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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.

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.

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.

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 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 .

The advantages of reactive ball grinding for preparation of new efficient Mg-based hydrogen storage materials are discussed. Magnesium-based nanocomposites were synthesized with additions of η-Zr4Fe2O0.5 intermetallic compound, which is characterized by enhanced resistance to disproportionation in hydrogen and can prolong the cyclic life of materials. The improvement of hydrogen absorption parameters for Mg–intermetallic composites was observed. It was shown that fourfold increase in the reaction rate during mechanochemical synthesis of MgH2 and decrease in hydrogen desorption temperature by 80°C were induced by catalytic additions.

New two ternary YMgCo4 and YMgCu4 and one quaternary YMgCo2Ni2 compounds have been synthesized by mechanical alloying with further annealing. The hydrogenation capacity of YMgCo4 reaches 6.8 at. H/f.u. The Pressure-Composition-Temperature studies of YMgCo4–H2 and YMgNi4–H2 systems revealed that introduction of magnesium, accompanied by shrinking of the unit cell, decreases the stability of hydrides comparing to binary YCo2 and YNi2 compounds. The values of heat and entropy of the YMgCo4H6.8 hydride formation were calculated: ΔH = −27.9 ± 0.8 kJ mol–1 H2 and ΔS = −93.4 ± 2.6 J mol−1 H2 K−1. The YMgCo2Ni2–H2 system shows intermediate thermodynamic properties compared to the ternary hydrides (ΔH = −28.8 ± 0.2 kJ mol–1 H2 and ΔS = −117.6 ± 2.4 J mol–1 H2 K−1). The YMgCo4H6.8 and YMgCo2Ni2H4.9 hydrides keep the cubic structure of the parent compounds with a cell volume expansion of 23 and 14.4% respectively. It is shown that the YMgCu4 compound does not interact with hydrogen under normal conditions.

Two new ternary intermetallic compounds, CeMgCo4 (C15b pseudo-Laves phase, MgCu4Sn type) and Ce2MgCo9 (substitution derivative of PuNi3 type) were synthesized by mechanical alloying method. The structural and hydrogenation properties of these compounds were studied by X-ray diffraction and Pressure–Composition–Temperature measurements. Both compounds absorb hydrogen at room temperature and pressures below 10 MPa forming hydrides with maximum compositions CeMgCo4H6 and Ce2MgCo9H12. Single plateau behavior was observed in P–C isotherm during hydrogen absorption/desorption by Ce2MgCo9 alloy. The CeMgCo4–H2 system is characterized by the presence of two absorption/desorption plateaus corresponding to formation of β-CeMgCo4H4 and γ-CeMgCo4H6 hydride phases. The structure of β-hydride CeMgCo4H(D)4 was determined from X-ray and neutron powder diffraction data. In this structure initial cubic symmetry of CeMgCo4 is preserved and hydrogen atoms fill only one type of interstitial sites, triangular MgCo2 faces. These positions are occupied by 70% and form octahedron around Mg atom with Mg–D bond distances 1.84 Å.

New ternary Mg–Mn–Ni alloys synthesised by high energy ball milling have been studied as hydrogen storage materials. A new Mg 3 MnNi 2 ternary intermetallic compound of the Ti 2 Ni type has been identified, its structure was studied by neutron diffraction. It has been shown that in the Mg–Mn–Ni system this intermetallic coexists with Mg, forming two-phase Mg–Mg 3 MnNi 2 alloys. The Mg 3 MnNi 2 compound reversibly absorbs about 1 wt.% of hydrogen already at room temperature and forms interstitial type Mg 3 MnNi 2 H ∼3 hydride. Substantially higher hydrogenation capacity has been observed in Mg–Mg 3 MnNi 2 alloys with high Mg content, e.g. 5.4 wt.% for the Mg 88 Mn 4 Ni 8 alloy at 250–350 °C. Hydrogen absorption–desorption kinetics of these alloys are drastically improved compared to undoped magnesium due to catalytic effect of the Mg 3 MnNi 2 phase.

