Search

MgH2-based nanocomposites were synthesized by high-energy reactive ball milling (RBM) of Mg powder with 0.5–5 mol% of various catalytic additives (nano-Ti, nano-TiO2, and Ti4Fe2Ox suboxide powders) in hydrogen. The additives were shown to facilitate hydrogenation of magnesium during RBM and substantially improve its hydrogen absorption-desorption kinetics. X-ray diffraction analysis showed the formation of nanocrystalline MgH2 and hydrogenation of nano-Ti and Ti4Fe2Ox. The possible reduction of TiO2 during RBM in hydrogen was not observed, which is in agreement with lower hydrogenation capacity of the corresponding composite, 5.7 wt% for Mg + 5 mol% nano-TiO2 compared to 6.5 wt% for Mg + 5 mol% nano-Ti. Hydrogen desorption from the as-prepared composites was studied by Thermal Desorption Spectroscopy (TDS) in vacuum. A significant lowering of the hydrogen desorption temperature of MgH2 by 30–90 °C in the presence of the additives is associated with lowering activation energy from 146 kJ/mol for nanosized MgH2 down to 74 and 67 kJ/mol for MgH2 modified with nano-TiO2 and Ti4Fe2O0.3 additives, respectively. After hydrogen desorption at 300–350 °C, these materials are able to absorb hydrogen even at room temperature. It is shown that nano-structuring and addition of Ti-based catalysts do not decrease thermodynamic stability of MgH2. The thermodynamic parameters, obtained from hydrogen desorption isotherms for the Mg–Ti4Fe2O0.3 nanocomposite, ΔHdes = 76 kJ/mol H2 and ΔSdes = 138 J/K·mol H2, correspond to the reported literature values for pure polycrystalline MgH2. Hydrogen absorption-desorption characteristics of the composites with nano-Ti remain stable during at least 25 cycles, while a gradual decay of the reversible hydrogen capacity occurred in the case of TiO2 and Ti4Fe2Ox additives. Cycling stability of Mg/Ti4Fe2Ox was substantially improved by introduction of 3 wt% graphite into the composite.

Bimetallic Ni-Cu nanoparticles with different (Ni/Cu) ratio have been synthesized via fast and simple one-pot reducing Ni(OH)2/Cu(OH)2 pulp by hydrazine in water/ethylene glycol solutions. Using scanning electron microscopy (SEM), it was found that all obtained nanopowders are polydisperse with the particles sizes within 20–70 nm and the mean diameter of particles slightly depends on the Ni/Cu ratio. Using XRD phase-structural analysis, it was found that with increasing Cu amount in the initial mixture from 20 to 50%, the lattice parameter for Ni phase increases from 3.527 to 3.560 A but the lattice parameter of Cu changes more slightly (3.594 … 3.606 A). Besides, using precision EDX technique, it was found that obtained nanoparticles may be considered as a core–shell type in which a core consists of copper but a shell consists of a nickel-copper solution. Hydrogenation properties of obtained Ni-Cu nanoparticles have been studied, and it has been shown that the initial capacity of Ni-Cu-NPs depends on the specific surface area and compositions of the samples.

New R1-xR’xMgNi4-yCoy (R, R’ = Y, La, Ce; x = 0.5; y = 0, 1, 2) alloys have been synthesized by powder sintering method, and their crystal structure and hydrogen storage properties have been studied. X-ray diffraction analysis showed that R1-xR’xMgNi4-yCo alloys belong to the MgCu4Sn-type structure. The synthesized alloys absorb hydrogen at room temperature and hydrogen pressure 0.1-10 bar. For some of the studied compounds, the formation of hydrides with cubic and orthorhombic structures was found. Highest hydrogen content is found for the Co-rich compounds: La0.5Y0.5MgNi2Co2H5.18 and La0.5Ce0.5MgNi2Co2H6.48. Electrochemical studies showed that Y-based electrode materials exhibit better electrochemical performance comparing with Ce-doped ones. Highest discharge capacity of 292 mА∙h/g was observed for La0.5Y0.5MgNi3Co, but the best cyclic stability after 50th cycle of 92% was seen for La0.5Y0.5MgNi2Co2. Additionally, obtained results of the electrochemical properties were compared with related compounds. High rate dischargeability of Co-free alloys at I = 1 A/g were twice higher than ones containing cobalt.

