Crystal structure and hydrogen absorption− desorption property of La5Co19

An intermetallic compound, La₅Co₁₉ is synthesized successfully for hydrogen storage, and its crystal structure is determined by X-ray diffraction. The alloy is formed by annealing the precursor at 1073 K for 10 h, and it has a Ce₅Co₁₉-type structure (space group R-3m, 3R) with a = 0.5130(1) nm and c = 4.882(1) nm. Its maximum hydrogen capacity reaches 0.92 H/M, but 0.40 H/M of hydrogen remains in the sample after the first desorption. Its reversible hydrogen capacity is 0.51 H/M. The formed hydride phases, phase I (La₅Co₁₉H₁₀) and phase II (La₅Co₁₉H₂₂) also have the Ce₅Co₁₉-type crystal structure; the hydride phases retain the same metal sublattice as that of the original alloy. Phase I is formed through anisotropic expansion of the La₅Co₁₉ lattice, while the unit cell, the MgZn₂-type and CaCu₅-type cells, of phase II is formed by the isotropic expansion of the La₅Co₁₉ lattice.     

Crystal structure and cyclic properties of hydrogen absorption–desorption in Pr2MgNi9

We investigated the crystal structure and cyclic hydrogen absorption–desorption properties of Pr₂MgNi₉. The structural model is based on the PuNi₃-type structure; the Mg atom is assumed to substitute for the Pr site in an MgZn₂-type cell. The refined lattice parameters were determined from X-ray diffraction. A wide plateau region was observed in the P–C (pressure composition) isotherm at 298 K. The maximum hydrogen capacity reached 1.12 H/M (1.62 mass%) under a hydrogen pressure of 2.0 MPa. After 1000 hydrogen absorption–desorption cycles, the hydrogen capacity was superior to that of LaNi₅ (82%). Anisotropic lattice strain occurred in the hydriding process. The anisotropic peak-broadening vector was determined to be <001>. The calculated anisotropic lattice strains of the initial cycle and after 1000 cycles were far smaller than those of LaNi₅.     

Effects of B addition on the hydrogen absorption–desorption property of Ti0.32Cr0.43V0.25 alloy

The effects of boron addition on the hydrogen absorption–desorption properties of the _{Ti0.32Cr0.43V0.25}${\mathrm{Ti}}_{0.32}{\mathrm{Cr}}_{0.43}{\mathrm{V}}_{0.25}$ alloy were studied. Boron was added either directly or indirectly through a mother alloy _Ti0.75B0.25${\mathrm{Ti}}_{0.75}{\mathrm{B}}_{0.25}$. Direct boron addition caused the decrease in the titanium content of the BCC matrix through formation of Ti–B phases, resulting in the decrease in the lattice constant. Conversely, mother alloy addition increased the titanium content and the lattice constant of the matrix, for it contained enough titanium to contribute to the matrix even after forming the second phase TiB. Such lattice constant changes caused by boron addition resulted in drastic changes in hydrogen plateau pressure and great decrease in effective hydrogen storage capacity.     

Local and crystal structure of Mg1.9Al0.1Ni hydrogen storage alloys during hydrogen absorption–desorption cycling

The evolution of crystal structure and chemical state of Mg_1.9Al_0.1Ni alloy during hydrogen absorption–desorption cycling was examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). We research the hydrogen storage capacity of the Mg_1.9Al_0.1Ni by the H/D kinetic curves. The H/D kinetic curves indicate that the hydrogen storage capacity increased with the increased cycles and the samples were activated after 10 cycles have the maximum hydrogen storage capacity. The local structure of Ni atoms was studied by extended X-ray absorption fine structure (EXAFS). The EXAFS results indicate the Ni–Ni bonds distance has no obviously change with the cycles increasing, whereas the Ni–Mg bond lengths increase, and the Ni–Mg bond lengths are longer obviously than before 10 cycles whereas it has no obviously change after 10 cycles.     

