Hydrogen Absorption Desorption Research Articles

Amorphous mixed transition metal oxides: A novel catalyst for boosting dehydrogenation of MgH2

Magnesium hydride (MgH2) has been recognized as a promising hydrogen storage material. However, the sluggish hydrogen desorption kinetics is one of the main factors hindering its practical applications. To enhance the dehydrogenation kinetics of MgH2, an amorphous mixed TiO2-ZrO2-V2O5 catalyst is synthesized in this work. After adding the as-synthesized catalyst into MgH2 by ball milling, the dehydrogenation activation energy can be decreased to 65.7 kJ mol−1. Meanwhile, the catalyzed MgH2 shows excellent cycling stability after fifty hydrogen absorption-desorption cycles. The significant improvement of hydrogen desorption kinetics is attributed to the synergistic effect of abundant oxygen vacancies and in situ formed multivalent species in the catalyst. This highlights the importance of designing and synthesizing efficient catalysts for dehydrogenation of MgH2.

Effect of Ce replacing La on the electrochemical performance of amorphous grain boundaries Mg-Ni-based materials

Aiming at enhancing the electrochemical characteristic of RE-Mg-based composite, the partial substituting La with Ce experiment in the composites was conducted, and the surface modification treatment of the alloys was performed by mechanical coating Ni. By means of mechanical trituration, The La10-xCexMg80Ni5 (x = 0–2) + y wt% Ni (y = 50–200) compound materials which have the structures of nanocrystalline and amorphous were synthesized. In order to make sense of the principle action of Ce and Ni elements in structural and electrochemical properties of the material, some deep research were carried out. According to the final results, the as-milled composites have the electrochemical hydrogen absorption and hydrogen desorption abilities at room temperature. Having no use for activation, the as-milled composites can reach the maximum discharge capacities when the first cycling was carried out. With the Ni value x changed from 50 to 200, the discharge capacity was varied from 70.5 mAh/g to 902.1 mAh/g; moreover, the capacity retention rate at 20th cycle (S20) and high rate dischargeability (HRD) of the (x = 0) composite were heightened from 67.2 % to 82.3 %, from 50.6 % to 55.7 % respectively. The composites' (y = 100) discharge capacity has a maximum value 118.5 mAh/g when the Ce value x is 1. The capacity retention rate (S20) is enhanced from 53.3 % to 68.5 % by lifting Ce content from x = 0 to x = 2. what's more, the high-rate discharge ability (HRD), the electrochemical impedance spectrum (EIS), potentiodynamic polarization curves, and potential-step measurements all intimate that substituting La with Ce clearly promotes the composites' electrochemical kinetic properties, but maximum values emerge only when the x value is 1.

Structural Evolution and Hydrogen Sorption Properties of YxNi2−yMny (0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3) Laves Phase Compounds

The YxNi2−yMny system was investigated in the region 0.825 ≤ x ≤ 0.95, 0.1 ≤ y ≤ 0.3. The alloys were synthesized by induction melting and corresponding annealing. The substitution of Mn for Ni (y = 0.1) favors the formation of a C15 structure with disordered Y vacancies against the superstructure of Y0.95Ni2. For y = 0.2 and 0.3, Mn can substitute in both Y and Ni sites. Single-phase compounds with a C15 structure can be formed by adjusting both the Y and Mn contents. Their hydrogen absorption–desorption properties were measured by pressure–composition isotherm (PCI) measurements at 150 °C, and the hydrides were characterized at room temperature by X-ray diffraction and TG–DSC experiments. The PCIs show two plateaus corresponding to the formation of crystalline and amorphous hydrides. The heating of the amorphous hydrides leads to an endothermic desorption at first and then a recrystallization into Y(Ni, Mn)3 and YHx phases. At higher temperatures, the Y hydride desorbs, and a recombination into a Y(Ni, Mn)2 Laves phase compound is observed. For y = 0.1, vacancy formation in the Y site and partial Mn substitution in the Ni site enhance the structural stability and suppress the hydrogen-induced amorphization (HIA). However, for a larger Mn content (y ≥ 0.2), Mn substitutes also in the Y sites at the expense of Y vacancies. This yields worse structural stability upon hydrogenation than for y = 0.1, as the mean ratio r(Y, Mn)/r(Ni/Mn) becomes larger than for y = 0.1 r(Y, ☐)/r(Ni/Mn).

