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In the present work, high energy ball milling of binary (Mg2Ni) and ternary powder mixtures (Mg1.75Nb0.25Ni and Mg2Ni0.75Nb0.25, i.e., substitution of Nb for Mg and Ni, respectively) was carried out. The effects of milling process parameters on the microstructure of binary and ternary milled products were studied. Also, electrochemical properties of the nano-structured electrodes made from the milled products were measured. It was found that Nb substitution for Mg (Mg1.75Nb0.25Ni) has beneficial effect on the formation kinetic of Mg2Ni-based nano-crystallites. Electrode made from the 20h milled product using initial composition of Mg1.75Nb0.25Ni exhibited a high discharge capacity of ~600mAhg-1 and relatively longer discharge life. Such electrode showed a microstructure consisting of an amorphous core surrounded by nano-crystallites.