Effect of Ti-doping on the dehydrogenation kinetic parameters of lithium aluminum hydride

Andreasen, Anders

doi:10.1016/j.jallcom.2005.09.067

Cited by 66 publications

(71 citation statements)

References 28 publications

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“…Moreover, the initial desorption temperature of LiAlH 4 remarkably decreased to 58°C by doping 5 mol % NiFe 2 O 4 nanopowders, which is quite lower than that of LiAlH 4 with the addition of other various previously reported catalysts. 4,5,[17][18][19][20]24,26,30,31 Meanwhile, combining these two considerations from the initial dehydrogenation temperature and hydrogen release capability, the optimal content of NiFe 2 O 4 additive of the doped sample with the best dehydrogenation performance is 3 mol %, and the LiAlH 4 +3 mol % NiFe 2 O 4 sample will be utilized for analyzing the catalytic effect and mechanism of NiFe 2 O 4 in the following tests. Although NiFe 2 O 4 nanopowder has exhibited superior catalytic performance by declining the onset dehydrogenation temperature of LiAlH 4 , the reversibility of the completely dehydrogenated 3 mol % doped sample cannot be tested at 140°C under 6.5 MPa hydrogen pressure, as shown in Figure S1 (Supporting Information), resulting from the thermodynamic properties of LiAlH 4 .…”

Section: Resultsmentioning

confidence: 99%

“…The first and the second exothermic peaks correspond to the interaction between LiAlH 4 and surface hydroxyl impurities 36 and the decomposition of liquid LiAlH 4 , respectively. Meanwhile, the two endothermic peaks reflect LiAlH 4 melting 36 and Li 3 AlH 6 decomposition, 17 respectively. As for the NiFe 2 O 4 -doped LiAlH 4 sample, the exo/endothermic reactions can be seen in Figure 3b.…”

Section: Resultsmentioning

confidence: 99%

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NiFe₂O₄ Nanoparticles Catalytic Effects of Improving LiAlH₄ Dehydrogenation Properties

Zhai

et al. 2013

J. Phys. Chem. C

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The effects of NiFe 2 O 4 nanoparticles addition on the dehydrogenation behavior of LiAlH 4 were investigated. The onset dehydrogenation temperature for LiAlH 4 +3 mol % NiFe 2 O 4 sample is 61°C, which decreased by 94°C compared with the as-received LiAlH 4 and released ∼7.2 wt % hydrogen when heated to 180°C. Isothermal desorption measurements show that the 3 mol % NiFe 2 O 4 -doped sample releases ∼7.0 wt % of hydrogen in 91 min at 120°C, which is 6.3 wt % higher than the as-received LiAlH 4 under the same conditions. Through calculating the apparent activation energy of the LiAlH 4 samples with and without NiFe 2 O 4 for the first two dehydrogenation stages, the E a of the LiAlH 4 +3 mol % NiFe 2 O 4 sample is 54.3 and 70.8 kJ/mol, resulting in 52.5 and 59% decrease, respectively, compared with the as-received LiAlH 4 . Analyzing the X-ray diffraction and Fourier transform infrared spectroscopy results, it is reasonable to believe that the remarkable improvement of dehydrogenation properties of NiFe 2 O 4 -doped LiAlH 4 results from the in situ formed LiFeO 2 and Al−Ni compounds, providing the active sites for nucleation and growth of the dehydrogenation products.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

NiFe₂O₄ Nanoparticles Catalytic Effects of Improving LiAlH₄ Dehydrogenation Properties

Zhai

et al. 2013

J. Phys. Chem. C

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“…Lithium aluminum hydride (LiAlH 4 ) has a high hydrogen storage capacity (10.5 wt % H 2 ) and an excellent performance of hydrogen desorption at low temperature; thus, it has received significant attention from researchers. LiAlH 4 decomposes through a two-step process into Al, LiH, and H 2 at T < 250 • C through the intermediate Li 3 AlH 6 , according to reaction scheme (3) [24][25][26][27][28][29].…”

