Effect of stoichiometry and Cu-substitution on the phase structure and hydrogen storage properties of Ml-Mg-Ni-based alloys

Abstract

To improve the electrochemical properties of rare-earth-Mg-Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the alloys were studied. Nonsubstituted Ml_0.80Mg_0.20(Ni_2.90Co_0.50-Mn_0.30Al_0.30) _x (x = 0.68, 0.70, 0.72, 0.74, 0.76) alloys and Cu-substituted Ml_0.80Mg_0.20(Ni_2.90Co_0.50−yCu _yMn_0.30Al_0.30)_0.70 (y = 0, 0.10, 0.30, 0.50) alloys were prepared by induction melting. Phase structure analysis shows that the nonsubstituted alloys consist of a LaNi₅ phase, a LaNi₃ phase, and a minor La₂Ni₇ phase; in addition, in the case of Cu-substitution, the Nd₂Ni₇ phase appears and the LaNi₃ phase vanishes. Thermodynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with increasing stoichiometry and increasing Cu content. The maximum discharge capacity, kinetic properties, and cycling stability of the alloy electrodes all increase and then decrease with increasing stoichiometry or increasing Cu content. Furthermore, Cu substitution for Co ameliorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.

Keywords

hydrogen storage alloys / electrode materials / stoichiometry / substitution / phase structure / thermodynamic properties / electrochemical properties

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