Ameliorated microstructure and hydrogen absorption/desorption properties of novel Mg–Ni–La alloy doped with MWCNTs and Co nanoparticles

Based on the positive influence of carbon materials and transition metals, a new type of Mg-based composites with particle size of ～800 nm has been designed by doping hydrogenated Mg–Ni–La alloy with multi-walled carbon nanotubes (MWCNTs) and/or Co nanoparticles. The microstructures, temperature related hydrogen absorption/desorption kinetics and dehydrogenation mechanisms are investigated in detail. The results demonstrate that MWCNTs and Co dispersedly distribute on the surface of Mg–Ni–La particles after high-energy ball milling due to powders’ repeated cold welding and tearing. The experimental samples exhibit improved hydrogen storage behaviors and the addition of MWCNTs and Co can further accelerate the de-/hydriding kinetics. For instance, the Mg–Ni–La–Co sample can absorb 3.63 wt% H₂ within 40 min at 343 K. Dehydrogenation analyses demonstrate that the positive effect of MWCNTs is more obvious than that of Co nanoparticles for the experimental samples. The addition of MWCNTs and Co leads to the average dehydrogenation activation energy of experimental samples decreasing to 82.1 and 84.5 kJ mol^?1, respectively, indicating a significant decrease of dehydrogenation energy barriers. In addition, analyses of dehydrogenation mechanisms indicate that the rate-limiting steps vary with the addition of MWCTNs and Co nanoparticles.     

Microstructures and hydrogen absorption–desorption behavior of an A2B7-based La-Mg-Ni alloy

The microstructural changes during hydrogen absorption–desorption cycles of an A₂B₇-based La-Mg-Ni alloy with a nominal composition of La_1.5Mg_0.5Ni_7.0 were systematically investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The ternary La-Mg-Ni alloy was mostly composed of 2H-A₂B₇ phase with minor inclusions of 3R-A₅B₁₉, 2H-A₅B₁₉ and 3R-AB₃ phases existing as parts of intergrowth structures with the major A₂B₇ phase. Most parts of the major 2H-A₂B₇ phase containing Mg exhibited an excellent crystal structure retention after the hydrogen absorption–desorption cycles at 80 °C. Two types of defected bands were found to develop after the first hydrogen absorption–desorption cycle. The first ones are amorphous bands developed inside the minor 3R-AB₃ phase, while the second ones develop as heterogeneously strained regions inside the major 2H-A₂B₇ phase. Both the defected bands are considered to be responsible for the irreversible hydrogen capacity of the A₂B₇-based La_1.5Mg_0.5Ni_7.0 alloy during the hydrogen absorption–desorption cycles at 80 °C.     

Development of hydrogen absorption–desorption experimental test bench for hydrogen storage material

A volumetric experimental set-up used for measuring hydrogen absorption–desorption characteristics of hydrogen storage material will be presented. Although the experimental set-up is mainly employed to do hydrogen absorption–desorption cycling (including pressure cycling and thermal cycling) measurement automatically, it also can incidentally provide general measurements such as pressure-composition-temperature (P–C–T) curves and kinetics measurements in manual way in the ranges of 0.004–12 MPa and 213–773 K. The experimental set-up can be used to investigate the influence of hydrogen absorption–desorption cycles to hydrogen storage properties of material. The leakage rate of the whole experimental set-up was evaluated systemically. The usability and reliability of the experimental set-up were checked with LaNi₅ and Pd/K (kieselguhr).     

Effect of La–Mg-based alloy addition on structure and electrochemical characteristics of Ti0.10 Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy

Effect of La–Mg-based alloy (AB₅) addition on Structure and electrochemical characteristics of Ti_0.10Zr_0.15V_0.35Cr_0.10Ni_0.30 hydrogen storage alloy has been investigated systematically. XRD shows that the matrix phase structure is not changed after adding AB₅ alloy, however, the amount of the secondary phase increases with increasing AB₅ alloy content. The electrochemical measurements show that the plateau pressure Ti_0.10Zr_0.15V_0.35Cr_0.10Ni_0.30 + x% La_0.85Mg_0.25Ni_4.5Co_0.35Al_0.15 (x = 0, 1, 5, 10, 20) hydrogen storage alloys increase with increasing x, and the width of the pressure plateau first increases when x increases from 0 to 5 and then decreases as x increases further, and the maximum discharge capacity changes in the same trend. The activation performance, the low temperature dischargeabilities, high-rate dischargeability and cyclic stability of composite alloy electrodes increase greatly with increasing x. The improvement of the electrochemical characteristics caused by adding AB₅ alloy seems to be related to formation of the secondary phase.     

