Phase relations and hydrogenation behavior of Sr(Al1−xMgx)2

The phase relations and hydrogenation behavior of Sr(Al_1−xMg_x)₂ alloys were studied. The pseudobinary C36-type Laves phase Sr(Al,Mg)₂ was found as a structural intermediate between the Zintl phase and the C14 Laves phase. The single-phase regions for the Zintl phase, C36 phase and C14 phase, were determined to be x=0–0.10, 0.45–0.68 and 0.80–1, respectively. The Mg-substituted Zintl phase Sr(Al_0.95Mg_0.05)₂ can be hydrogenated to Sr(Al,Mg)₂H₂ at about 473 K. However, the Sr(Al,Mg)₂H₂ directly decomposes into SrH₂ and Sr(Al,Mg)₄ starting at 513 K. When the temperature is 573 K, the C36 Laves phase Sr(Al_0.5Mg_0.5)₂ can be hydrogenated into SrMgH₄ and Al, while the C14 Laves phase Sr(Al_0.1Mg_0.9)₂ is hydrogenated into SrMgH₄, Mg₁₇Al₁₂ and Mg.     

Effect of partial substitution of Co with Fe on the properties of LaNi3.55Mn0.4Al0.3Co0.75−xFex (x=0, 0.15, 0.55) alloys electrodes

The effect of iron substitution on the electrochemical behaviour of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x compounds (x=0, 0.15, 0.55) has been studied by chronopotentiometry and cyclic voltammetry techniques. The maximum capacity decreases linearly from 308 to 239 mAhg⁻¹ when the iron content increases from 0 to 7.3 wt.% (x=0.55). This decrease can be explained by the corrosion of the alloy in the aqueous KOH electrolyte. In spite of this decrease and of the long time needed for the activation, a good stability of discharge capacity was observed in LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x compounds. The reversibility of the electrochemical redox reaction of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x alloy electrodes has been observed in the alloys least rich in iron. The hydrogen diffusivity in LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x alloy electrodes decreases when increasing the iron content. The obtained values of the hydrogen diffusion coefficient D_H, varies between 2.1×10⁻⁷ and 8.2×10⁻⁹ cm² s⁻¹ depending on the iron content of the electrode.     

Structural and electrochemical properties of TixZr7−xNi10

Simple ternary alloys with formula Ti_xZr_7−xNi₁₀ (x between 0 and 2.5) were studied as a potential replacement for Laves phase alloys used in the negative electrodes of nickel metal hydride batteries. The samples were prepared by arc-melting and were not annealed. The samples retained a high degree of disorder, which contributed positively to activation and other electrochemical properties. Before hydrogenation, the alloys have a Zr₇Ni₁₀ orthorhombic structure mixed with some C15 and ZrO₂ secondary phases. The amount of C15 secondary phase is important to the bulk diffusion of hydrogen and the surface electrochemical kinetics. That is, the diffusion coefficient and the exchange current both increase in the presence of C15 secondary phase. The proportion of C15 secondary phase is controllable by stoichiometry design. For instance, a slightly higher Zr content reduces the C15 content. Further, as the titanium substitution level increases: (1) the lattice constants decrease; (2) the PCT plateau pressure increases; (3) activation becomes easier; and (4) the high rate dischargeability improves.     

Characterization and hydrogenation of CeNi5−xCrx (x = 0, 1, 2) alloys

The effect of partial substitution of Ni by Cr in CeNi₅ intermetallic compound has been studied by pressure–composition isotherm measurements for different temperatures. The samples were prepared of high purity materials using the standard arc melting technique in argon atmosphere. The structure and the elemental composition of different alloys have been investigated by means of XRD, SEM and EDX techniques. The unit cell volume of the alloy was found to increase with increasing Cr content. In order to calculate the hydrogen storage capacity pressure–composition isotherm has been investigated for CeNi_5−xCr_x (x = 1, 2) alloys in the temperature and pressure ranges of 293 ≤ T ≤ 333 K and 0.5 ≤ P ≤ 35 bar, respectively. The P–C–T isotherm for different alloys clearly shows the presence of three regions ,  + β and β. The enthalpy and entropy for the systems has also been calculated using Van’t Hoff plot. The variation of enthalpy and entropy with hydrogen content has also been studied.     