Structure and bonding in TiNiSi type LaMgSnH intermetallic hydride

The work was aimed on reaching a better understanding of the effect of magnesium as a component of the hydride-forming LaMgSn intermetallic compound crystallising with the orthorhombic TiNiSi type of structure on the hydrogenation behaviours, crystal structure and bonding interactions with hydrogen. The LaMgSn structure is significantly expanded as compared to the earlier studied isotypic LaNiSn H storage material (volume expansion of 23%), as a result of a substitution of the smaller Ni atoms by much larger Mg atoms. This significantly affects the chemistry of the interaction of the intermetallic compound with hydrogen because a transition metal, Ni, in replaced by an active hydride-forming metal, Mg. The work involved computational studies of the electronic structure of the intermetallic compound and its hydride, and experimental studies of the hydrogenation behaviour and thermal stability of the formed hydride LaMgSnH, its structural characterisation by SR XRD and neutron powder diffraction, and Mössbauer spectroscopic studies of the stannide and its hydride. These studies showed that in the system LaMgSn-H2 a monohydride LaMgSnH is a thermodynamically favourable hydride composition. PDOS levels show that hydrogen and all constituting elemental metals, La, Mg and Sn, have peaks of electron density in the range between − 6 and − 4 eV indicating their hybridisation. The results show the hybridization of H atoms not only with bonded La and Mg atoms forming H-filled tetrahedra La3Mg, but also with Sn despite its atoms do not have bonding interactions with H. This explains the high stability of the metal substructure which does not disproportionate into the binary hydrides of La and Mg even when heated to 200 °C @ 20 bar H2, but instead forms an insertion type hydride. Formation of the monohydride LaMgSnH (Sp.gr. Pnma; a=8.1628(4); b= 4.5555(3); c= 9.2391(5) Å; V= 343.56(5) Å3) causes a small (1.26%) expansion of the unit cell volume compared to LaMgSn, and mainly proceeds along the [100] direction. Hydrogen absorption-desorption cycle results in a reversible formation of the initial compound LaMgSn, with the peak of hydrogen release occurring in vacuum at 355 °C, which is intermediate between the temperatures for the vacuum decomposition of the dihydrides MgH2 and LaH2. From the combined refinements of the Synchrotron (SR) XRD and Neutron Powder Diffraction (NPD) data, deuterium atoms completely and in an ordered way fill a half of the available La3Mg interstitial sites with metal-H/D distances of Mg-D= 2.026 Å; La-D= 2.381 and 2.502 Å. The occupied La3Mg sites are smaller in size than the vacant Mg3La tetrahedra. Sn and D exhibit a nonbonding interaction with the closest Sn-D separation of 3.033 Å. 119Sn Mössbauer spectra of LaMgSn and LaMgSnH show isomer shifts of 1.98(2) and 1.99(1) mm/s which are typical for the chemically similar stannides.

Bulk Nanostructured Silicide Thermoelectric Materials by Reversible Hydrogen Absorption-Desorption.

The production of bulk nanostructured silicide thermoelectric materials by a reversible hydrogen absorption-desorption process is demonstrated. Here, high-pressure reactive milling under 100bar hydrogen is used to decompose the Ca2Si phase into CaH2 and Si. Subsequent vacuum heat treatment results in hydrogen desorption and recombination of the constituents into the original phase. By changing the heat treatment temperature, recombination into Ca2Si or Ca5Si3 can be achieved. Most importantly, the advanced synthesis process enables drastic and simple microstructure refinement by more than two orders of magnitude, from a grain size of around 50µm in the initial ingot to 100-200nm after the hydrogen absorption-desorption process. Fine precipitates with sizes ranging from 10-50nm are forming coherently inside the grains. Thus, the route is promising and can be used for reducing thermal conductivity due to phonon scattering from grain boundaries as well as through nanostructuring with second-phase precipitates. Moreover, the process is environmentally friendly since hydrogen is reversibly absorbed, desorbed, and can be fully recovered.

