -xCaX 2 (x = 0, 0.1, and 0.15; X = Cl or Br). The addition of calcium halides reduced the hydrogen desorption temperature in all samples. The ball-milled undoped sample (2LiNH 2 -MgH 2 ) began to desorb hydrogen at around 125°C and peaked at 170°C. Hydrogen desorption from the 0.15 mol CaCl 2 -containing sample began ca 30°C lower than that of the undoped sample and peaked at 150°C. Both the onset and peak temperatures of the CaBr 2 sample (x = 0.15) were reduced by 15°C compared to the chloride. Kissinger's method was used to calculate the effective activation energy (E a ) for the systems: E a for the 0.15 mol CaCl 2 -containing sample was found to be 91.8 kJ mol À1 and the value for the 0.15 mol CaBr 2 -containing sample was 78.8 kJ mol À1 .

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“…To this regard, in order to improve the kinetic performance of the LiNH 2 -LiH system, several strategies have been proposed in the recent past, as the particle size reduction by high-energy ball milling and addition of metal catalysts [5][6][7][8][9]. Durojaiye and Goudy, demonstrated that the addition of KH to the 2LiNH 2 -MgH 2 system, decreased the desorption temperature with respect to the undoped system (75.3°C vs 109°C) while keeping similar gravimetric capacity of 5 wt.% [8].…”

Section: Introductionmentioning

confidence: 99%

Kinetic improvement on the CaH2-catalyzed Mg(NH2)2+ 2LiH system

Torre

Valentoni

Milanese

et al. 2015

Journal of Alloys and Compounds

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Hydrogen release and structural transformations in LiNH2–MgH2 systems

Cited by 14 publications

References 28 publications

Hydrogenation Reaction Pathways in the Systems Li₃N–H₂, Li₃N–Mg–H₂, and Li₃N–MgH₂–H₂ by in Situ X-ray Diffraction, in Situ Neutron Diffraction, and in Situ Thermal Analysis

Hydrogenation Reaction Pathways in the Systems Li₃N–H₂, Li₃N–Mg–H₂, and Li₃N–MgH₂–H₂ by in Situ X-ray Diffraction, in Situ Neutron Diffraction, and in Situ Thermal Analysis

Effect of the calcium halides, CaCl2 and CaBr2, on hydrogen desorption in the Li–Mg–N–H system

Kinetic improvement on the CaH2-catalyzed Mg(NH2)2+ 2LiH system

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Hydrogen release and structural transformations in LiNH2–MgH2 systems

Cited by 14 publications

References 28 publications

Hydrogenation Reaction Pathways in the Systems Li3N–H2, Li3N–Mg–H2, and Li3N–MgH2–H2 by in Situ X-ray Diffraction, in Situ Neutron Diffraction, and in Situ Thermal Analysis

Hydrogenation Reaction Pathways in the Systems Li3N–H2, Li3N–Mg–H2, and Li3N–MgH2–H2 by in Situ X-ray Diffraction, in Situ Neutron Diffraction, and in Situ Thermal Analysis

Effect of the calcium halides, CaCl2 and CaBr2, on hydrogen desorption in the Li–Mg–N–H system

Kinetic improvement on the CaH2-catalyzed Mg(NH2)2+ 2LiH system

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Product

Resources

About

Hydrogenation Reaction Pathways in the Systems Li₃N–H₂, Li₃N–Mg–H₂, and Li₃N–MgH₂–H₂ by in Situ X-ray Diffraction, in Situ Neutron Diffraction, and in Situ Thermal Analysis

Hydrogenation Reaction Pathways in the Systems Li₃N–H₂, Li₃N–Mg–H₂, and Li₃N–MgH₂–H₂ by in Situ X-ray Diffraction, in Situ Neutron Diffraction, and in Situ Thermal Analysis