In-situ hydrogen-induced evolution and de-/hydrogenation behaviors of the Mg93Cu7-xYx alloys with equalized LPSO and eutectic structure

Nanosizing is efficient as the dual-tuning of thermodynamics and kinetics for Mg-based hydrogen storage materials. The in-situ synthesis of nanocomposites through hydrogen-induced decomposition from long-period stacking ordered phase is proved effective to achieve active nano-sized catalysts with uniform dispersion. In this study, the Mg₉₃Cu_7-xY_x (x = 0.67, 1.33, and 2) alloys with equalized Mg–Mg₂Cu eutectic and 14H long-period stacking ordered phase of Mg₉₂Cu_3.5Y_4.5 are prepared. Its solidification path is determined as α-Mg, 14H–Mg₂Cu pair and Mg–Mg₂Cu eutectic. The increased Y/Cu atomic ratio lowers the first-cycle hydrogenation rate of the alloys due to the increased 14H–Mg₂Cu structure and reduced Mg–Mg₂Cu eutectic interfaces. After the hydrogen-induced decomposition of the long-period stacking ordered phase, MgCu₂ and YH₃ nanoparticles are in-situ formed, and the following activation process significantly accelerates. The YH₃ nanoparticles partly decompose to YH₂ at 300 °C in vacuum and Mg–Mg₂Cu-YH_x nanocomposites are in-situ formed. The nano-sized YH₂ helps catalyze H₂ dissociation and the YH_x/Mg interfaces stimulate H diffusion and the nucleation of MgH₂. Therefore, the Mg₉₃Cu₅Y₂ composite shows the fastest absorption rates. However, due to the positive effect of YH_x/Mg interfaces on H diffusion and the negative effect of YH₃ nanophases on the hydride decomposition, the minimum activation energy of 115.43 kJ mol⁻¹ is obtained for the desorption of the Mg₉₃Cu_5.67Y_1.33 hydride.     

Solid solubility of Mg in Ca2Ni7 and hydrogen storage properties of (Ca2−xMgx)Ni7 alloys

The phase relations and hydrogen storage properties of the (Ca_2−xMg_x)Ni₇ alloys were investigated. It was found that the maximum solid solubility of Mg in the (Ca,Mg)₂Ni₇ phase is about x = 0.5 in the present study. The ‘inter-block-layer’ type stacking faults exist in the (Ca,Mg)₂Ni₇ phase when Mg content is very low. However, the density of stacking faults decreases and the lattice parameters reduce as Mg content increases to its maximum solid solubility. Thus the (Ca_1.5Mg_0.5)Ni₇ alloy has a good reversibility of hydrogen absorption–desorption.     

Tuning the de/hydriding thermodynamics and kinetics of Mg by mechanical alloying with Sn and Zn

Mg₉₅Sn₃Zn₂ alloy was prepared by mechanical alloying. The phase constituents and phase transition were analyzed by X-ray diffraction (XRD) method. The microstructure was characterized by scanning electron microscope (SEM). The hydrogen storage properties were evaluated in detail by the measurements of isothermal hydrogen absorption and desorption, and pressure-composition isotherms (PCI) using the Sieverts method. The addition of Zn benefits to extend the solubility of Sn in the Mg lattice, as a result supersaturated Mg(Sn, Zn) ternary solid solution was synthesized by mechanical alloying, which decomposed to MgH₂, Sn and MgZn₂ in the hydrogenating process. The in situ formed nanostructure Mg₂Sn and MgZn₂ have positive effects on the hydrogen absorption and desorption of Mg. Mg₉₅Sn₃Zn₂ alloy showed significantly improved kinetics with lowered hydrogen absorption and desorption activation energies of 38.1 kJ/mol and 86.6 kJ/mol respectively, and exhibited a reduced dehydriding enthalpy of 67.0 ± 1.9 kJ/(mol·H₂).     