Electrochemical hydrogen storage of ball-milled MmMg12 alloy–Ni composites

MmMg₁₂–Ni amorphous or nanocrystalline composites (Mm: Ce-rich mischmetal) were prepared through the ball-milling method, and their electrochemical hydrogen storage performance was investigated and compared with that of ball-milled CeMg₁₂–Ni composites. It was found that the ball-milled MmMg₁₂–Ni composites had larger initial discharge capacities and better high rate dischargeability. Analysis of electrochemical impedance spectra (EIS) shows that the reaction resistance and hydrogen diffusion resistance of the ball-milled MmMg₁₂–Ni composites are lower as a result of the decrease in Ce content, and thus can contribute to the larger discharge capacity and better high rate dischargeability. Additionally, the cycle performance of the ball-milled MmMg₁₂–Ni composites is better than those of the ball-milled CeMg₁₂–Ni composites. This may be related to the formation of a Nd oxide or Nd(OH)₃ film on surface of the MmMg₁₂ alloys.     

Nanostructured rapidly solidified LaMg11Ni alloy. II. In situ synchrotron X-ray diffraction studies of hydrogen absorption–desorption behaviours

Recently, the present authors [17] have reported dramatic improvements in the hydrogenation behaviours of nanostructured LaMg₁₁Ni prepared by Rapid Solidification, caused by modifications of the microstructure and crystal structure. The aim of the present work was to study the mechanism and kinetics of the hydrogen interaction with rapidly solidified LaMg₁₁Ni by employing in situ synchrotron X-Ray diffraction studies of hydrogen absorption–desorption processes in hydrogen gas or in vacuum.     

Improving the hydrogen absorption properties of commercial Mg–Zn–Zr alloy

Commercial alloy ZK60 (Mg-6 wt%Zn-0.8 wt% Zr) was used as a hydrogen-storage material to study the effect of cold rolling, ball milling, and plus graphite additives on hydrogen-storage characteristics, hydrogen absorption–desorption behavior, and the related microstructural change of the alloy. Experimental results showed that cold-rolled alloy could not be activated easily. Even after ball milling for 20 h and hydrogen absorption–desorption cycling for 10 times, no saturated hydrogen absorption was observed for cold-rolled alloy. In contrast, alloys with 5 wt% graphite additives could be easily activated after the first hydrogen absorption–desorption cycle, and a saturated hydrogen absorption of 6.9 wt% was obtained after absorption–desorption cycling for five times. A hydrogen absorption of 5.52 wt%, equivalent to 80% of the saturated absorption amount, was measured in 5 min, showing a hydrogen absorption rate of 1.104 wt%/min. The sample reached saturation in 30 min.     

A comparative study for synthesis methods of nano-structured (9Ni–2Mg–Y) alloy catalysts and effect of the produced alloy on hydrogen desorption properties of MgH2

9Ni–2Mg–Y alloy powders were prepared by arc melting, induction melting, mechanical alloying, solid state reaction and subsequent ball milling processes. The results showed that melting processes are not suitable for preparation of 9Ni–2Mg–Y alloy due to high losses of Mg and Y. Therefore, 9Ni–2Mg–Y alloy powder was prepared by three methods including: 1) mechanical alloying, 2) mechanical alloying + solid state reaction + ball milling, and 3) mixing + solid state reaction + ball milling. The prepared 9Ni–2Mg–Y alloy powders were compared for their catalytic effects on hydrogen desorption of MgH₂. It is found that 9Ni–2Mg–Y alloy powder prepared by mechanical alloying + solid state reaction + ball milling method has a smaller particle size (1–5 μm) and higher surface area (1.7 m² g⁻¹) than that of other methods. H₂ desorption tests revealed that addition of 9Ni–2Mg–Y alloy prepared by mechanical alloying + solid state reaction + ball milling to MgH₂ decreases the hydrogen desorption temperature of MgH₂ from 425 to 210 °C and improves the hydrogen desorption capacity from 0 to 3.5 wt.% at 350 °C during 8 min.     

Hydrogen desorption/absorption properties of the extensively cold rolled β Ti–40Nb alloy