In Ukrainian

The proposed work considers: hydrogen sorption properties of systems of magnesium intermetallic compounds with a complex cubic structure C15b, as promising, reliable, reversible hydrogen accumulators. Considered thermal processes. A statistical theory is proposed for the cubic structure C15b of composition MgRT4Hx, where R = Ce, La, Nd, Pr, Y; T = Co, Ni; 0 ≤ x ≤ 6 at phase transitions in the process of hydrogenation, taking into account pressure. The concentration dependences of the maximum values of the order parameter and a priori probabilities are established. Hydrogen solubility isopleths and isotherms are calculated and considered, and a graphical concentration dependence of the hydrogen atom ordering temperature in MgCeCo4-type crystals is created. The order-disorder transition is considered with allowance for temperature, and the process of absorption-desorption of hydrogen by the C15b structure is also studied. The equation of thermodynamic equilibrium with the calculation of free energy is derived. And also considered the graphical dependence of the value of the order parameter on temperature and pressure. The temperature dependence of hydrogen solubility in the α, β phases for the MgCeCo4 crystal is considered. The configurational heat capacity of a crystal of the MgSnCu4Hx type structure has been studied, taking into account the temperature and the order parameter. A graph of hydrogen absorption-desorption of the MgCeCo4Hx crystal has been constructed. A comparative analysis of the experimental and practical results of the absorption-desorption of hydrogen by the working fluid of the composition MgRT4Hx has been carried out.

Thermodynamic and kinetic isotope effects on hydrogen absorption by Pd–Al2O3 pellets

Palladium has been widely served as the separation material in the hydrogen isotope separation process on account of its unique hydrogenation characteristics. To reduce Pd pulverization effect and improve the gas flow rate, Pd–Al2O3 (Pd deposited on Al2O3) is commonly used as the separation material. It is crucial to grasp the hydrogen absorption and desorption thermodynamics and kinetic isotope effect of Pd–Al2O3 material, which favours raising the separation efficiency. In this work, the effect of PdO existing in the fresh Pd–Al2O3 on the thermodynamic character of Pd–Al2O3–H(D) system and the porous substrate effect on the hydrogen absorption kinetics of Pd–Al2O3 were investigated. It shows that PdO could totally reduce to Pd after primary hydrogen adsorption-desorption, leading to decreased hydrogen absorption capacity. However, it has no effect on the enthalpy and entropy values of Pd–Al2O3–H (D) system. The kinetic analysis of hydrogen adsorption of Pd–Al2O3 shows that the hydrogen absorption of Pd–Al2O3 could be fitted by Mample model, a special case of the JMAK model, and the interface-controlled model can be deduced. The porous substrate influences the rate of hydrogen adsorption of Pd–Al2O3. The SEM and XRD results show that after 60 hydrogen absorption-desorption cycles, the surface of Pd–Al2O3 pellet has a slight change with a pulverization rate of 3.3 wt%, although the high-strength alumina support can withstand the stress caused by Pd expansion during hydrogen absorption.

Application of nitrogen-doped graphene-supported titanium monoxide as a highly active catalytic precursor to improve the hydrogen storage properties of MgH2

MgH2 has broad prospects in energy storage applications; however, its poor thermodynamic properties and slow hydrogen absorption and desorption rates are unsuitable for commercial needs. In the present work, TiO@N-C (denoted as TTONC), a highly active catalytic precursor, was employed to improve the hydrogen storage properties of MgH2. The TTONC-catalyzed MgH2 could uptake hydrogen at room temperature, and the onset dehydrogenation temperature of TTONC-catalyzed MgH2 was 94 °C lower than that of pristine MgH2 (∼300 °C). Dehydrogenated TTONC-catalyzed MgH2 had a capacity retention rate of 95.2% after 50 hydrogen absorption-desorption cycles. The dehydrogenation and hydrogenation apparent activation energies of MgH2-TTONC were 90.5 kJ.mol−1 and 52.7 kJ.mol−1, respectively. The catalytic mechanism analysis revealed that the in situ formed Ti generated TiH2 in the hydrogenation process, and Ti/TiH2 acted as a hydrogen pump to diffuse hydrogen atoms in the hydrogen absorption/desorption process. The formation of stable CN layers with carbon structural defects on the surface of MgH2 inhibited the fragmentation and agglomeration of MgH2 particles, and they served as nucleation sites to enhance hydrogen diffusion. Hence, the dehydrogenation/hydrogenation properties and cyclic stability of MgH2 were greatly enhanced by the addition of TTONC.

