Achieving superior hydrogen storage properties via in-situ formed nanostructures: A high-capacity Mg–Ni alloy with La microalloying

Mg-based hydride is a promising hydrogen storage material, but its capacity is hindered by the kinetic properties. In this study, Mg–Mg₂Ni–LaH_x nanocomposite is formed from the H-induced decomposition of Mg₉₈Ni_1·67La_0.33 alloy. The hydrogen capacity of 7.19 wt % is reached at 325 °C under 3 MPa H₂, attributed to the ultrahigh hydrogenation capacity in Stage I. The hydrogen capacity of 5.59 wt % is achieved at 175 °C under 1 MPa H₂. The apparent activation energies for hydrogen absorption and desorption are calculated as 57.99 and 107.26 kJ/mol, which are owing to the modified microstructure with LaH_x and Mg₂Ni nanophases embedding in eutectic, and tubular nanostructure adjacent to eutectic. The LaH_2.49 nanophase can catalyze H₂ molecules to dissociate and H atoms to permeate due to its stronger affinity with H atoms. The interfaces of these nanophases provide preferential nucleation sites and alleviate the “blocking effect” together with tubular nanostructure by providing H atoms diffusion paths after the impingement of MgH₂ colonies. Therefore, the superior hydrogenation properties are achieved because of the rapid absorption process of Stage I. The efficient synthesis of nano-catalysts and corresponding mechanisms for improving hydrogen storage properties have important reference to related researches.     

Precipitation of nanocrystalline LaH3 and Mg2Ni and its effect on de-/hydrogenation thermodynamics of Mg-rich alloys

Based on the catalytic effects of transition metals and rare earth metals on magnesium hydride, precipitation behavior of nanocrystalline LaH₃ and Mg₂Ni has been discussed and correlated with the de-/hydrogenation thermodynamic of Mg-rich alloys in this work. The results show that a significant enhancement of de-/hydrogenation properties has been achieved due to in-situ formed Mg–Mg₂Ni–LaH₃ nanocomposites. It is observed that the Mg₂Ni-rich alloy exhibiting superior performance can desorb about 5.7 wt% hydrogen within 2.5 min at 623 K. The formation of LaH₃ tends to promote the hydrogenation process and the Mg₂Ni is beneficial for improving the dehydrogenation performance. Meanwhile, the phase boundaries between LaH₃, Mg₂Ni and Mg also play positive roles due to stored extra energy on the interface. Fitting kinetics model shows that rate-limiting steps of the as-prepared alloys have changed and the desorption activation energy significantly decreases due to precipitation of nanocrystalline LaH₃ and Mg₂Ni. It is worth noting that desorption activation energy of the preferable composite decreases to 94.03 kJ mol⁻¹. Thermodynamic properties are also investigated and analyzed based on plateau pressure and van't Hoff equation. It is revealed that precipitation of nanocrystalline LaH₃ and Mg₂Ni significantly enhances the hydrogen storage kinetics of Mg-based alloys.     

Microstructure characteristics,hydrogen storage thermodynamic and kinetic properties of Mg–Ni–Y based hydrogen storage alloys

In this paper, the Mg_95-X-Ni_x-Y₅ (x = 5, 10, 15) alloy were prepared by vacuum induction melting. The X-ray diffraction was used to analytical phase composition in different states, and the Scanning Electron Microscope and Transmission Electron Microscope were used to characterize the microstructure and crystalline state. Meanwhile, the kinetic properties of isothermal hydrogen adsorption and desorption at different temperatures also were tested by the Sievert isometric volume method. The results indicate that the hydrogenated Mg–Ni–Y samples is a nanocrystalline structure consists of MgH₂, Mg₂NiH₄, and YH₃ phases. And, the in-situ formed YH₃ phase not decompose in the process of dehydrogenation and evenly dispersed in the mother alloy, which plays a paly a positive the catalytic role for the reversible cyclic reaction of Mg and Mg₂Ni phases. In addition, the Ni elements are effectively to improve the thermodynamic properties of the Mg-based hydrogen storage alloy, the desorption enthalpy of the Ni₅, Ni₁₀, and Ni₁₅ samples successively decrease to 84.5, 69.1, and 63.5 kJ/mol H₂. The hydrogen absorption and desorption kinetics of the Mg–Ni–Y alloy are improved obviously with the increase of Ni content, especially for Mg₈₀Ni₁₅Y₅ alloy, which the optimal hydrogenated temperature is reduced to 200 °C, and the 90% of the maximum hydrogen storage capacity can be absorbed within 1 min, about 5.4 wt % H₂. Besides, the dehydrogenated activation energy of the Mg₈₀Ni₁₅Y₅ alloy also is reduced to 67.0 kJ/mol, and it can completely release hydrogen at 320 °C within 5 min, which is almost reached the hydrogen desorption capability of Ni₅ alloy at 360 °C. This means that Ni element is a very positive element to reduce the hydrogen desorption temperature.     