Magnesium hydride (MgH2) is a hydrogen-rich compound generating significant amounts of hydrogen in the process of hydrolysis, i.e., in the course of its chemical interaction with water or with aqueous solutions. This process is of great interest for the on-site hydrogen generation aimed at application of H2 as a fuel for PEM fuel cells. We propose a review of recent reference publications in the field and also present the results of our own research. The increase of the rates of H2 release and the completeness of transformation of MgH2 are two important goals, which can be attained by optimizing the size of the powders of MgH2 by ball milling, by using catalysts added to MgH2 and to aqueous solutions, and by increasing the interaction temperature. The effect of these parameters on the degree of conversion and the rates of hydrogen evolution are analyzed in detail and the best systems to reach the efficient hydrolysis performance are identified. The mechanism of catalytic hydrolysis is proposed, while further improvements of the process of hydrolysis are required and additional studies of this important topic are needed.

Amorphous MgNi and MgNi0.5Co0.5 composites were prepared by mechanical ball grinding in an argon atmosphere. The electrodes made of these composites are characterized by high electrochemical discharge capacity: 872 mA · h/g for MgNi and 309 mA · h/g for MgNi0.5Co0.5. The cyclic stability (S30) of the MgNi0.5Co0.5 electrode (42%) is somewhat higher compared to MgNi (26%). Reduction in the capacity of electrodes is associated with bulk and corrosion processes. The MgNi0.5Co0.5 electrode increases its capacity to a greater extent than MgNi after deep discharge.

The influence of substitution Pr for La and Ni for Co on hydrogen storage properties of Pr1-xLaxMgNi4-yCoy (х = 0; 0.5, у = 0–3) alloys were studied. The existences of solid solutions have been found. It is shown that the synthesized alloys absorb hydrogen at room temperature and hydrogen pressure 0.1–10 bar. For some of the studied compounds, the formation of hydrides with cubic and orthorhombic structures was found. Hydrogen capacity for Pr1-xLaxMgNi4-yCoy alloys increases with Co content increasing and reaches 6.6 H/f.u. for PrMgNi2Co2. For electrochemical hydrogenation different trend was observed. With increasing of Co content discharge capacity slightly increases only to y = 0.5, and after y > 0.5, decreases. Highest discharge capacity is equal to 305 mА∙h/g for Pr0.5La0.5MgNi3.5Co0.5, and 268 mА∙h/g for PrMgNi3.5Co0.5 at current densities 50 mА/g and 200 mA/g, respectively. Influence of Co and number of activation cycles on HRD value of PrMgNi4-yCoy alloys was investigated. Additionally, obtained results of the electrochemical properties were compared with related compounds.

New La1-xNdxMgNi4-yCoy (x = 0, 0.5, 1; y = 0, 0.5, 1) alloys have been synthesized by powder sintering method, and their crystal structure and hydrogen storage properties have been systematically studied. X-ray diffraction analysis showed that La1-xNdxMgNi4-yCoy alloys belong to the MgCu4Sn-type structure. Hydrogen storage capacity of the alloys is in the 1.1–1.7 wt % H range. The alloy hydrides of are stable in air at room temperature. XRD studies have shown that hydrides retain the crystalline structure of the starting alloy while increasing the cellular volume by 15–23%. Pressure–composition–temperature (PСT) measurements demonstrated that thermodynamic stability of hydrides decreases with an increasing Nd content whereas increasing Co content in the alloys leads to the increase their stability which is demonstrated by the lowering desorption plateau pressure with Co content. Electrochemical studies showed that La-rich electrode materials exhibit the maximum discharge capacity (300–330 mAh/g), but Nd-doped ones show better cyclic stability.