Structural and thermodynamic properties of the pseudo-binary TiCr2−xVx compounds with 0.0≤x≤1.2

The TiCr_2−xV_x compounds with 0.0≤x≤1.2 series have been synthesised and characterised by X-ray powder diffraction. X-Ray qualitative and quantitative phase analysis has been carried out on the as-cast alloys using the Rietveld method. The refinements of the structure shows that the materials crystallise either in the hexagonal or in the cubic Laves phase type for low V contents. For x>0.6, the system is found of b.c.c.-type structure only. The pressure–composition–temperature (P–C–T) isotherms measured at 298 K show that the as-cast alloys absorb large amounts of hydrogen, from 4 to 5.2 H/f.u. The P–C–T diagrams reveal also the presence of a relatively flat plateau, and a large hysterisis effect, and correspondingly the hydride cannot be completely dehydrogenated.     

Hydrogen sorption in transition metal modified NaETS-4

Transition metals nickel (Ni), rhodium (Rh) and palladium (Pd) both exchanged and in situ loaded in NaETS-4 samples were synthesized and characterized. Hydrogen adsorption studies in the synthesized NaETS-4 samples were performed at 77.4 K up to 1 bar and at 303 K up to 40 bar pressure. The reversible adsorption isotherms at 77.4 K showed physisorption of hydrogen but at 303 K chemisorption was the major mechanism for hydrogen uptake, which is clear from the irreversible nature of adsorption isotherms at 303 K. Rhodium loaded NaETS-4 showed the highest hydrogen adsorption capacity of 66 cc/g at 77.4 K and 35 cc/g at 303 K. The hydrogen adsorption in transition metal modified NaETS-4 at 303 K is driven by the chemical interactions leading to the formation of transition metal hydrides inside the micropores of NaETS-4. The absorbed hydrogen at 303 K can be desorbed by heating the modified titanosilicates up to 423 K.     

Hydrogen absorption properties of the slurry system composed of liquid C6H6 and F-treated Mg2Ni

The hydrogenation characteristics of the slurry composed of the NH₄F solution treated Mg₂Ni and liquid C₆H₆ were studied. The F-treatment results in a net-shaped MgF₂ surface and higher nickel content in the sub-layer. It is found that the hydride of the NH₄F treated alloy has a much higher activity for the hydrogenation of benzene. The catalytic activity for hydrogenation of the alloy depended strongly on the surface properties of the catalyst. At 483 K and under a hydrogen pressure of 4.0 MPa, the alloy absorbed hydrogen first, transformed into hydride and then the benzene was hydrogenated to cyclohexane with the hydride as the catalyst. The hydrogen absorption capacity of slurry system composed of 20 wt.% treated alloy and benzene reached 6.4 wt.% and the hydrogenation completed in 20 min. Results of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis on the crystal structure, surface composition and surface morphology of the untreated and treated alloy are presented and discussed.     

Rate determining step in the absorption and desorption of hydrogen by magnesium

The kinetics of hydrogen absorption and desorption by magnesium has been investigated by a volumetric technique. Experimental data have been analysed in order to find the rate determining step for both the absorption and desorption processes. It is shown that a nucleation and growth (NG) mechanism, with exponent values n=2 for desorption and n=0.5 to n=l for absorption provides suitable equations in order to fit the experimental data. The influence of hydrogen pressure and temperature on the process rate has been studied to obtain an expression for the driving force of the reaction and its activation energy. The driving force for desorption seems to follow a parabolic law though the experimental data are also compatible with a linear law. According to our data, the rate determining step in the desorption of hydrogen by magnesium, and probably also in the absorption process, seems to be the hydrogen diffusion through the β phase. An activation energy for such a diffusion process of 100±10 kJ mol⁻¹H has been obtained from the desorption data.     