Effect of LaH3 additive on microstructures and hydrogen storage properties of V40Ti26Cr26Fe8 alloys prepared by hydride powder sintering method

Hydride-Powder-Sintering(HPS) as a new preparation approach was applied in the low cost V₄₀Ti₂₆Cr₂₆Fe₈ hydrogen storage alloys successfully, which provides an alternative preparation route for other types of hydrogen storage alloys. V₄₀Ti₂₆Cr₂₆Fe₈ alloy exhibits ideal hydrogen absorption-desorption performance after adding moderate content of LaH₃. Optimizing sintering process by increasing the sintering temperature and time has improved hydrogen desorption plateau evidently. X-ray diffraction analysis results show that the Ti-Oxide phase basically no longer exists when the LaH₃ content is greater than or equal to 3 wt% as compared to that of LaH₃ content below 3 wt%. Pressure-Compose-Temperature(PCT) curves show that the hydrogen absorption and desorption capacities increase gradually with the increase of LaH₃ content. The lattice parameters calculated by Rietveld refinement has the same variety rule as the hydrogen absorption-desorption capacities with the increase of LaH₃ content. It can be inferred that the addition of LaH₃ has reduced the content of Ti-Oxide and then the lattice parameters increase, which leads to the improvement of hydrogen performance of the alloy. The most appropriate preparation process is 3 wt% of LaH₃ additive with a sintering process 1673 K-6h, correspondingly, the hydrogen absorption and desorption capacities are 3.13 wt% and 1.97 wt%, respectively.     

Tunable microstructure,de-/hydrogenation kinetics and thermodynamics performance of Mg–Ni–La–Ti–H systems

In the light of positive effects of rare earth and transition metals on the hydrogen absorption/desorption properties of magnesium, the Mg20La–5TiH₂, Mg20Ni–5TiH₂ and Mg10Ni10La–5TiH₂ composites have been prepared in this work to ameliorate the de-/hydrogenation kinetics and thermodynamic performance. The results indicate that the as-prepared composites are mainly composed of Mg, Mg₂Ni/LaH₃ and TiH₂ phases after activation, and LaH₃ and TiH₂ are stable during de-/hydrogenation cycles. The morphology observations give evidences that LaH₃ with size about ~20 nm and Mg₂Ni with size about ~1 μm are uniformly distributed in the composites. It is noted that the de-/hydriding kinetics of the as-prepared composites are significantly improved after internal and surface modification, of which the Mg10Ni10La–5TiH₂ composite can desorb as high as 5.66 wt% hydrogen within 3 min at 623 K. Moreover, the thermodynamic properties of the experimental composites have also been investigated and discussed according to the pressure-composition isothermal curves and corresponding calculation by Van't Hoff equation. The improved hydrogen storage properties of the as-prepared composites are mainly attributed to the uniformly distributed LaH₃, Mg₂Ni and TiH₂ phases, which provide a large amount of phase boundaries, diffusion paths and nucleation sites for de-/hydrogenation reactions.     