Tailor-designed vanadium alloys for hydrogen storage in remote area and movable power supply systems

Vanadium-based alloys are potential materials for hydrogen storage applications in Remote Area Power Supply (RAPS) and Movable Power Supply (MPS). In this study, V80Ti8Cr12 alloys are tailor-made to meet the RAPS and MPS working conditions (293–323 K and 0.2–2 MPa). The effects of pulverization methods and particle sizes on the alloy's hydrogen storage properties have been systematically investigated. In addition, a novel Pressure-Composition-Isotherm approach is employed for the first time to accurately evaluate the hydrogen storage capacities. The reduction of particle size enhances the absorption kinetics due to the increased surface area. However, mechanical pulverization causes lattice distortion that decreases the hydrogen absorption capacity and desorption rate. In contrast, hydrogen embrittlement can effectively pulverize the alloys without generating lattice distortion. The results reveal that 5 mm sample, which is simply subjected to hydrogen embrittlement, achieves the largest usable hydrogen storage capacity up to 2.1 wt% and the fastest hydrogen desorption rate of ∼4 sccm/g that is nine times quicker than required for RAPS and MPS applications. After 500 cycles, the 5 mm alloy retains 90 % of its capacity, demonstrating excellent durability. Hence, 5 mm hydrogen-embrittled V80Ti8Cr12 alloy is an ideal hydrogen storage material in RAPS and MPS systems.

Destabilization of the LiBH4–NaBH4 Eutectic Mixture through Pore Confinement for Hydrogen Storage

Both LiBH4 and NaBH4 are well known for having high hydrogen contents, but also high decomposition temperatures and slow hydrogen absorption–desorption kinetics, preventing their use for hydrogen storage applications. The low melting temperature (219 °C) of their eutectic mixture 0.71 LiBH4–0.29 NaBH4 allowed the synthesis of a new composite material through the melt infiltration of the hydrides into the ~5 nm diameter pores of a CMK-3 type carbon. A composite of 0.71 LiBH4–0.29 NaBH4 and non-porous graphitic carbon discs was also prepared by similar methods for comparison. Both composites showed improved kinetics and a partial reversibility of the dehydrogenation/rehydrogenation reactions. However, the best results were observed for the CMK-3 nanoconfined hydrides; a consistent uptake of about 3.5 wt.% H2 was recorded after five hydrogenation/dehydrogenation cycles for an otherwise non-reversible system. The improved hydrogen release kinetics are attributed to carbon–hydride surface interactions rather than nanoconfinement, while enhanced heat transfer due to the carbon support may also play a role. Likewise, the carbon–hydride contact proved beneficial in terms of reversibility, without, however, ruling out the potential positive effect of pore confinement.

Research on the Creep and Fatigue Evaluation Method of the Double-Layered Annulus Metal Hydride Bed Combined with Numerical Modeling and ASME Code

Applied to a hydrogen absorption-desorption cycle, the hydrogen storage bed will experience higher exchange temperatures and variety of mechanical load. Due to the complex structure of the double-layered annulus metal hydride bed and the importance of thermal stress on the failure of a metal hydride bed, the numerical modeling of its hot spot stress was carefully carried out. Moreover, in this paper, an analysis method considering the limit failure mode condition is proposed to deal with the stress analysis in the process of hydrogen absorption and desorption. According to the proposed analysis method, the maximum stress of thermal-structural coupling in the process of hydrogen absorption occurs at about 1/3 along the diameter direction and at the geometric mutation of the connection between the cooling pipe and the main body of the hydrogen storage bed in the process of hydrogen desorption. Apart from that, the hydrogen storage bed is also subjected to thermal-mechanical fatigue by the iterative process of absorption and desorption, and its operating temperature range is in the thermal creep temperature region. Based on the distribution of the stress and temperature, evaluation hot sites were selected and the ASME-NB and ASME-NH codes were used to evaluate fatigue and fatigue creep, respectively. The evaluation showed that the fatigue damage generated during its service life is small, while the creep damage is relatively large and the total damage generated during the service life of the hydrogen storage bed is within the safe range. Aiming at the structure and complex process of a double-layer hydrogen storage bed, creep and fatigue evaluation methods are proposed, various failure modes of hydrogen storage bed are highlighted, and the relationship between process parameters and life is established.