Section: N + H 2 ↔ LI 2 Nh + Lih + H 2 ↔ Linh 2 + 2lihmentioning

confidence: 99%

Improved Dehydrogenation Properties of 2LiNH2-MgH2 by Doping with Li3AlH6

Qiu

Wang

et al. 2017

Metals

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Doping with additives in a Li-Mg-N-H system has been regarded as one of the most effective methods of improving hydrogen storage properties. In this paper, we prepared Li 3 AlH 6 and evaluated its effect on the dehydrogenation properties of 2LiNH 2 -MgH 2 . Our studies show that doping with Li 3 AlH 6 could effectively lower the dehydrogenation temperatures and increase the hydrogen content of 2LiNH 2 -MgH 2 . For example, 2LiNH 2 -MgH 2 -0.1Li 3 AlH 6 can desorb 6.43 wt % of hydrogen upon heating to 300 • C, with the onset dehydrogenation temperature at 78 • C. Isothermal dehydrogenation testing indicated that 2LiNH 2 -MgH 2 -0.1Li 3 AlH 6 had superior dehydrogenation kinetics at low temperature. Moreover, the release of byproduct NH 3 was successfully suppressed. Measurement of the thermal diffusivity suggests that the enhanced dehydrogenation properties may be ascribed to the fact that doping with Li 3 AlH 6 could improve the heat transfer for solid-solid reaction.

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“…[8,[12][13][14][15][16][17][18][19][20][21][22][23] For example, ball-milling LiAlH 4 with NiCl 2 was found to reduce the onset decomposition temperature by about 50…”

Section: Introductionmentioning

confidence: 99%

Decomposition mechanism and the effects of metal additives on the kinetics of lithium alanate

Hoang

Janotti

Walle

2012

Phys. Chem. Chem. Phys.

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First-principles density functional theory studies have been carried out for native defects and transition-metal (Ti and Ni) impurities in lithium alanate (LiAlH4), a potential material for hydrogen storage. On the basis of our detailed analysis of the structure, energetics, and migration of lithium-, aluminum-, and hydrogen-related defects, we propose a specific atomistic mechanism for the decomposition and dehydrogenation of LiAlH4 that involves mass transport mediated by native point defects. We also discuss how Ti and Ni impurities alter the Fermi-level position with respect to that in the undoped material, thus changing the concentration of charged defects that are responsible for mass transport. This mechanism provides an explanation for the experimentally observed lowering of the temperature for the onset of decomposition and of the activation energy for hydrogen desorption from LiAlH4.

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Effect of Ti-doping on the dehydrogenation kinetic parameters of lithium aluminum hydride

Cited by 66 publications

References 28 publications

NiFe₂O₄ Nanoparticles Catalytic Effects of Improving LiAlH₄ Dehydrogenation Properties

NiFe₂O₄ Nanoparticles Catalytic Effects of Improving LiAlH₄ Dehydrogenation Properties

Improved Dehydrogenation Properties of 2LiNH2-MgH2 by Doping with Li3AlH6

Decomposition mechanism and the effects of metal additives on the kinetics of lithium alanate

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Effect of Ti-doping on the dehydrogenation kinetic parameters of lithium aluminum hydride

Cited by 66 publications

References 28 publications

NiFe2O4 Nanoparticles Catalytic Effects of Improving LiAlH4 Dehydrogenation Properties

NiFe2O4 Nanoparticles Catalytic Effects of Improving LiAlH4 Dehydrogenation Properties

Improved Dehydrogenation Properties of 2LiNH2-MgH2 by Doping with Li3AlH6

Decomposition mechanism and the effects of metal additives on the kinetics of lithium alanate

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NiFe₂O₄ Nanoparticles Catalytic Effects of Improving LiAlH₄ Dehydrogenation Properties

NiFe₂O₄ Nanoparticles Catalytic Effects of Improving LiAlH₄ Dehydrogenation Properties