Improvement of the electrochemical hydrogen storage performance of Mg2Ni by the partial replacements of Mg by Al, Ti and Zr

Mg₂Ni, Mg_1.5Al_0.5Ni, Mg_1.5Zr_0.5Ni, Mg_1.5Ti_0.5Ni, Mg_1.5Zr_0.25Al_0.25Ni, Mg_1.5Zr_0.25Ti_0.25Ni and Mg_1.5Ti_0.25Al_0.25Ni alloys were synthesized by mechanical alloying and their electrochemical hydrogen storage characteristics were investigated. X-ray diffraction studies showed that while Al was retarding, Zr and Ti were facilitating the amorphization of Mg₂Ni phase. The initial discharge capacities of Mg_1.5Ti_0.5Ni, Mg_1.5Zr_0.5Ni and Mg_1.5Al_0.5Ni alloys were 414, 322 and 166 mA h g⁻¹, respectively. Although Mg_1.5Al_0.5Ni alloy had very low initial discharge capacity, the capacity retaining rate of this alloy was much better than those of Ti- and Zr-including alloys. The potentiodyanamic polarization experiments in 6 M KOH solution presented that Mg was passive and Ni was immune in the charge/discharge potential range (−1.0 V_Hg/HgO and −0.5 V_Hg/HgO). At the same conditions Ti and Zr had moderate, and Al had extremely higher dissolution rates. The analysis by the electrochemical impedance spectroscopy revealed that the increase in the charge transfer resistance of Mg_1.5Al_0.5Ni alloy was relatively low with the increase in depth of discharge. This observation was attributed to the formation of the porous unstable Mg(OH)₂ layer due to the high rate dissolution of the disseminated Al₂O₃ and thus the exposition of the underlying electro-catalytically active Ni sites. The charge transfer resistance of Mg_1.5Ti_0.5Ni alloy increased sharply with the increase in depth of discharge possibly due to the stabilizing effect of Ti-oxide on Mg(OH)₂. The presence of Ti-oxide, however, was predicted to make Mg(OH)₂ barrier layer more penetrable by hydrogen atoms, since the increased stability of the surface layer the cyclic stability of Mg_1.5Ti_0.5Ni alloy was relatively satisfactory.