β Ti–Nb BCC alloys are potential materials for hydrogen storage in the solid state. Since these alloys present exceptional formability, they can be processed by extensive cold rolling (ECR), which can improve hydrogen sorption properties. This work investigated the effects of ECR accomplished under an inert atmosphere on H₂ sorption properties of the arc melted and rapidly solidified β Ti40Nb alloy. Samples were crushed in a rolling mill producing slightly deformed pieces within the millimeter range size, which were processed by ECR with 40 or 80 passes. Part of undeformed fragments was used for comparison purposes. All samples were characterized by scanning electron microscopy, x-ray diffractometry, energy-dispersive spectroscopy, hydrogen volumetry, and differential scanning calorimetry. After ECR, samples deformed with 40 passes were formed by thick sheets, while several thin layers composed the specimens after 80 passages. Furthermore, deformation of β Ti–40Nb alloys synthesized samples containing a high density of crystalline defects, cracks, and stored strain energy that increased with the deformation amount and proportionally helped to overcome the diffusion's control mechanisms, thus improving kinetic behaviors at low temperature. Such an improvement was also correlated to the synergetic effect of resulting features after deformation and thickness of stacked layers in the different deformation conditions. At the room temperature, samples deformed with 80 passes absorbed ∼2.0 wt% of H₂ after 15 min, while samples deformed with 40 passes absorbed ∼1.8 wt% during 2 h, excellent results if compared with undeformed samples hydrogenated at 300 °C that acquired a capacity of ∼1.7 wt% after 2 h. The hydrogen desorption evolved in the same way as for absorption regarding the deformation amount, which also influenced desorption temperatures that were reduced from ∼270 °C, observed for the undeformed and samples deformed with 40 passes, to ∼220 °C, for specimens rolled with 80 passes. No significant loss in hydrogen capacity was observed in the cold rolled samples.     

Mechanical property and hydrogen permeability of ultrafine-grained Pd–Ag alloy processed by high-pressure torsion

A process of high-pressure torsion (HPT) was used to produce an ultrafine-grained Pd–Ag alloy, and to improve mechanical property and hydrogen permeability simultaneously. Hardness values of the HPT-processed sample were much higher than those of a cold-rolled sample which is strengthened by dislocation accumulation. Additionally, in contrast to the degradation of hydrogen permeability in the cold-rolled sample due to a high density of dislocations which act as trapping sites of hydrogen atoms, the hydrogen permeability in the HPT-processed sample was improved due to a high density of high-angle grain boundaries which act as a fast diffusion path. The ultrafine-grained structure in the Pd–Ag alloy was retained during permeation testing at 300 °C due to the addition of silver.     

Energetics and diffusion of hydrogen in hydrogen permeation barrier of α-Al2O3/FeAl with two different interfaces

To provide insights into the interface structure of hydrogen permeation barrier of α-Al₂O₃/FeAl and its effect on stability and diffusion of hydrogen isotopes, the thermodynamics and kinetics of H diffusion in α-Al₂O₃ (001)/FeAl (111) slab with Al/O and Al/Fe/O interfaces have been studied by the density functional theory. Hexagonal alumina layers above the FeAl plane in interface region are predicted. The interfacial binding involves cation–anion and metal–metal interactions. H-surface interaction on the α-Al₂O₃/FeAl slab resembles that on pure α-Al₂O₃ (001) slab, and the H interstitials in the α-Al₂O₃ part of the slab with the Al/O interface are significantly less stable than in bulk of α-Al₂O₃ slab, whereas that with the Al/Fe/O interface are slightly more stable. H diffusion into the α-Al₂O₃ part of both slabs must overcome a larger barrier of about 1.66–2.02 eV at surface-to-subsurface step, as pure α-Al₂O₃ case. For the bulk path, the migration of H atom can occur more readily in the α-Al₂O₃ part of the slab with the Al/O interface compared to that with the Al/Fe/O interface. Thus α-Al₂O₃/FeAl barrier with interface region of the Al, Fe mix-oxide is predicted to be much effective at protection against H permeation of the underlying steel.     

Hydrogen absorption and desorption kinetics of Ag–Mg–Ni alloys

The hydrogen absorption/desorption (A/D) kinetics of hydrogen storage alloys Mg_2−xAg_xNi (x=0.05, 0.1) prepared by hydriding combustion synthesis in two-phase (α–β) region in the temperature range of 523–$\text{573}\text{K}$ have been investigated. The hydriding/dehydriding (H/D) reaction rate constants were extracted from the time-dependent A/D curves. The obtained hydrogen A/D kinetic curves were fitted using various rate equations to reveal the mechanism of the H/D processes. The relationships of rate constant with temperature were established. It was found that the three-dimensional diffusion process dominates the hydrogen A/D. The apparent activation energies of 63±5 and $\text{61±7}\text{kJ/mol}\text{H}{}_2$ in Mg_1.95Ag_0.05Ni alloy and $\text{52±2}\text{kJ/mol}\text{H}{}_2$ and of $\text{50±2}\text{kJ/mol}\text{H}{}_2$ in Mg_1.9Ag_0.1Ni alloy were found for the H/D processes in two-phase (α–β) coexistence region from 523 to $\text{573}\text{K}$, respectively. With the increasing content of Ag in Ag–Mg–Ni alloys, the apparent energy was decreased and the reaction rate was faster. It is reasonable to explain that the hydriding kinetics of Mg₂Ni was improved by adding Ag.     