Dual-tuning of de/hydrogenation kinetic properties of Mg-based hydrogen storage alloy by building a Ni-/Co-multi-platform collaborative system

The Mg-based hydrogen storage alloy with multiple platforms is successfully prepared by ball milling Co powder and Mg-RE-Ni precursor alloy, and its hydrogen storage behavior was investigated in detail by XRD, EDS, TEM, PCI, and DSC methods. The ball-milled alloy consists of the main phase Mg, the catalytic phases Mg₂Ni, Mg₂Co as well as a small amount of Mg₁₂Ce, and convert into the MgH₂–CeH_2.73-Mg₂NiH₄–Mg₂CoH₅ composite after hydrogenation. The composite has three PCI platforms corresponding to the reversible de/hydrogenation reaction of Mg/MgH₂, Mg₂Ni/Mg₂NiH₄ and Mg₆Co₂H₁₁/Mg₂CoH₅. Among them, the transformation between Mg₂Ni and Mg₂NiH₄ triggers the “spill-over” effect which promote the decomposition of MgH₂ phases and enhances the hydrogen desorption kinetics. Meanwhile, the conversion of the Mg₆Co₂H₁₁ to Mg₂CoH₅ phase induces the “chain reaction” effect, which leads to preferential nucleation of Mg phase and improves the hydrogen absorption kinetics. Therefore, the Mg-RE-Ni-Co alloy has a double improvement on hydrogen absorption and desorption kinetics. Concretely, the alloy has an optimal hydrogen absorption temperature of 200 °C, at which it can absorb 5.5 wt. % H₂ within 40 s. Under the conditions, the capacity of absorption almost reaches the maximum reversible value (about 5.6 wt. %). Besides, the alloy has a dehydrogenation activation energy of 67.9 kJ/mol and can desorb 5.0 wt. % H₂ within 60 min at the temperature of 260 °C.     

Hydrogen storage behavior of Mg/Ni layered nanostructured composite materials produced by accumulative fold-forging

An advanced and newly developed severe plastic deformation (SPD) method called accumulative fold-forging (AFF) was applied to produce layered nanostructured MgNi alloys exhibiting superior hydrogen storage capacity. Microstructural developments and storage properties were characterized in depth to correlate the structure and performance of this advanced material. The enhanced hydrogen storage performance of the magnesium-based layered composite material was investigated in comparison to the pristine state by conducting hydrogenation and dehydrogenation testing. It was also shown that the hydrogen uptake and release characteristics can be controlled by adjusting the layered structure or the Mg: Ni stoichiometry ratio. Refining the grain structure of the magnesium alloy down to the nano-scale range (～400–900 nm) by applying high cycles AFF consolidation to promote creation of multi-million nanometric interfaces led to superior storage performance with a remarkable hydrogen absorption capacity of up to ～1.425 wt%. X-ray diffraction (XRD) analysis of the hydrogenated products revealed the formation of MgH₂ that indicates the dominance of the magnesium matrix for controlling the hydrogen storage behavior of the layered Mg/Ni composite material. Finally, the relationship between the directional hydrogen storage behavior and the induced structural features upon AFF treatment were also established using quantitative characterization and analytical tools.     

Improvement in the hydrogen storage properties of Mg by mechanical grinding with Ni, Fe and V under H2 atmosphere

Mg-5wt%Ni-2.5wt%Fe-2.5wt%V (named Mg-5Ni-2.5Fe-2.5V) powder was prepared by reactive mechanical grinding using a planetary ball mill. The activation process, the changes in phase and microstructure with hydriding-dehydriding cycling, and the variations in the hydriding and dehydriding rates with temperature were investigated. The rate-controlling step for the dehydriding reaction of Mg-5Ni-2.5Fe-2.5V was analyzed by using a spherical moving boundary model. As the temperature increased from 473 K through 623 K, the initial hydrogen absorption rate under 12 bar H₂ decreased, while the hydrogen desorption rate under 1.0 bar H₂ increased.     

Synthesis of Mg2FeH6 by hydrogenation of Mg/Fe powder mixture prepared by cold roll milling in air: Effects of microstructure and oxygen distribution

Herein, we describe the synthesis of Mg₂FeH₆ by hydrogenation of a 2.1 Mg:Fe (mol/mol) powder mixture prepared by cold roll milling (CRM) in air. The thickness of Fe layers and the amount and distribution of oxygen with number of CRM passes were systematically analyzed. CRM-induced microstructural changes were shown to play an important role in Mg₂FeH₆ formation. Although repeated CRM effectively decreased the Fe layer thickness to values sufficient for the fast formation of Mg₂FeH₆, too much CRM passes decreased the total degree of hydrogenation due to inevitable oxidation of Mg in air. Both microstructure refinement and minimal oxidation are the prerequisites for efficient Mg₂FeH₆ synthesis, with the former condition being achievable by optimizing the number of milling passes, and the latter one requiring CRM under an inert atmosphere.