Microwave-assisted synthesis and characterization of Nd1.5Mg17Ni0.5-Fe3O4 hydrogen storage composite

This work reports the preparation of Nd_1.5Mg₁₇Ni_0.5-Fe₃O₄ hydrogen storage composite in a single mode 2.45 GHz microwave cavity. The physicochemical properties (thermodynamic and kinetic characteristics, hydrogen absorption/desorption properties, thermal behavior, phase composition and morphology) were characterized by pressure-composition isotherms, differential scanning calorimetry, X-ray diffraction, scanning electron microscope with an energy dispersive X-ray spectrometer, transmission electron microscopy, and laser granulometry. The proposed microwave synthesis, in contrast with conventional sintering method, offers rapid heating, makes homogenous composition and hence improves the hydrogen storage properties of the composite.     

Modification of the hydrogenation properties of LaNi5 upon Ni substitution by Rh, Ir, Pt or Au

The hydrogenation properties of the LaNi_5−xM_x (M = Rh, Ir, Au) compounds have been studied. The Ni substitution has several consequences: pressure plateau splitting and increase of plateau pressure. This latter observation disagrees with the general rule that a cell volume increase of the alloy should result in a plateau pressure lowering. In order to elucidate the origin of this anomalous behaviour, DFT calculations have been performed on both LaNi_5−xRh_x and LaNi_5−xPt_x intermetallic compounds, which, according to the present and previous experimental work, present a similar anomaly. We discuss our results in light of the models proposed in the literature. We conclude that, in the case of a Ni substitution by 4d or 5d elements, the size effect alone fails in predicting the hydrogen absorption properties while the rule of reverse stability is obeyed.     

Investigation of hydrogen discharging and recharging processes of Ti-doped NaAlH4 by X-ray diffraction analysis (XRD) and solid-state NMR spectroscopy

The processes occurring in the course of two sequential hydrogen discharging and recharging cycles of Ti-doped sodium alanate were investigated in parallel using XRD analysis and solid-state NMR spectroscopy. Both methods demonstrate that in hydrogen storage cycles (Eq. (1)) the majority phases involved are NaAlH₄, Na₃AlH₆, Al and NaH. Only traces of other, as yet unidentified phases are observed, one of which has been tentatively assigned to an Al–Ti alloy on the basis of XRD analysis. The unsatisfactory hydrogen storage capacities heretofore observed in cycle tests are shown to be due entirely to the reaction of Na₃AlH₆ with Al and hydrogen to NaAlH₄ (Eq. (1), 2nd hydrogenation step) being incomplete. Using XRD and NMR methods it has been shown that a higher level of rehydrogenation can be achieved by adding an excess of Al powder.     

Hydrogen redistribution in the solid solutions ZrV2Dx, 2.2≤x≤2.7.: II. Structure of the intermediate phase: ‘Lattice liquid crystal’. A neutron-diffraction study

We have studied the crystal structure of the uncommon phase with k=0 in ZrV₂D_x, 2.2<x<2.5, which is an intermediate between the hydrogen-disordered phase and two hydrogen superstructures, ZrV₂D_<2 with k=(1/2 1/2 1/2) and ZrV₂D_>2.7 with k=(001). This phase is a primary superstructure combining the features of the disordered phase and, depending on the hydrogen concentration, one or another superstructure with k≠0. Its lattice (translational symmetry) is the same as in the disordered phase, which is k=0. Simultaneously, the lattice sites (the hydrogen arrangement in them) are prototypes of the sites of the subsequent superstructure with k≠0. Specifically, each site of the primary superstructure with k=0 is a mix of the sites with different spatial orientation of the superstructure with k≠0. In this sense the primary superstructure can be considered as a ‘lattice liquid crystal’ whereas usual superstructure with k≠0 is a ‘lattice crystal’. In addition, we have determined the crystal structure of the ‘ordered’ phase with k=(001) in ZrV₂D_2.73. It is a transitional state between the primary superstructure and the regular superstructure with the same k.     

