Deflagration characteristics of freely propagating flames in magnesium hydride dust clouds

The flame propagation processes of MgH_(2)dust clouds with four different particle sizes were recorded by a high-speed camera.The dynamic flame temperature distributions of MgH_(2)dust clouds were reconstructed by the two-color pyrometer technique,and the chemical composition of solid combustion residues were analyzed.The experimental results showed that the average flame propagation velocities of 23μm,40μm,60μm and 103μm MgH_(2)dust clouds in the stable propagation stage were 3.7 m/s,2.8 m/s,2.1 m/s and 0.9 m/s,respectively.The dust clouds with smaller particle sizes had faster flame propagation velocity and stronger oscillation intensity,and their flame temperature distributions were more even and the temperature gradients were smaller.The flame structures of MgH_(2)dust clouds were significantly affected by the particle sinking velocity,and the combustion processes were accompanied by micro-explosion of particles.The falling velocities of 23μm and 40μm MgH_(2)particles were 2.24 cm/s and 6.71 cm/s,respectively.While the falling velocities of 60μm and 103μm MgH_(2)particles were as high as 15.07 cm/s and 44.42 cm/s,respectively,leading to a more rapid downward development and irregular shape of the flame.Furthermore,the dehydrogenation reaction had a significant effect on the combustion performance of MgH_(2)dust.The combustion of H_(2)enhanced the ignition and combustion characteristics of MgH_(2)dust,resulting in a much higher explosion power than the pure Mg dust.The micro-structure characteristics and combustion residues composition analysis of MgH_(2)dust indicated that the combustion control mechanism of MgH_(2)dust flame was mainly the heterogeneous reaction,which was affected by the dehydrogenation reaction.

Recent progress in thermodynamic and kinetics modification of magnesium hydride hydrogen storage materials

Hydrogen energy has emerged as a pivotal solution to address the global energy crisis and pave the way for a cleaner,low-carbon,secure,and efficient modern energy system.A key imperative in the utilization of hydrogen energy lies in the development of high-performance hydrogen storage materials.Magnesium-based hydrogen storage materials exhibit remarkable advantages,including high hydrogen storage density,cost-effectiveness,and abundant magnesium resources,making them highly promising for the hydrogen energy sector.Nonetheless,practical applications of magnesium hydride for hydrogen storage face significant challenges,primarily due to their slow kinetics and stable thermodynamic properties.Herein,we briefly summarize the thermodynamic and kinetic properties of MgH2,encompassing strategies such as alloying,nanoscaling,catalyst doping,and composite system construction to enhance its hydrogen storage performance.Notably,nanoscaling and catalyst doping have emerged as more effective modification strategies.The discussion focuses on the thermodynamic changes induced by nanoscaling and the kinetic enhancements resulting from catalyst doping.Particular emphasis lies in the synergistic improvement strategy of incorporating nanocatalysts with confinement materials,and we revisit typical works on the multi-strategy optimization of MgH2.In conclusion,we conduct an analysis of outstanding challenges and issues,followed by presenting future research and development prospects for MgH2 as hydrogen storage materials.

Properties of radiation defects and threshold energy of displacement in zirconium hydride obtained by new deep-learning potential

Zirconium hydride(ZrH_(2)) is an ideal neutron moderator material. However, radiation effect significantly changes its properties, which affect its behavior and the lifespan of the reactor. The threshold energy of displacement is an important quantity of the number of radiation defects produced, which helps us to predict the evolution of radiation defects in ZrH_(2).Molecular dynamics(MD) and ab initio molecular dynamics(AIMD) are two main methods of calculating the threshold energy of displacement. The MD simulations with empirical potentials often cannot accurately depict the transitional states that lattice atoms must surpass to reach an interstitial state. Additionally, the AIMD method is unable to perform largescale calculation, which poses a computational challenge beyond the simulation range of density functional theory. Machine learning potentials are renowned for their high accuracy and efficiency, making them an increasingly preferred choice for molecular dynamics simulations. In this work, we develop an accurate potential energy model for the ZrH_(2) system by using the deep-potential(DP) method. The DP model has a high degree of agreement with first-principles calculations for the typical defect energy and mechanical properties of the ZrH_(2) system, including the basic bulk properties, formation energy of point defects, as well as diffusion behavior of hydrogen and zirconium. By integrating the DP model with Ziegler–Biersack–Littmark(ZBL) potential, we can predict the threshold energy of displacement of zirconium and hydrogen in ε-ZrH_(2).

Phase-field simulations of the effect of temperature and interface for zirconiumδ-hydrides

Hydride precipitation in zirconium cladding materials can damage their integrity and durability.Service temperature and material defects have a significant effect on the dynamic growth of hydrides.In this study,we have developed a phasefield model based on the assumption of elastic behaviour within a specific temperature range(613 K-653 K).This model allows us to study the influence of temperature and interfacial effects on the morphology,stress,and average growth rate of zirconium hydride.The results suggest that changes in temperature and interfacial energy influence the length-to-thickness ratio and average growth rate of the hydride morphology.The ultimate determinant of hydride orientation is the loss of interfacial coherency,primarily induced by interfacial dislocation defects and quantifiable by the mismatch degree q.An escalation in interfacial coherency loss leads to a transition of hydride growth from horizontal to vertical,accompanied by the onset of redirection behaviour.Interestingly,redirection occurs at a critical mismatch level,denoted as qc,and remains unaffected by variations in temperature and interfacial energy.However,this redirection leads to an increase in the maximum stress,which may influence the direction of hydride crack propagation.This research highlights the importance of interfacial coherency and provides valuable insights into the morphology and growth kinetics of hydrides in zirconium alloys.

