Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
1272662 | International Journal of Hydrogen Energy | 2014 | 6 Pages |
•Reaction mechanisms of Mg3Ag and Mg3Y alloys were presented.•The Mg3Ag system was completely reversible.•Relationship between the thermodynamic stability and size interstice was investigated.•The destabilized effect of ΔS to the thermodynamic stability of Mg3Ag was proposed.
The hydrogenation/dehydrogenation characteristics and hydrogen storage properties of nominal Mg3Ag and Mg3Y alloys prepared by induction melting were investigated. The as-melted Mg3Ag alloy was composed of Mg54Ag17 phase, while Mg3Y consisted of Mg24Y5 and Mg2Y phases. Mg54Ag17 transformed into MgAg and MgH2 during the first hydrogenation, and the phase transition of the following hy/dehydrogenation cycles was Mg3Ag + 2H2 ↔ MgAg + 2MgH2. Both Mg24Y5 and Mg2Y undertook disproportion reactions and decomposed into MgH2 and YH3. Experimental and calculated results demonstrated that there was no necessary relation between the thermodynamic stabilities and the size interstices in these alloys. The dehydrogenation enthalpy change (ΔH) and entropy change (ΔS) of Mg3Ag were calculated and compared with that of pure Mg, which indicated that the increase of ΔS could counteract the stabilization effect of ΔH, which offered a method for tuning the thermodynamic properties of Mg-based alloys.