Synergetic effect of C (graphite) and Nb2O5 on the H2 sorption properties of the Mg-MgH2 system

Ternary Mg–Nb2O5 – graphitic C mixtures (molar ratio % = 97.5:0.5:2.0) were prepared by high-energy ball milling (BM) under Ar for different times (from 0.25 h to 4 h) and thoroughly characterized by manometric, calorimetric, X-ray powder diffraction, and scanning electron microscopy analyses. The aims of the work were: - to assess the effect of the simultaneous presence of the two dopants on the reactivity and the sorption properties of the Mg–MgH2 system; - to study the influence of the milling time on the performance of the mixtures. Neither milling nor the high temperature/high pressure treatments led to reactions among the components of the mixtures, and Mg was the only hydrogen active phase. After 4 activation cycles at 623 K and 35 bar/1 bar charging/discharging pressure, the mixture milled for 1 h was the best performing one: it reversibly charged up to 6.8 wt% H2 with absorption/desorption rates 64/4.5 times higher than those of a pure Mg sample BM for the same time and activation energies 3.6/2 times lower. The desorption temperature and the dehydrogenation enthalpy of the ternary mixture were respectively 40 K and 4 kJ/mol H2 lower than those of pure MgH2

Effect of C (graphite) doping on the H2 sorption performance of the Mg – Ni storage system.

Binary Mg – Ni mixtures and ternary Mg – Ni – C (graphite) samples with fixed proportions of metals (Mg 85 %: Ni 15 % by weight) and amount of C increasing in increments of 5 wt % from 5 wt % to 15 wt % were prepared by high energy ball milling (BM) in Ar for tBM = 2 h. The purpose of the study was to evaluate the effect of C addition on the reactivity, the sorption activation and the storage performance of the Mg - Ni system. Increasing the amount of C had the effect of decreasing (from 10 to 3) the number of cycles needed for activation (performed at 623 K and 40 bar/0.9 bar charging/discharging H2 pressure). After full activation, the 5 wt % C-containing sample exhibited the best absorption kinetics performance: the average rate to charge up to 5 wt % H2 was about 3 times higher than that observed for the undoped sample. Unfortunately, increasing the amount of C had a negative impact on the desorption behaviour, causing an increase in the dehydrogenation activation energy and a decrease in the discharging rates. Within the present study, C reacted neither with H2 nor with the H2 active phases (the two discharged phases Mg and Mg2Ni and the related hydrides) and consequently did not lead to variation in the sorption enthalpies of the Mg-Ni system. But, its presence did cause a small increase (4 K at 0.9 bar H2) in the minimum desorption temperatures of the hydrides and a consequent minor decrease (0.2 bar) in the equilibrium pressures. The best sorption properties were obtained for the 5 wt % C-sample, that on the whole worked better than the binary mixture