Structural features of 18R-type long-period stacking ordered phase in Mg85Zn6Y9 alloy and the Ni doping effect on its hydrogen storage properties

Magnesium-based alloys with 18R-type long-period stacking ordered (LPSO) structures have attracted wide attention for structural and functional applications. To understand hydrogen storage properties of 18R phase, the Mg85Zn6Y9 alloy with 94 wt.% of 18R-type LPSO phase is prepared in this work. The 18R phase has a layered structure where Y-Zn-Mg and Mg layers alternately stack along the c-axis. In the Y-Zn-Mg layers, Y, Zn and partial Mg sites are co-occupied by Y and Mg, Zn and Mg, and Mg and Zn/Y atoms, respectively. Thus the 18R phase is easily decomposed into α-MgH2, γ-MgH2, YH2, YH3, C14-type Laves phase MgZn2 and minor CsCl-type Y(Mg,Zn) during ball milling under hydrogen atmosphere. After further hydrogen absorption-desorption cycling, Y(Mg,Zn) disappears gradually and C14 phase transforms into C15-type Laves phase. By contrast, the Mg85Zn6Y9 alloy has better hydrogen storage kinetics and cycle durability than pure Mg because of the catalytic effect of YH2/YH3 on hydrogen absorption-desorption and inhibition role of Laves phase in Mg crystallite growth. Moreover, the introduction of Ni into Mg85Zn6Y9 sample leads to a further decrease in activation energy of hydrogen desorption from 106.39 to 96.78 kJ mol−1 due to the formation of Mg2Ni. This work not only provides new insights into structural features and hydrogen storage characteristics of 18R phase but offers an effective method for improving hydrogen storage properties.

Remarkable enhancement in durability of ZrCo alloy against hydrogen induced disproportionation by Ti and Nb co-substitution

Considering the thermodynamic stability of various hydrides, a strategy has been employed to improve the hydrogen isotope storage properties of ZrCo alloy which involves partial co-substitution of Zr with Ti and Nb. Herein, alloys of composition Zr0.8Ti0.2-xNbxCo (x = 0.05, 0.1, 0.15) is prepared, characterized and the effect of Ti and Nb doping on hydrogen storage properties of parent ZrCo alloy is investigated. XRD analysis confirmed the formation of desired pure cubic phase of all the synthesized alloys similar to ZrCo phase. The presence of a single plateau in hydrogen desorption pressure-composition isotherms confirms single step hydrogen absorption-desorption behavior in Zr0.8Ti0.2-xNbxCo alloys. The equilibrium pressure of hydrogen desorption decreases marginally with increasing Nb content in Zr0.8Ti0.2-xNbxCo alloys which is further corroborated by differential scanning calorimetry measurements. Investigation of hydrogen induced disproportionation behavior in ITER-simulating condition revealed substantial impact of co-substitution of Ti and Nb on anti-disproportionation properties of ZrCo alloy. These remarkable properties make the Ti and Nb co-substituted quaternary alloys a desirable material for hydrogen isotope storage and delivery application.

Influence of heat exchanger structure on hydrogen absorption-desorption performance of hydrogen storage vessel

The influence of heat exchanger structure on hydrogen absorption-desorption performance of hydrogen storage vessel was studied, in which the AB5 (La0.25Ce0.75Ni4.4Al0.1Mn0.1Co0.4) hydrogen storage alloy was used as a typical representative. In order to obtain the data on reaction enthalpy, the PCT curve of the alloy was measured with three different temperatures, and the linear fitting was carried out according to the Van't Hoff relation curve. The SMCR (Spiral-mini-channel Reactor) reactor structure was adopted. The heat transfer method and its simplified model were studied by finite element method to explore the effect of size of heat transfer structure, particularly for heat pipe diameter, on the hydrogen absorption-desorption performance of hydrogen storage alloy in the vessel.

