Abstract

The influence of MgCo on the reaction paths during hydriding and dehydriding processes of Mg–Co mixtures was studied using a combined HP-DSC and XRD approach. Mg–Co mixtures with different compositions were mechanically milled under argon to prepare Mg–Co nanocomposites and then submitted to thermal treatment at 300 °C for 5 days to induce MgCo formation. The local Mg–Co composition in the milled and milled-heated samples determines the nature of the phases obtained after hydriding/dehydriding cycling. The formation of Mg 6Co 2H 11, Mg 2CoH 5 and MgH 2 hydrides occurs after the first hydriding stage of the 2Mg–Co and Mg–Co milled mixtures due to kinetic restrictions. On the contrary, Mg–Co milled-heated mixture exhibits the selective formation of Mg 2CoH 5 during first hydriding via two-step reaction. In the first one, MgCo disproportion to MgH 2 and Co takes place simultaneously with Mg hydriding (<200 °C). The second step involves MgCo hydriding to Mg 2CoH 5 through MgH 2 as intermediate phase (>200 °C). Dehydriding reaction is enhanced by dispersion of Co into Mg-matrix, which reduces more than 100 °C the hydrogen desorption temperature when compared with the Mg–Co milled sample without previous heating.

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