The Zr 9 V 4 SH ∼23 hydride was synthesized by saturation from gaseous hydrogen at room temperature and 0.12 MPa hydrogen pressure. The measured hydrogen absorption capacity of the κ -Zr 9 V 4 S was 1.77 H/M. The refinement of the hydride structure with the use of X-ray powder diffraction data confirmed the preserved symmetry of the metallic matrix (sp.gr. P 6 3 / mmc , a = 9.2715 ( 2 ) , c = 9.0756 ( 4 ) A , Δ a / a = 7.3 % , Δ c / c = 6.1 % , Δ V / V = 22.1 % , Δ V / at.H = 2.62 A 3 ). The analysis of interstices in this compound revealed that without positioning hydrogen atoms in triangular Zr 3 interstices it is impossible to model the structure of k -hydride with the experimentally observed capacity. Neutron powder diffraction study of the Zr 9 V 4 SD ∼23 deuteride (sp.gr. P 6 3 / m m c , a = 9.2779 ( 5 ) , c = 9.0779 ( 5 ) A) revealed deuterium atoms filling two tetrahedral and three triangular interstices. A full occupancy of only one site (D4) was observed in our sample giving the refined deuterium content of 20.8(2) D/f.u. Filling of the D4 site causes a displacement of the sulphur atoms from the three-fold axis (splitting of 2c to 6h position).

This work was focused on the studies of vanadium-based “low-temperature” bcc alloys as H storage materials. Both as cast and annealed at 1100 ° C quaternary alloys V92.5−x−yZr7.5Ti7.5+x−yMy (M = Cr, Mn, Fe, Co, Ni; x = 0 , 10; y = 0 , 7.5) were studied. They were characterised by XRD, PCT hydrogen absorption–desorption measurements ( T = 30 –120 ° C) and thermal desorption spectroscopy studies of H desorption from the saturated hydrides ( T = − 100 to 800 ° C). The thermodynamics of the VH∼2↔ VH∼1 transition and hydrogen sorption capacities ( 1.55 , … , 1.80 H/M) were found to be significantly influenced by the substituting M-element. The reversible hydrogen storage capacity ( T 100 ° C, P > 0.1 bar) reaches 50–60% of its overall value. Complete hydrogen desorption proceeds in vacuum at T 300 ° C. The major future challenge of the work is in increasing of the easy-reversible part of the H storage capacity corresponding to transformation VH∼2↔ VH∼1 by reducing the content of H in the monohydride.

Hydrogenation of RECu2 (RE=Dy, Ho, Y) at room temperature and pressures of 100–1500-bar H2 has not resulted in the formation of ternary hydrides. The interaction of hydrogen with Pr(Cu1−xNix)2 (x=0, 0.1, 0.17, 0.25, 0.32) at room temperature and pressure of 25 bar resulted in the formation of Pr(Cu1−xNix)2H∼3 hydrides. It was found that the PrCu2H3 and Pr(Cu0.9Ni0.1)2H2.9 hydrides are poorly crystallized, but that an increase of the Ni-content leads to improved crystallinity of the hydrides. The hydrides Pr(Cu0.75Ni0.25)2H∼3 and Pr(Cu0.68Ni0.32)2H∼3 preserve, shortly after the hydrogen absorption, the CeCu2 type structure of their metallic matrix with a hydrogen induced volume expansion up to 28% compared to the parent compound. During long-term exposure in the air they undergo a structural transformation from the orthorhombic CeCu2 to the hexagonal Fe2P type with a hydrogen induced volume expansion up to 16.6% compared to the parent compound.

Crystal chemistry aspects of hydrogen behaviour in the zirconium–iron intermetallic deuterides (hydrides), Zr2FeD1.80–5.00, Zr3FeD1.27–6.70 and Zr4Fe2O0.6H7.80, were studied with a focus on the application of high resolution powder neutron diffraction. The effects of crystal structure, chemical composition of the metal matrices, temperature and hydrogen contents on preferences in the interstices occupation and H ordering were investigated and discussed in relation to the H absorption–desorption properties. The Hydrogenation–Disproportionation–Desorption–Recombination process was successfully applied to all materials studied, including the first reported example of an oxygen-containing compound, Zr4Fe2O0.6.