The isothermal sections of the Nd–Mg–Co phase diagram at 300 and 500 °C have been constructed on the basis of X-ray diffraction (XRD), Wavelength Dispersive Spectrometry (WDS) and Electron Probe Micro Analyzer (EPMA) analysis. The existence of two ternary compounds Nd 4 Mg 3 Co 2 (own structure type) and Nd 4 MgCo (Gd 4 RhIn type) was confirmed. The latter has homogeneity range defined as Nd 4- x Mg 1+ x Co with 0 ≤ x ≤ 0.2 at 300 °С and 0 ≤ x ≤ 0.3 at 500 °С. Four new ternary compounds were identified in this work: Nd 23- x Mg 4+ x Co 7 (Pr 23 Mg 4 Ir 7 type; −1.5 ≤ x ≤ 0.1 at 300 °С and −0.6 ≤ x ≤ 0.3 at 500 °С); NdMg 2 Co 9 (YIn 2 Ni 9 type), ∼Nd 77 Mg 14 Co 9 (cubic) and ∼Nd 56 Mg 6 Co 38 (unknown crystal structure). Two binary compounds, NdCo 2 and NdCo 3 , were found to dissolve significant amount of Mg with the formation of substitutional solid solutions Nd 1- x Mg x Co 2 (MgCu 2 type; x ≤ 0.1 at 300 °С and x ≤ 0.15 at 500 °C) and Nd 1- x Mg x Co 3 (PuNi 3 type; x ≤ 0.33 at 300 °С and x ≤ 0.5 at 500 °C), respectively. The Nd 4 Mg 3 Co 2 , Nd 4- x Mg 1+ x Co, Nd 23- x Mg 4+ x Co 7 and Nd 1- x Mg x Co 2 compounds irreversibly absorb hydrogen at room temperature and pressure 1–10 bar to form crystalline or amorphous hydrides with hydrogen content 1.6–2.1 wt. %. Hydrogen thermal desorption from these hydrides in vacuum results in their disproportionation with formation of binary NdH 2 hydride. The Nd 1- x Mg x Co 3 (0 ≤ x ≤ 0.5) alloys reversibly absorb up to 1.3 wt. % of hydrogen. NdMg 2 Co 9 compound has small hydrogenation capacity, absorbing only 0.5 wt. % at room temperature and hydrogen pressure 185 bar.

New Nd 3− x Mg x Co 9 alloys have been synthesized by powder sintering method and their crystal structure, hydrogen storage and magnetic properties have been systematically studied. X-ray diffraction analysis showed that Nd 3− x Mg x Co 9 ( x ≤ 1.5) alloys belong to the PuNi 3 -type structure and NdMg 2 Co 9 is an individual ternary compound with YIn 2 Ni 9 -type structure. Hydrogen storage capacity of the PuNi 3 -type Nd 3− x Mg x Co 9 alloys is in the range 1.1–1.6 wt % H at room temperature, while for NdMg 2 Co 9 it is below 0.5 wt % H. PСT measurements demonstrated that thermodynamic stability of hydrides decrease with increasing Mg content. Hydrides of the alloys with lower Mg content ( x ≤ 1.0) are stable in air at room temperature. XRD study of these hydrides showed preserved PuNi 3 -type structure with hydrogen-induced volume expansion 16.7–24%. The positions of hydrogen atoms were determined by neutron powder diffraction study of Nd 2 MgCo 9 D 10 . In the Nd 2 MgCo 9 D 10 structure D atoms partially occupy four types of interstices, including octahedral Nd 2 Co 4 sites, tetrahedral Nd 2 Co 2 sites and two types of trigonal bipyramids (Nd,Mg) 3 Co 2 . Electrochemical investigations of the Nd 2 MgCo 9 electrode demonstrated rather low discharge capacity, 100 mAh/g, which is about 30% of its theoretical capacity. Magnetic measurements have shown that Nd 2 MgCo 9 is ferromagnetic with high Curie temperature (T C = 633 K) and spin reorientation at 225 K, its hydrogenation causes a significant decrease of the magnetization.

The structure of hydrogen sublattice of the Mg2NiH0.3 phase has been studied by computational methods to overcome some ambiguities of the experimental method. Seven types of possible hydrogen sites (marked as X1 to X7) were found. Models with occupation of X1 or X2+X3 sites were found in the literature. Further analysis of geometry and electronic density of the Mg2Ni compound revealed three additional types of voids X4-X6. Models having from 1 to 3 hydrogen atoms per unit cell were tested. The optimization of some of the models with occupied X2 and X5 sites led to shift of hydrogen atoms into the new type of voids X7. It was revealed that two the most energetically favorable ordered models have two types of tetrahedral sites occupied by hydrogen: X3 (H@Mg3Ni) and X7(H@Mg2Ni2). It was suggested that the real structure was a superposition of these models with either two X3 or both X3+X7 voids occupied. The developed structure is close to and has the advantage over one of the models mentioned in the literature, since the trigonal X2 site presented in the literature model is split here into two adjacent tetrahedral X7 sites.

