H2 absorption and desorption reactions in MgH2 promoted by ball-milling with 1 mol% MgNb2O6, Mg 4Nb2O9 and Mg3Nb6O 11 have been investigated. MgH2 was milled with the bare oxides for 12 h under a high purity Ar atmosphere. Absorption and desorption reactions in the ball-milled samples were studied by in situ X-ray diffraction (XRD) in isothermal conditions with Anton Paar XRK 900 reaction chamber. XRD patterns for absorption were recorded at 573 K under hydrogen pressure of 0.9 MPa and for desorption at 623 K in vacuum. Experimental data were analysed according to the Rietveld method. Ball-milled samples showed the presence of a mixture of β and γ allotropes of MgH2, with significantly broadened diffraction peaks due to reduced crystallite size and strain, together with bare additives. The presence of Mg-Nb oxides significantly accelerates the hydrogen absorption and desorption processes. The amount of hydrogen absorbed in the presence of Mg-Nb-O phases is lower than the maximum stoichiometric capacity, because of the presence of a non-reactive MgO layer on the surface of the powders or at the grain boundaries. Experimental results are discussed on the basis of thermodynamic and kinetic arguments. © 2011 Elsevier B.V. All rights reserved.
Effect of Mg-Nb Oxides Addition on Kinetics of Hydrogen Storage in MgH2
CASTELLERO, Alberto;LIVRAGHI, Stefano;GIAMELLO, Elio;BARICCO, Marcello
2011-01-01
Abstract
H2 absorption and desorption reactions in MgH2 promoted by ball-milling with 1 mol% MgNb2O6, Mg 4Nb2O9 and Mg3Nb6O 11 have been investigated. MgH2 was milled with the bare oxides for 12 h under a high purity Ar atmosphere. Absorption and desorption reactions in the ball-milled samples were studied by in situ X-ray diffraction (XRD) in isothermal conditions with Anton Paar XRK 900 reaction chamber. XRD patterns for absorption were recorded at 573 K under hydrogen pressure of 0.9 MPa and for desorption at 623 K in vacuum. Experimental data were analysed according to the Rietveld method. Ball-milled samples showed the presence of a mixture of β and γ allotropes of MgH2, with significantly broadened diffraction peaks due to reduced crystallite size and strain, together with bare additives. The presence of Mg-Nb oxides significantly accelerates the hydrogen absorption and desorption processes. The amount of hydrogen absorbed in the presence of Mg-Nb-O phases is lower than the maximum stoichiometric capacity, because of the presence of a non-reactive MgO layer on the surface of the powders or at the grain boundaries. Experimental results are discussed on the basis of thermodynamic and kinetic arguments. © 2011 Elsevier B.V. All rights reserved.
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