Hydrogen redistribution in the solid solutions ZrV2Dx, 2.2≤x≤2.7: I. Interconnection between hydrogen-ordered phases: intermediate phase instead of phase separation

We have studied, by means of neutron powder diffraction, the temperature evolution of the hydrogen solid solutions ZrV₂D_x in the intermediate range, 2.18≤x≤2.73, separating two hydrogen-ordered phases, ZrV₂D_≤2 with k=(1/2, 1/2, 1/2) and ZrV₂D_≥2.8 with k=(0, 0, 1−δ). Instead of ordinary phase separation, we have found an uncommon phase. This phase is a kind of a disordered one and, simultaneously, it keeps a modulation of hydrogen density with the same k as for the ordered phase, one or another. Under favourable conditions this modulation transforms into the regular ordered phase.     

Influence of hydrogenation on structure and magnetic properties of HoFe11−xCoxTi

Magnetic properties and crystal structure of the hydrides of ferromagnetic compounds HoFe_11−xCo_xTi (x = 1, 2, 4, 6, 7, 11) are investigated. The crystal structure was determined by X-ray diffraction (XRD) analysis and the magnetization was measured in applied magnetic fields up to 10 T and at temperatures ranging from 5 K to room temperature. Results show that the crystal structure of the hydrides is the same as for parent compounds but with a moderate unit cell increase. Other properties such as saturation magnetization are affected by H insertion within the lattice. The effect of hydrogenation on magnetic anisotropy energy leads to disappearance of the FOMPs observed in the parent compounds.     

Hydrogen storage properties of melt-spun LaNi4.25Al0.75

Rapidly solidified LaNi_4.25Al_0.75 alloy was prepared by melt spinning and its hydrogen storage properties were examined. The hydrogen storage capacities and the equilibrium pressures of the unannealed melt-spun (UMS) LaNi_4.25Al_0.75 alloy were found to be nearly identical to those of the annealed induction-melt (AIM) alloy. However, the resistance to pulverization was greatly improved and the hysteresis was markedly decreased for the UMS alloy, while its activation became rather difficult.     

Self-ignition combustion synthesis of TiFe in hydrogen atmosphere

This paper describes the self-ignition combustion synthesis (SICS) of highly active titanium iron (TiFe) in a high-pressure hydrogen atmosphere without employing an activation process. In the experiments, well-mixed powders of Ti and Fe in the molar ratio of 1:1 were uniformly heated up to 1085 °C, the eutectic temperature of Ti–Fe binary system, in pressurized hydrogen at 0.9 MPa. The electric source was disconnected immediately after the ignition between Ti and Fe, and the mixture was cooled naturally. In this study, the exothermic reaction Ti + Fe = TiFe + 40 kJ occurred at around 1085 °C after the hydrogenation and decomposition of Ti. X-ray diffraction analysis showed that the final product had only one phase—TiFeH_0.06—which can store hydrogen of 1.55 mass% under hydrogen pressure of 4 MPa. The product obtained by SICS contained considerably more hydrogen quickly as compared to the commercially available product; this fact can be explained by the porous structure of the obtained product, which was observed using a scanning electron microscope. In conclusion, the SICS of TiFe saved time and energy, yields products with high porosity and small crystals, enabled easy hydrogenation, and did not require activation processes.     

Cobalt-free over-stoichiometric Laves phase alloys for Ni–MH batteries

The charge–discharge cycling behavior of the over-stoichiometric Laves phase alloy Zr_0.75Ti_0.25V_0.9Mn_0.4Cr_0.3Ni_1.4 as hydride electrode has been studied in a negative electrode-limited sealed cell. This cobalt-free alloy shows a maximum discharge capacity C_max=373 mAh g⁻¹ at 160 mA g⁻¹ discharge current and a high rate dischargeability of 285 mAh g⁻¹ at 1500 mA g⁻¹ discharge rate. After 600 cycles the discharge capacity is 81% of the C_max; the alloy also shows good charging efficiency (98%) and low temperature discharge rate.     