Experimental studies on the series of ternary intermetallic compounds, Zr6MeX2, where Me=Fe, Co, and Ni, and X=Al, Ga, and Sn, show that they have large hydrogen storage capacities ranging from 9.3 to 10.8 H-atoms per formula unit. The crystal structure of the parent intermetallic compounds changes upon hydrogenation with a two-fold increase of the crystallographic c-axis length and a corresponding change in space group from P 6 m2 to P 6 2c . Full profile (Rietveld) refinement using X-ray powder diffraction data indicates that the crystal structures of the new hydrides, Zr6CoAl2H10, Zr6NiAl2H9.7 and Zr6NiSn2H10.8 are analogous to Zr6FeAl2D10, which was examined by neutron powder diffraction. Thermal desorption of hydrogen in all hydrides occurs in the temperature range between 400 and 900 K and is characterized by two similar events. The compounds Zr6FeAl2Hx (x=0, 10 and 0.1–0.2) order magnetically at 45, 155 and 10 K, respectively. Electronic structure calculations are carried out on Zr6FeAl2Hx (0≤x≤10) to interpret their structural and thermal behavior. Site energies for hydrogen incorporation, energetics of hydrogen desorption, as well as quantitative details of the densities of states are evaluated. Site energies and metal–metal bonding largely affect the maximum hydrogen content, while H–H repulsions constitute the greatest driving force for the change in space group upon hydrogenation.

Hydrogen absorption properties of ZrVO alloys where some of the Zr or V is substituted by Ti, Hf, or Nb, Fe, respectively have been investigated. Phase structural characteristics of these alloys and their hydrides have been determined by X-ray powder diffraction. The interdependence of obtained crystallographic and hydrogenation characteristics has been discussed.

The effect of Cu-for-Ni substitution on the structural and hydrogenation properties of the LaCu2 compound with hexagonal AlB2 type structure has been studied. An extended solid solution was found from LaCu2 to La(Cu0.35Ni0.65)2. The La(Cu1−xNix)2 compounds easily absorb hydrogen at room temperature under 1 bar pressure, after preliminary activation treatment by heating in vacuum. Hydrogenation of LaCu2 resulted in the formation of amorphous LaCu2H3.3 hydride. For all Ni-substituted compounds formation of crystalline hydrides with CeCu2 or AlB2 type structure of the metallic sublattice and hydrogen content up to 4.4 at.H/f.u was observed. As found, long-term exposure of the La(Cu0.4Ni0.6)2H4.2 and La(Cu0.35Ni0.65)2H4.0 hydrides to the air or their heating under vacuum up to 100 °C is accompanied by structural transition of the metallic sublattice to Fe2P type structure, previously observed for Pr(Cu,Ni)2-based hydrides.

It is shown that the oxygen-stabilised compounds Zr3Fe(Co)Ox (x = 0–1.0) interact with hydrogen at ambient temperature and pressure forming saturated hydrides with filled Re 3B type structure. The hydrogen storage capacity decreases with increasing oxygen content from 6.7 H/f.u. for Zr3Fe down to 5.35 H/f.u. for Zr3FeO1.0 and from 6.9 H/f.u. for Zr3Co down to 5.3 H/f.u. for Zr3CoO1.0. A small change of the unit cell volumes for the Zr3Fe(Co)Ox parent compounds and a substantial increase of these parameters for the corresponding saturated hydrides were observed with increasing oxygen content. The partial hydrogen-induced lattice expansion, � V/at. H, increases from 2.25 A 3 for Zr3FeH6.7 up to 3.38 A 3 for Zr3FeO1.0H5.35 and from 2.08 A 3 for Zr3CoH6.9 up to 3.25 A 3 for Zr3CoO1.0H5.3. Rietveld refinement using neutron powder diffraction data for Zr 3FeO0.4D6.25 showed a distribution of deuterium atoms and a redistribution of oxygen atoms from octahedral to tetrahedral sites in a similar way as in Zr3NiOxDy. Both 57 Fe Mossbauer spectroscopy and magnetic susceptibility measurements of Fe-containing hydrides indicated weak hydrogen-induced magnetic ordering at low temperatures. The ordering temperatures of Zr3FeO0.2H6.52 and Zr3FeO0.6H6.25 are 105 and 140 K, respectively. © 2004 Elsevier B.V. All rights reserved.

Zirconium-based Zr-V and Zr-Fe alloys are known to be highly efficient absorbers of low pressure hydrogen. Their working performance is structure-dependent and can be improved by modifying the composition of the basic alloys with doping elements. Particularly promising in this respect are modifications of oxide materials where both H-sorption capacity and hydrogenation activity can be increased substantially, especially when boron or rare earth oxides are introduced into the matrices of Zr-V and Zr-V-Fe[1–3].