Dual-tuning of de/hydrogenation kinetic properties of Mg-based hydrogen storage alloy by building a Ni-/Co-multi-platform collaborative system

The Mg-based hydrogen storage alloy with multiple platforms is successfully prepared by ball milling Co powder and Mg-RE-Ni precursor alloy, and its hydrogen storage behavior was investigated in detail by XRD, EDS, TEM, PCI, and DSC methods. The ball-milled alloy consists of the main phase Mg, the catalytic phases Mg₂Ni, Mg₂Co as well as a small amount of Mg₁₂Ce, and convert into the MgH₂–CeH_2.73-Mg₂NiH₄–Mg₂CoH₅ composite after hydrogenation. The composite has three PCI platforms corresponding to the reversible de/hydrogenation reaction of Mg/MgH₂, Mg₂Ni/Mg₂NiH₄ and Mg₆Co₂H₁₁/Mg₂CoH₅. Among them, the transformation between Mg₂Ni and Mg₂NiH₄ triggers the “spill-over” effect which promote the decomposition of MgH₂ phases and enhances the hydrogen desorption kinetics. Meanwhile, the conversion of the Mg₆Co₂H₁₁ to Mg₂CoH₅ phase induces the “chain reaction” effect, which leads to preferential nucleation of Mg phase and improves the hydrogen absorption kinetics. Therefore, the Mg-RE-Ni-Co alloy has a double improvement on hydrogen absorption and desorption kinetics. Concretely, the alloy has an optimal hydrogen absorption temperature of 200 °C, at which it can absorb 5.5 wt. % H₂ within 40 s. Under the conditions, the capacity of absorption almost reaches the maximum reversible value (about 5.6 wt. %). Besides, the alloy has a dehydrogenation activation energy of 67.9 kJ/mol and can desorb 5.0 wt. % H₂ within 60 min at the temperature of 260 °C.     

Synthesis,characterization and first hydrogen absorption/desorption of the Mg35Al15Ti25V10Zn15 high entropy alloy

In this work, a novel Mg-containing high entropy alloy (HEA), namely Mg₃₅Al₁₅Ti₂₅V₁₀Zn₁₅, was synthesized, characterized, and the phases formed after synthesis and after first hydrogen absorption/desorption were analyzed. The alloy composition was conceptualized aiming at increasing the atomic fraction of lightweight elements (35 at.% Mg and 15 at.% Al) to increase its gravimetric hydrogen storage capacity. Ti and V were selected to increase the hydrogen affinity of the alloy. Finally, Zn was selected as an alloying element because of its negative enthalpy of mixing with Mg, which could favor the formation of solid solution and avoid Mg segregation. The Mg₃₅Al₁₅Ti₂₅V₁₀Zn₁₅ HEA was synthesized by high-energy ball milling (HEBM) in two different routes: under argon atmosphere (mechanical alloying – MA) and under hydrogen pressure (reactive milling – RM). The sample produced by MA was composed of a body-centered cubic (BCC) phase with an amount of unmixed Mg. When hydrogenated at 375 °C and under 4.0 MPa of H₂, the MA sample absorbed about 2.5 wt% of H₂ by forming a mixture of MgH₂, a face-centered cubic (FCC) hydride, a body-centered tetragonal (BCT) phase and MgZn₂. The desorption sequence upon heating was investigated and it was shown that the MgH₂ is the first to desorb. The sequence of desorption is completed by the decomposition of the FCC hydride and BCT phase leading to the formation of the BCC phase. On the other hand, the alloy produced by RM was composed of a mixture of an FCC hydride and MgH₂. During desorption upon heating, the MgH₂ is also the first to desorb. At lower temperatures (below 350 °C), the FCC hydride decomposes partially forming the BCT phase. At higher temperatures, both FCC hydride and BCT phase decomposes forming the BCC phase. The desorption capacity of the RM sample was 2.75 wt% H₂.     