Interaction of hydrogen with the LaNi4.9In0.1, LaNi4.8In0.2 and LaNi4.8 alloys and their Nd analogues

The single phase nature of the alloys LaNi_4.9In_0.1, LaNi_4.8In_0.2, NdNi_4.9In_0.1, NdNi_4.8In_0.2 of the systems LaNi_5−xIn_x and NdNi_5−xIn_x was confirmed by means of X-ray powder diffractometry. Nonstoichiometric alloys LaNi_4.8 and NdNi_4.8 were prepared and were also found to be good single phase materials. All these alloys crystallize with the same hexagonal structure of the CaCu₅ type (space group P6/mmm) as do their prototypes LaNi₅ and NdNi₅. In order to determine the interaction with hydrogen the alloys were exposed to hydrogen gas and the pressure composition desorption isotherms were measured. It was found that all alloys react readily and reversibly absorb large amounts of up to 6.54 hydrogen atoms per alloy formula unit. Generally the equilibrium pressure and the hydrogen capacity decrease with the decreasing nickel content. Presence of indium in the alloy acts in favour of these trends. Furthermore, the increasing content of indium in the alloy system drastically alters the slope and the pressure of the plateau observed at higher pressure of the two isotherm plateaux of the NdNi₅–hydrogen system. The final result is a merge of both plateaux into a single one for the hydrogen desorption isotherms of NdNi_4.8In_0.2. However, the isotherms of nonstoichiometric NdNi_4.8 still exhibit two separated pressure plateau regions. The thermodynamic parameters of hydride formation, i.e., the entropy change, the enthalpy and the Gibbs free energy of formation have also been extracted for all alloy–hydrogen systems.     

Structural, electrical and magnetic properties of Cu1−xZnxFe2O4 ferrites (0 ≤ x ≤ 1)

Copper–zinc ferrites bearing chemical formula Cu_1−xZn_xFe₂O₄ for x ranging from 0.0 to 1.0 with the step increment of 0.2 were prepared by the standard solid-state technique. The variation of Zn substitution has a significant effect on the structural, electrical and magnetic properties. Lattice parameters ‘a’ increased from 8.370 to 8.520 Å. Dielectric constant decreased up to 311 with the increase in frequency from 80 Hz to 1 MHz at room temperature. All the samples follow the Maxwell–Wagner's interfacial polarization. Saturation magnetization, magnetic moment and Yafet–Kittel angles were also determined. The possible reasons responsible for the change in density related, electrical and magnetic properties with the increase in Zn concentration are undertaken.     

Nanocrystalline LaNi4−xMn0.75Al0.25Cox electrode materials prepared by mechanical alloying (0≤x≤1.0)

Polycrystalline hydrogen storage alloys based on lanthanum (La) are commercially used as negative electrode materials for the nickel–metal hydride (Ni–MH_x) batteries. In this paper, mechanical alloying (MA) was used to synthesize nanocrystalline LaNi_4−xMn_0.75Al_0.25Co_x (x=0, 0.25, 0.5, 0.75 and 1.0) hydrogen storage materials. XRD analysis showed that, after 30 h milling, the starting mixture of the elements decomposed into an amorphous phase. Following the annealing in high purity argon at 700 °C for 0.5 h, XRD confirmed the formation of the CaCu₅-type structures with a crystallite sizes of about 25 nm. The nanocrystalline materials were used as negative electrodes for a Ni–MH_x battery. Cobalt substituting nickel in LaNi₄Mn_0.75Al_0.25 greatly improved the discharge capacity and cycle life of the LaNi₅ material. For example, in the nanocrystalline LaNi_3.75Mn_0.75Al_0.25Co_0.25 powder, discharge capacities up to 258 mA h g⁻¹ (at 40 mA g⁻¹ discharge current) were measured. Mechanical alloying is a suitable procedure to obtain LaNi₅-type alloy powders for electrochemical energy storage.