Phase transformation of hydride-phase Nd2Co7 with superlattice structure

We investigated the phase stability of Nd2Co7 with a superlattice structure, its hydrogenation properties, and phase transformation during hydrogen absorption–desorption process. The results showed that Ce2Ni7-type and Gd2Co7-type structures coexisted in the annealed sample up to 1273 ​K. The Gd2Co7-type phase disappeared at temperatures above 1323 ​K. We successfully synthesized a largely single-phase Ce2Ni7-type Nd2Co7 when the alloy was annealed at 1373 ​K, followed by quenching in ice water. The phase transformation follows the order: hexagonal Nd2Co7 (space group P63/mmc) → hexagonal Nd2Co7H2.7 (space group P63/mmc) → orthorhombic Nd2Co7H8.1 (space group Pbcn), upon hydrogen absorption. Anisotropic lattice expansion along the c axis was observed in Nd2Co7H2.7. The unit cell of Nd2Co7H8.1 underwent isotropic expansion along the a, b, and c axes. However, the volume expansions of the MgZn2-type cell, CaCu5-type cell I, and CaCu5-type cell II were uneven at 36.0%, 8.9%, and 13.0%, respectively.

The role of magnesium on properties of La3-xMgxNi9 (x=0, 0.5, 1.0, 1.5, 2.0) hydrogen storage alloys from first-principles calculations

The present work gives the electronic structures of La3-xMgxNi9 (x = 0.0–2.0) alloys by first-principles calculations using the generalized gradient approximation of Perdew-Wang 91 (GGA-PW91) method within Cambridge Serial Total Energy Package (CASTEP), aiming at gaining insight into the hydrogen storage mechanism of La3-xMgxNi9 alloys modified by Mg. The results show that the La3-xMgxNi9 alloys consist predominantly of interactions between La-Ni, Ni-Ni or/and Mg-Ni. Among them, La-Ni interaction is the major factor controlling the structural stability of the alloys. Mg substitution increases the La-Ni bonding interactions to achieve stable Mg-containing metal matrices for reversible hydrogen absorption-desorption. This is particularly obvious at high Mg composition, as the La-Ni interactions gradually increase with Mg content. The increase of La-Ni interactions coupled with the decrease of Mg-Ni and Ni-Ni interactions will relieve the hydrogen-induced amorphization and disproportionation, and subsequently enhance the cyclic stability of La3-xMgxNi9 alloys at high Mg content. However, Mg substitution for La leads to a subsequent contraction in cell volume, dramatically reducing the reversible H capacity at high Mg composition such as LaMg2Ni9. Suitable Mg content in La-Mg-Ni systems, such as an approximately range x = 1.0–1.4 in La3-xMgxNi9 alloys, is required in trade-off between hydrogen storage capacity and cycle life.

Crystal structure of deuteride phase of Nd-Ni alloy by X-ray and neutron diffraction

The hydrogen-absorbing alloys currently used in industry form residual hydrogen that reduces the alloy’s reversible hydrogen capacity, decreasing its useful life. RNi3 intermetallic compounds, which have a PuNi3-type crystal structure composed of MgZn2-type and CaCu5-type cells that exhibit structural change in relation to their hydrogenation properties, have been the focus of much research, but only a few of those reports focus on the interplay between residual hydrogen and alloy structure. Thus, this study seeks to clarify the residual hydrogen occupation mechanisms in MgZn2-type and CaCu5-type cells during the hydrogen absorption-desorption process. The structural changes and deuterium occupation in NdNi3Dx were investigated using X-ray diffraction (XRD) and neutron powder diffraction (NPD). Rietveld refinement was performed for NdNi3, NdNi3D2.6, NdNi3D3.2, NdNi3D4.0, and NdNi3D4.8, during the deuterium absorption-desorption process. The deuterium capacity reached 0.9 D/M at the first absorption process and 0.7 D/M of residual deuterium was formed after the first desorption at 248 K. For NdNi3D2.6 (phase II), the residual deuterium contents of MgZn2-type and CaCu5-type cells were determined to be 1.0 D/M and 0.4 D/M, respectively. The residual deuterium preferred the deuterium site in the MgZn2-type cell. The deuterium capacity was 1.2 D/M in the first absorption process at 213 K and the residual deuterium was 1.0 D/M at the end of the first desorption. The severe peak broadening observed in the XRD and neutron diffraction patterns of NdNi3D4.0 and NdNi3D4.8 indicate that the deformation of the metal sublattice of the deuteride phase was deformed over 0.8 D/M.