Composition dependent microstructure evolution,activation and de-/hydrogenation properties of Mg–Ni–La alloys

In this work, in order to elucidate the effect of different alloying elements on the microstructure, activation and the de-/hydrogenation kinetics performance, the Mg–20La, Mg–20Ni and Mg–10Ni–10La (wt.%) alloys have been prepared by near equilibrium solidification combined with high-energy ball milling treatment to realize the internal optimization as well as particle refinement. The results show that the microstructures of the prepared alloys are significantly refined by forming different types and sizes of intermetallic compounds. Meanwhile, the effects of LaH₃ and Mg₂Ni within the activated samples on de-/hydrogenation kinetics are also discussed. It is observed that the alloy containing LaH₃ preserves stable hydrogenation behavior between 573 and 623 K, while the hydrogenation properties of the alloy containing Mg₂Ni is susceptible to temperature. A preferable hydrogenation performance is observed in Mg–10Ni–10La alloy, which can absorb as high as 5.86 wt% hydrogen within 15 min at 623 K and 3.0 MPa hydrogen pressure. Moreover, the desorption kinetics and the desorption activation energies are evaluated to illustrate the mechanism based on improved dehydrogenation performance. The addition of proper alloying elements Ni and La in combination with reasonable processing is an effective strategy to improve the de-/hydrogenation performance of Mg-based alloys.     

Tuning the de/hydriding thermodynamics and kinetics of Mg by mechanical alloying with Sn and Zn

Mg₉₅Sn₃Zn₂ alloy was prepared by mechanical alloying. The phase constituents and phase transition were analyzed by X-ray diffraction (XRD) method. The microstructure was characterized by scanning electron microscope (SEM). The hydrogen storage properties were evaluated in detail by the measurements of isothermal hydrogen absorption and desorption, and pressure-composition isotherms (PCI) using the Sieverts method. The addition of Zn benefits to extend the solubility of Sn in the Mg lattice, as a result supersaturated Mg(Sn, Zn) ternary solid solution was synthesized by mechanical alloying, which decomposed to MgH₂, Sn and MgZn₂ in the hydrogenating process. The in situ formed nanostructure Mg₂Sn and MgZn₂ have positive effects on the hydrogen absorption and desorption of Mg. Mg₉₅Sn₃Zn₂ alloy showed significantly improved kinetics with lowered hydrogen absorption and desorption activation energies of 38.1 kJ/mol and 86.6 kJ/mol respectively, and exhibited a reduced dehydriding enthalpy of 67.0 ± 1.9 kJ/(mol·H₂).     

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.     

New mechanism and improved kinetics of hydrogen absorption and desorption of Mg(In) solid solution alloy milling with CeF3

This paper presents improving the hydrogen absorption and desorption of Mg(In) solid solution alloy through doped with CeF₃. A nanocomposite of Mg_0.95In_0.05-5 wt% CeF₃ was prepared by mechanical ball milling. The microstructures were systematically investigated by X-ray diffraction, scanning electron microscopy, scanning transmission electron microscopy. And the hydrogen storage properties were evaluated by isothermal hydrogen absorption and desorption, and pressure-composition-isothermal measurements in a temperature range of 230 °C–320 °C. The mechanism of hydrogen absorption and desorption of Mg_0.95In_0.05 solid solution is changed by the addition of CeF₃. Mg_0.95In_0.05-5 wt% CeF₃ nanocomposite transforms to MgH₂, MgF₂ and intermetallic compounds of MgIn and CeIn₃ by hydrogenation. Upon dehydrogenation, MgH₂ reacts with the intermetallic compounds of MgIn and CeIn₃ forming a pseudo-ternary Mg(In, Ce) solid solution, which is a fully reversible reaction with a reversible hydrogen capacity～4.0 wt%. The symbiotic nanostructured CeIn₃ impedes the agglomeration of MgIn compound, thus improving the dispersibility of element In, and finally improving the reversibility of hydrogen absorption and desorption of Mg(In) solution alloy. For Mg_0.95In_0.05-5 wt% CeF₃ nanocomposite, the dehydriding enthalpy is reduced to about 66.1 ± 3.2 kJ⋅mol⁻¹⋅H₂, and the apparent activation energy of dehydrogenation is significantly lowered to 71.9 ± 10.0 kJ⋅mol⁻¹⋅H₂, a reduction of ～73 kJ⋅mol⁻¹⋅H₂ relative to that for Mg_0.95In_0.05 solid solution. As a result, Mg_0.95In_0.05-5 wt% CeF₃ nanocomposite can release ～57% H₂ in 10 min at 260 °C. The improvements of hydrogen absorption and desorption properties are mainly attributed to the reversible phase transition of Mg(In, Ce) solid solution combing with the multiphase nanostructure.     