The LaMgNi4–xCox (x = 0, 0.33, 0.67, 1) alloys are prepared by sintering and prolonged heat treatment at 500°C, with the main cubic phase of MgCu4Sn type. The alloy samples ball-milled in an argon atmosphere show the glass-forming ability. Electrochemical experiments of the LaMgNi4–xCox electrodes are performed at charge and discharge current densities of 100 mAh. The maximum discharge capacity is exhibited by the powdered alloys (218–302 mAh/g) compared to the ball-milled ones (92–134 mAh/g). The cobalt content of the LaMgNi4–xCox alloys influences the electrode characteristics. The highest discharge capacity is shown by the powdered alloy with x = 0.33. The ball-milled alloys have slightly higher cyclic stability.

Ni and Ni-Cu,Co nanopowders have been synthesized by chemical reduction method. It was demonstrated early that hydrogenation properties are critically dependent from the structure of the particles. Therefore the crystal structure of Ni-based nanopowders has been studied precisely by SEM, XRD and SAXS methods. X-ray diffraction and SEM analysis showed that the size of the obtained nickel nanoparticles covered the range from 20 to 200 nm. The particles consist from crystallites, which are characterized by the size about 5–20 nm. The complicated structure of the particles was confirmed by SAXS method.

The isothermal section of the Tb–Mg–Co phase diagram at 500 °C has been built on the basis of XRD analysis of forty samples prepared by powder metallurgy. The existence of two ternary compounds Tb4Mg3Co2 and Tb4MgCo was confirmed. The formation of two solid solutions, Tb1−xMgxCo3 (0≤x≤0.4) and Tb1-−xMgxCo2 (0≤x≤0.6), was found for the first time. It is shown that Tb5Mg24 also dissolves a small amount of Co. Other binary compounds do not dissolve the third component. The Tb4MgCo and TbMgCo4 compounds form hydrides (12.7 and 5.3 at.H/f.u. capacity, respectively) that retain the original structure of metallic matrices. Upon thermal desorption the Tb4MgCoH12.7 hydride was stable up to 300 °C and disproportionated at higher temperature. Two other hydrides, Tb4Mg3Co2H∼4 and Tb2MgCo9H12, are unstable in air and decompose into the initial compounds.

The hydrogen absorption properties of the R 4 MgCo compounds ( R =Y, La, Nd, Tb; str. type Gd 4 RhIn; sp.gr. F 4 ¯ 3 m ) have been studied for the first time. It was shown that their hydrogen storage capacity reaches about 2 wt%. At low pressure hydrogenation and moderately elevated temperatures the formed hydrides preserve the original structure of the metallic matrix. The crystal structure of the R 4 MgCoH x hydrides have been determined by XRD. Experimental hydrogen storage capacity (12 at.H/f.u. for Y 4 MgCo) is in good agreement with the theoretically calculated models, which allow also to estimate the distribution of H-atoms in metal lattice. TDS and DSC experiments demonstrated the multistep desorption process. XRD studies of the Tb 4 MgCoH x sample after TDS demonstrated the formation of TbH 2 as the main phase and disproportionation of the parent compound.

The influence of Co substitution on the structural and magnetic properties of NdMgNi 4− x Co x ( x ⩽ 3) alloys and their hydrides has been investigated. The formation of NdMgCo 4 compound has not been observed. The gas hydrogenation of these alloys resulted in the formation of NdMgNi 4 H 4 , NdMgNi 3 CoH 4.8 , NdMgNi 2 Co 2 H 5.6 and NdMgNiCo 3 H 6.2 hydrides. Transformation from cubic into orthorhombic structure upon hydrogenation has been confirmed for NdMgNi 4 H 4 hydride, whereas it has been found that Co-containing hydrides preserved the parent cubic structure. PC diagrams at 50 °C for NdMgNi 4− x Co x –H 2 ( x = 0, 2, 3) showed only one absorption/desorption plateau, which equilibrium pressure decrease as the cell volume increase. The NdMgCu 4 ternary compound has been synthesized, but it does not interact with hydrogen under normal conditions. Electrochemical investigations demonstrated that substitution of the nickel atoms by the cobalt ones in NdMgNi 4 does not significantly influence on the maximum discharge capacity (244–261 mA h/g) and all alloys are characterized by high cyclic stability. NdMgNi 4 and its hydride display a Pauli paramagnet behavior. NdMgNi 2 Co 2 displays a magnetic order below 50 K whereas its hydride shows a Pauli paramagnet behavior similar to that of NdMgNi 4 H 4 .