Electrochemical hydrogen storage characteristics of Mg1.5Al0.5-xZrxNi (x=0, 0.1, 0.2, 0.3, 0.4, 0.5) alloys synthesized by mechanical alloying


ANIK M., GAŞAN H., Topcu S., AKAY ERDOĞAN I., Aydinbeyli N.

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol.34, no.6, pp.2692-2700, 2009 (SCI-Expanded) identifier identifier

Abstract

Mg1.5Al0.5-xZrxNi (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) type alloys were synthesized by mechanical alloying and their electrochemical hydrogen storage characteristics were investigated. Xray diffraction studies showed that Zr facilitated the amorphization. Of Mg2Ni phase, while Al retarded the amorphization. of this phase. The increase in the Zr content was observed to bring about significant improvement in the discharge capacities at all the ball milling durations. The stepwise replacement of Al with Zr, however, caused considerable reduction in the initial discharge capacities of the alloys. Despite the adverse effect of Al on the initial discharge capacity, it prevented the rapid degradation of Mg2Ni phase with the charge/discharge cycles. When the beneficial effects of Zr and Al were combined by designing Mgl.sAlo.s-.Zr.Ni type alloys, Mg1.5Al0.2Zr0.3Ni alloy was found to have the highest discharge capacity at almost all the charge/discharge cycle steps. Among the obtained capacity retaining rates, Mg1.5Al0.4Zr0.1Ni alloy had the best performance. This alloy has kept at least 50% of its initial discharge capacity at 20th cycle. The analysis by the electrochemical impedance spectroscopy revealed that the charge transfer resistances of Al-rich alloys were low at high depth of discharges. This observation was attributed to the formation of the porous unstable Mg(OH)(2) layer due to the intercalation of Al2O3 layers, which have the high rate of solubility in strongly basic solutions, and thus the exposition of the underlying electrocatalytically active Ni sites. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.