Room temperature conversion of Mg to MgH2 assisted by low fractions of additives

In recent works, it was noticed that Mg/MgH₂ mixed with additives by high energy ball milling allows temperature reductions of H₂ absorption/desorption without necessarily changing thermodynamic properties. Thus, the objective of this work was to investigate which additives, mixed in low fractions with MgH₂ powder would act as efficient hydrogen absorption/desorption catalysts at low temperatures, mainly at room temperature (RT). MgH₂ mixtures with 2 mol% additives (Fe, Nb₂O₅, TiAl and TiFe) were prepared by high energy reactive ball milling (RM). MgH₂–TiFe mixture showed the best results, both during desorption at 330 °C and absorption at RT. The hydrogen absorption was ≈ 2.67 wt% H₂ in 1 h and ≈ 4.44 wt% H₂ in 16 h (40% and 67% of maximum theoretical capacity, respectively). The MgH₂–TiFe superior performance was attributed to the hydrogen attraction by the created high energy interfaces and strong TiFe catalytic action facilitating the H₂ flow during Mg/MgH₂ reactions.     

Mechanisms of hydrides’ nucleation and the effect of hydrogen pressure induced driving force on de-/hydrogenation kinetics of Mg-based nanocrystalline alloys

Aiming to gain insight on the hydrogen storage properties of Mg-based alloys, partial hydrogenation and hydrogen pressure related de-/hydrogenation kinetics of Mg–Ni–La alloys have been investigated. The results indicate that the phase boundaries, such as Mg/Mg₂Ni and Mg/Mg₁₇La₂, distributed within the eutectics can act as preferential nucleation sites for β-MgH₂ and apparently promote the hydrogenation process. For bulk alloy, it is observed that the hydrogenation region gradually grows from the fine Mg–Ni–La eutectic to primary Mg region with the extension of reaction time. After high-energy ball milling, the nanocrystalline powders with crystallite size of 12～20 nm exhibit ameliorated hydrogen absorption/desorption performance, which can absorb 2.58 wt% H₂ at 368 K within 50 min and begin to desorb hydrogen from ～508 K. On the other side, variation of hydrogen pressure induced driving force significantly affects the reaction kinetics. As the hydrogenation/dehydrogenation driving forces increase, the hydrogen absorption/desorption kinetics is markedly accelerated. The dehydrogenation mechanisms have also been revealed by fitting different theoretical kinetics models, which demonstrate that the rate-limiting steps change obviously with the variation of driving forces.     

Fast hydrogen absorption/desorption kinetics in reactive milled Mg-8 mol% Fe nanocomposites

This study aims to better understand the Fe role in the hydrogen sorption kinetics of Mg–Fe composites. Mg-8 mol% Fe nanocomposites produced by high energy reactive milling (RM) for 10 h resulted in MgH₂ mixed with free Fe and a low fraction of Mg₂FeH₆. Increasing milling time to 24 h allowed formation of a high fraction of Mg₂FeH₆ mixed with MgH₂. The hydrogen absorption/desorption behavior of the nanocomposites reactive milled for 10 and 24 h was investigated by in-situ synchrotron X-ray diffraction, thermal analyses and kinetics measurements in Sieverts-type apparatus. It was found that both 10 and 24 h milled nanocomposites presents extremely fast hydrogen absorption/desorption kinetics in relatively mild conditions, i.e., 300–350 °C under 10 bar H₂ for absorption and 0.13 bar H₂ for desorption. Nanocomposites with MgH₂, low Fe fraction and no Mg₂FeH₆ are suggested to be the most appropriate solution for hydrogen storage under the mild conditions studied.     

