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 Ml0.80Mg0.20（Ni2.90Co0.50-Mn0.30Al0.30）x （x=0.68, 0.70, 0.72, 0.74, 0.76） alloys and Cu-substituted Ml0.80Mg0.20（Ni2.90Co0.50-yCuyMn0.30Al0.30）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. Ther-modynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with in-creasing 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 ame-liorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.
Yttrium （Y） has been used as the partial substitution element for lanthanum （La） to improve the electrochemical kinetic performances of La-Mg-Ni-based hydrogen storage alloys. Lao.80-xYxMg0.20Ni2.85Mn0.10Coo.55Al0.10 （x=0.00, 0.05 and 0.10） alloys were prepared by the inductive melting technique. The alloys were composed of LaNi5 and （La,Mg）2Ni7 phases, the introduction of Y promoted the formation of （La,Mg）2Ni7 phase, and thus the Y-substituted alloy electrodes exhibited higher discharge capacities. Y substitution was also found to be effective to improve the discharge kinetics of the alloy electrodes. When the Y content x increased from 0.00 to 0.10, the high-rate dischargeability of the alloy electrodes at a discharge current density of 1800 mA/g （HRDl800） in- creased from 23.6% to 39.7% at room temperature. In addition, the measured HRD1800 showed a linear dependence on both the ex- change current density and the hydrogen diffusion coefficient at different temperatures, respectively.
In this paper, the Co-free hydrogen storage alloys with the nominal compositions of La0.75R0.05Mg0.20Ni3.40Al0.10（R = La, Nd and Sm） were prepared by induction melting, and then the phase structure and electrochemical properties of these alloys were comparatively investigated. It is found that the alloys mainly consist of（La, Mg）2Ni7phase, La Ni5 phase and（La, Mg）5Ni19phase.Refinement results further show that Nd substitution for La remarkably promotes the formation of La Ni5 phase, while Sm is beneficial for the formation of（La, Mg）5Ni19phase.At discharge current density of 1,875 m A g-1, the highrate dischargeability（HRD） of alloy electrodes increases by 13.9 % and 6.5 % with La substituted by Nd and Sm,respectively. The electrochemical kinetic measurements reveal that the exchange current density（I0）, charge transfer resistance（R） and hydrogen diffusion coefficient（D） for the alloy electrode are all facilitated with Nd and Sm partial substitution for La. Subsequently, a linear correlation between the HRD1875 and the corresponding I0/D is found.
Zhi-Ping LiuShu-Qin YangYuan LiJing-Jing LiuMing-Zhen MaShu-Min Han