A comparative study on effect of microwave sintering and conventional sintering on properties of Nd–Mg–Ni–Fe3O4 hydrogen storage alloy

The hydrogen storage samples of Nd–Mg–Ni–Fe₃O₄ alloy were prepared by microwave sintering (MS) and conventional sintering (CS) methods, respectively. Their phase structures, morphologies, hydrogen storage properties were intensively studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and pressure–composition–temperature (PCT). XRD and SEM analysis results show that the microwave sintered Nd–Mg–Ni–Fe₃O₄ alloy has multiphase structure involving Mg and homogeneous grains, whereas the alloy prepared by CS has Mg₄₁Nd₅ phase and coarse grains. The alloy prepared by MS can release 85% of the saturated hydrogen capacity at 573 K in 600 s and its characteristic reaction time (t_c) is less than 2900 s, while the alloy prepared by CS releases less than 70% of the absorbed hydrogen at 573 K within 1300 s and its t_c is more than 3000 s. It is found that the alloy prepared by MS not only has high hydrogen capacity, but also better dehydriding kinetic property than the alloy prepared by CS.     

Synthesis and characterization of composite visible light active photocatalysts MoS2–g-C3N4 with enhanced hydrogen evolution activity

Molybdenum disulfide (MoS₂) and graphitic carbon nitride (g-C₃N₄) composite photocatalysts were prepared via a facile impregnation method. The physical and photophysical properties of the MoS₂–g-C₃N₄ composite photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microcopy (HRTEM), ultraviolet–visible diffuse reflection spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectroscopy. The photoelectrochemical (PEC) measurements were tested via several on–off cycles under visible light irradiation. The photocatalytic hydrogen evolution experiments indicate that the MoS₂ co-catalysts can efficiently promote the separation of photogenerated charge carriers in g-C₃N₄, and consequently enhance the H₂ evolution activity. The 0.5wt% MoS₂–g-C₃N₄ sample shows the highest catalytic activity, and the corresponding H₂ evolution rate is 23.10 μmol h⁻¹, which is enhanced by 11.3 times compared to the unmodified g-C₃N₄. A possible photocatalytic mechanism of MoS₂ co-catalysts on the improvement of visible light photocatalytic performance of g-C₃N₄ is proposed and supported by PL and PEC results.     

Improved hydrogen storage performance of MgH2–NaAlH4 composite by addition of TiF3

In a previous paper, it was demonstrated that a MgH₂–NaAlH₄ composite system had improved dehydrogenation performance compared with as-milled pure NaAlH₄ and pure MgH₂ alone. The purpose of the present study was to investigate the hydrogen storage properties of the MgH₂–NaAlH₄ composite in the presence of TiF₃. 10 wt.% TiF₃ was added to the MgH₂–NaAlH₄ mixture, and its catalytic effects were investigated. The reaction mechanism and the hydrogen storage properties were studied by X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry (DSC), temperature-programmed-desorption and isothermal sorption measurements. The DSC results show that MgH₂–NaAlH₄ composite milled with 10 wt.% TiF₃ had lower dehydrogenation temperatures, by 100, 73, 30, and 25 °C, respectively, for each step in the four-step dehydrogenation process compared to the neat MgH₂–NaAlH₄ composite. Kinetic desorption results show that the MgH₂–NaAlH₄–TiF₃ composite released about 2.4 wt.% hydrogen within 10 min at 300 °C, while the neat MgH₂–NaAlH₄ sample only released less than 1.0 wt.% hydrogen under the same conditions. From the Kissinger plot, the apparent activation energy, E_A, for the decomposition of MgH₂, NaMgH₃, and NaH in the MgH₂–NaAlH₄–TiF₃ composite was reduced to 71, 104, and 124 kJ/mol, respectively, compared with 148, 142, and 138 kJ/mol in the neat MgH₂–NaAlH₄ composite. The high catalytic activity of TiF₃ is associated with in situ formation of a microcrystalline intermetallic Ti–Al phase from TiF₃ and NaAlH₄ during ball milling or the dehydrogenation process. Once formed, the Ti–Al phase acts as a real catalyst in the MgH₂–NaAlH₄–TiF₃ composite system.