Composition dependent hydrogen storage performance and desorption factors of Mg–Ce based alloys

The widespread application of Mg as a hydrogen storage material has been limited by its slow absorption and desorption kinetics at moderate temperatures. Aiming at improving the de-/absorption kinetics of Mg-based alloys by in situ formed catalysts and understanding the desorption factors, Mg–Ce and Mg–Ce–Ni alloys with different Ce contents are prepared. The phase components, microstructure and hydrogen storage properties have been carefully investigated. It is shown that an 18R-type long-period stacking ordered (LPSO) phase is formed in as-melt Mg–Ce–Ni ternary alloy together with random stacking faults. Abundant in situ formed CeH_2.73 particles with particle size less than 100 nm are observed on the matrix after hydrogenation. It is found in isothermal hydrogenation and dehydrogenation kinetic curves that Ni significantly favors desorption process, while Ce is more conducive to absorption. After partial dehydrogenation of Mg–Ce binary alloy, the initial desorption temperature decreases significantly when desorbing again. The primary-formed Mg phase on the surface of MgH₂ accounts for the improved desorption performance.     

Thermal decomposition of titanium hydrides in electrochemically hydrogenated electron beam melting (EBM) and wrought Ti–6Al–4V alloys using in situ high-temperature X-Ray diffraction

Thermal decomposition of titanium hydrides in electrochemically hydrogenated electron beam melting (EBM) and wrought Ti–6Al–4V alloys containing 6 wt% β is compared. Differential scanning calorimetry (DSC) is used to identify phase transitions. High-temperature X-ray diffraction (HTXRD) is used to identify phases and determine their contents and crystallographic parameters. Both alloys are found to contain α_H (hcp) and β_H (bcc) solid solutions, as well as δ_a (fcc) and δ_b (fcc) hydrides after hydrogenation. δ_a is found to decompose between room temperature and 350 °C to α_H (in both alloys) plus either β_H and δ_b (wrought alloy) or δ_b only (EBM alloy). δ_b fully decomposes at either 450 °C (wrought alloy) or 600 °C (EBM alloy) to α_H plus H₂ desorption (which starts at 300 and 350 °C in the wrought and EBM alloys, respectively). In the case of the wrought alloy, β_H is also formed in this decomposition reaction due to faster diffusion of hydrogen. The non-continuous, finer needle-like morphology of the β-phase in the as-printed EBM alloy combined with its smaller lattice constants seem to inhibit hydrogen diffusion into the bulk alloy through the β-phase, thus triggering δ_a dissociation into δ_b (rather than to β_H+δ_b) and δ_b decomposition into α_H (rather than to α_H + β_H). Hydrogen incorporation in the α_H phase results in its expansion in the c direction in both alloys. HTXRD allows to conclude that both δ_a and δ_b hydrides decompose up to 600 °C. Hydrogen peaks measured at higher temperatures are due to hydrogen desorption from the hydride that is decomposed from the sample's bulk and/or hydrogen desorption from β_H and/or α_H during heating. These findings indicate that the EBM Ti–6Al–4V alloy might be more prone to hydrogen damage at elevated temperatures than its wrought counterpart when both have a similar β-phase content.     

The catalytic effect of Fe and Cr on hydrogen and deuterium absorption in Mg thin films

We examined the deuterium absorption and desorption of 55 nm thick Mg films alloyed with Fe and Cr using in-situ neutron reflectometry. The Mg alloy films were covered with bimetallic catalyst layers and could be fully absorbed at room temperature at a pressure of 8 mbar. The NR experiments revealed a deuterium gradient within the Mg alloy layers during absorption and a large deuterium uptake up to a D/M ratio of about 0.45 before the layer started to expand and form magnesium deuteride (MgD₂). Our NR data suggest that the catalytic effect of the Fe–Cr alloy is based on the avoidance of the formation of a blocking MgD₂ layer in the early stages of the absorption process leading to a fast hydrogen absorption kinetics.     