In situ incorporation of highly dispersed nickel and vanadium trioxide nanoparticles in nanoporous carbon for the hydrogen storage performance enhancement of magnesium hydride

Slow hydrogen absorption-desorption kinetics and high thermal stability hinder the industrial application of Mg/MgH2 systems. In order to overcome these drawbacks, the in situ incorporation of highly dispersed nickel and vanadium trioxide nanoparticles in nanoporous carbon ((Ni-V2O3)@C) was introduced to enhance the hydrogen storage performance of Mg/MgH2. It was found that the 10 wt% (Ni-V2O3)@C-containing sample demonstrated excellent hydrogen storage performance. The 10 wt% (Ni-V2O3)@C-containing sample could uptake hydrogen at room temperature, and its initial hydrogenation temperature was reduced by 100 °C as compared to that of pristine MgH2. Moreover, this system could absorb 5.50 wt% of H2 at 25 °C and release 6.05 wt% of H2 at 275 °C in 10 min. In addition, the hydrogenation and dehydrogenation activation energies of the 10 wt% (Ni-V2O3)@C-containing sample were calculated as 42.1 kJ·mol−1 and 84.6 kJ·mol−1, respectively, which were 46.8 kJ·mol−1 and 51.6 kJ·mol−1 lower than those of pristine MgH2, respectively. Mechanism analysis results revealed that V2O3 was partially converted into VO during milling with MgH2, and Ni reacted with Mg to form in situ Mg2Ni after the first dehydrogenation. The in situ Mg2Ni/Mg2NiH4 coating around Mg/MgH2 acted as a “hydrogen pump” to drive hydrogen diffusion and dissociation, and the presence of C inhibited the agglomeration of Mg/MgH2 particles. Therefore, the addition of (Ni-V2O3)@C was found to be a good strategy to improve the hydrogen storage performance of MgH2.

Hydrogen absorption-desorption characteristic of (Ti0.85Zr0.15)1.1Cr1-xMoxMn based alloys with C14 Laves phase

The microstructure and hydrogen absorption-desorption characteristic of (Ti0.85Zr0.15)1.1Cr1-xMoxMn (x ​= ​0.05, 0.1, 0.15, 0.2 ​at.%) alloys were investigated. The results showed that the corresponding alloys were determined as a single phase of C14-type Laves structure. With the increase of Mo content, the maximum and reversible hydrogen absorption capacity decreased, the slope factor Hf increased. Among the studied alloys, (Ti0.85Zr0.15)1.1Cr0.95Mo0.05Mn had the best overall properties for practical application of hydrogen storage materials. The maximum and reversible hydrogen storage capacity were 1.76 ​wt% and 1.09 ​wt%, the slope factor Hf was 0.51, and its dissociation enthalpy (ΔHd) and entropy change (ΔSd) were 23.1 ​kJ ​mol−1H2, 93.8J ​K−1mol−1H2 at 303K, respectively. By studying the dissociation pressures of the synthesized metal hydrides, it was found that Mo had a special effect on the dissociation pressure of Ti–Zr–Cr–Mo–Mn alloys. Among the four alloys, (Ti0.85Zr0.15)1.1Cr0.95Mo0.05Mn alloy had the largest hydrogen absorption capacity and the fastest hydrogen desorption rate, which can meet the commercialization demand of hydrogen fuel cell hydrogen supply system.

Hydrogen absorption–desorption characteristics of R3MgNi14(R = Nd, Gd and Er) alloys

Hydrogen absorption–desorption characteristics of R3MgNi14(R = Nd, Gd and Er) alloys