Enhanced hydrogen desorption/absorption properties of magnesium hydride with CeF3@Gn

In order to improve the hydrogen storage performance of MgH₂, graphene and CeF₃ co-catalyzed MgH₂ (hereafter denoted as MgH₂+CeF₃@Gn) were prepared by wet method ball milling and hydriding, which is a simple and time-saving method. The effect of CeF₃@Gn on the hydrogen storage behavior of MgH₂ was investigated. The experimental results showed that co-addition of CeF₃@Gn greatly decreased the hydrogen desorption/absorption temperature of MgH₂, and remarkably improved the dehydriding/hydriding kinetics of MgH₂. The onset hydrogen desorption temperature of Mg + CeF₃@Gn is 232 °C，which is 86 °C lower than that of as-milled undoped MgH₂, and its hydrogen desorption capacity reaches 6.77 wt%, which is 99% of its theoretical capacity (6.84 wt%). At 300 °C and 200 °C the maximum hydrogen desorption rates are 79.5 and 118 times faster than that of the as-milled undoped MgH₂. Even at low temperature of 150 °C, the dedydrided sample (Mg + CeF₃@Gn) also showed excellent hydrogen absorption kinetics, it can absorb 5.71 wt% hydrogen within 50 s, and its maximum hydrogen absorption rate reached 15.0 wt% H₂/min, which is 1765 times faster than that of the undoped Mg. Moreover, no eminent degradation of hydrogen storage capacity occurred after 15 hydrogen desorption/absorption cycles. Mg + CeF₃@Gn showed excellent hydrogen de/absorption kinetics because of the MgF₂ and CeH_2-3 that are formed in situ, and the synergic catalytic effect of these by-products and unique structure of Gn.     

Activation and de/ hydriding behavior in Ti23V40Mn37 alloy by Hf and Hf/Cr substitutions

To improve absorption/desoprtion rate and hydrogen desorption capacity of Ti–V–Mn alloy, Ti₂₃V₄₀Mn₃₇ alloys by Hf and Hf/Cr substitutions were prepared, the activation and hydriding/dehydriding behaviors of the alloys are investigated. Results show that the lattice parameter of BCC phase increases and the ratio of C14 Laves phase also increases by the substitutions. Ti₁₉Hf₄V₄₀Mn₃₅Cr₂ alloy exhibits the rapid absorption/desoprtion rate and the highest hydrogen desorption capacity of 1.58 wt% H₂ at 293 K. The Hydrogenation kinetic mechanism of the alloys is transformed from nucleation-growth to diffusion, and the dehydrogenation kinetic mechanism is only nucleation-growth. The activation energy of Hf/Cr substituted alloy is lower than that of Hf-free alloy, with the values of 53.79 kJ mol⁻¹ H₂ and 90.13 kJ mol⁻¹ H₂ respectively, which is accounted for the easily absorption of hydrogen molecules on the particle surface and the rapid H diffusion of the interior of alloy, thus the substituted alloys have rapid absorption/desoprtion rate.     

Study on the eutectic formation and its correlation with the hydrogen storage properties of Mg98Ni2-xLax alloys

Transition metals and rare-earth elements have excellent catalytic effects on improving the de-/hydrogenation properties of Mg-based alloys. In this study, a small amount of La is used to substitute the Ni in Mg₉₈Ni₂ alloy, and some Mg₉₈Ni_2-xLa_x (x = 0, 0.33, 0.67, and 1) alloys show the better overall hydrogen storage properties. The effects of La on the solidification and de-/hydrogenation behaviors of the alloys are revealed. The results indicate that different factors dominate the processes of hydrogen absorption and desorption. The Mg₉₈Ni_1·67La_0.33 alloy absorb 7.04 wt % hydrogen at 300 °C, with the highest isothermal absorption rate, the Mg₉₈Ni_1·33La_0.67 hydride show the highest isothermal desorption rates and the lowest peak desorption temperature of 327 °C. The La addition can increase the driving force of hydrogenation, thus the hydrogenation rates and capacities of the Mg₉₈Ni_1·67La_0.33 and Mg₉₈Ni_1·33La_0.67 alloys are improved. The formation of refined eutectic structures is a key factor that facilitates the desorption processes of the Mg₉₈Ni_2-xLa_x hydrides with x = 0.67 and 1. High-density LaH₃ nanophses are in-situ formed from the LaMg_x (8.5 < x < 12) phase, which results in the improved de-/hydrogenation properties. The further La addition deteriorates the hydrogen storage properties of Mg₉₈Ni_2-xLa_x alloy.