Unveiling a novel metal-to-metal transition in LuH_(2):Critically challenging superconductivity claims in lutetium hydrides

Following the recent report by Dasenbrock-Gammon et al.[Nature 615,244–250(2023)]of near-ambient superconductivity in nitrogendoped lutetium trihydride(LuH_(3-δ)N_(ε)),significant debate has emerged surrounding the composition and interpretation of the observed sharp resistance drop.Here,we meticulously revisit these claims through comprehensive characterization and investigations.We definitively identify the reported material as lutetium dihydride(LuH_(2)),resolving the ambiguity surrounding its composition.Under similar conditions(270–295 K and 1–2 GPa),we replicate the reported sharp decrease in electrical resistance with a 30%success rate,aligning with the observations by Dasenbrock-Gammon et al.However,our extensive investigations reveal this phenomenon to be a novel pressure-induced metal-to-metal transition intrinsic to LuH_(2),distinct from superconductivity.Intriguingly,nitrogen doping exerts minimal impact on this transition.Our work not only elucidates the fundamental properties of LuH_(2)andLuH_(3),but also critically challenges the notion of superconductivity in these lutetium hydride systems.These findings pave the way for future research on lutetium hydride systems,while emphasizing the crucial importance of rigorous verification in claims of ambient-temperature superconductivity.

Understanding the catalysis of chromium trioxide added magnesium hydride for hydrogen storage and Li ion battery applications

This study explores how the chemical interaction between magnesium hydride(MgH_(2))and the additive CrO_(3) influences the hydrogen/lithium storage characteristics of MgH_(2).We have observed that a 5 wt.%CrO_(3) additive reduces the dehydrogenation activation energy of MgH_(2) by 68 kJ/mol and lowers the required dehydrogenation temperature by 80℃.CrO_(3) added MgH_(2) was also tested as an anode in an Li ion battery,and it is possible to deliver over 90%of the total theoretical capacity(2038 mAh/g).Evidence for improved reversibility in the battery reaction is found only after the incorporation of additives with MgH_(2).In depth characterization study by X-ray diffraction(XRD)technique provides convincing evidence that the CrO_(3) additive interacts with MgH_(2) and produces Cr/MgO byproducts.Gibbs free energy analyses confirm the thermodynamic feasibility of conversion from MgH_(2)/CrO_(3) to MgO/Cr,which is well supported by the identification of Cr(0)in the powder by X ray photoelectron spectroscopy(XPS)technique.Through high resolution transmission electron microscopy(HRTEM)and energy dispersive spectroscopy(EDS)we found evidence for the presence of 5 nm size Cr nanocrystals on the surface of MgO rock salt nanoparticles.There is also convincing ground to consider that MgO rock salt accommodates Cr in the lattice.These observations support the argument that creation of active metal–metal dissolved rock salt oxide interface may be vital for improving the reactivity of MgH_(2),both for the improved storage of hydrogen and lithium.

Magnesium nickel hydride monocrystalline nanoparticles for reversible hydrogen storage

Although Mg-based hydrides are extensively considered as a prospective material for solid-state hydrogen storage and clean energy carriers,their high operating temperature and slow kinetics are the main challenges for practical application.Here,a Mg-Ni based hydride,Mg_(2)NiH_(4) nanoparticles(~100 nm),with dual modification strategies of nanosizing and alloying is successfully prepared via a gas-solid preparation process.It is demonstrated that Mg_(2)NiH_(4) nanoparticles form a unique chain-like structure by oriented stacking and exhibit impressive hydrogen storage performance:it starts to release H2 at~170℃ and completes below 230℃ with a saturated capacity of 3.32 wt%and desorbs 3.14 wt% H_(2) within 1800 s at 200℃.The systematic characterizations of Mg_(2)NiH_(4) nanoparticles at different states reveal the dehydrogenation behavior and demonstrate the excellent structural and hydrogen storage stabilities during the de/hydrogenated process.This research is believed to provide new insights for optimizing the kinetic performance of metal hydrides and novel perspectives for designing highly active and stable hydrogen storage alloys.

Dinitrogen fixation mediated by lanthanum hydride

Dinitrogen fixation is one of the key reactions in chemistry, which is closely associated with food, environment, and energy. It has been recently recognized that the hydride materials containing negatively charged hydrogen(H~-) show promises for Nfixation and hydrogenation to ammonia. Herein, we report that rare earth metal hydrides such as lanthanum hydride can also fix Neither by heating to 200 °C or ball milling under ambient Npressure and temperature. The Nfixation by lanthanum hydride may proceed via an intermediate lanthanum hydride-nitride(La-H-N) structure to form the final lanthanum nitride product. The hydride ion functions as an electron donor, which provides electrons for Nactivation possibly mediated by the lanthanum atoms. It is observed that N–H bond is not formed during the Nfixation process, which is distinctly different from the alkali or alkaline earth metal hydrides. The hydrolysis of La-H-N to ammonia is feasible using water as the hydrogen source. These results provide new insights into the nitrogen fixation by hydride materials and more efforts are needed for the development of rare earth metal-based catalysts and/or nitrogen carriers for ammonia synthesis processes.

A new mutually destabilized reactive hydride system:LiBH4–Mg2NiH4

In this work,the hydrogen sorption properties of the LiBH4-Mg2NiH4 composite system with the molar ratio 2:2.5 were thoroughly investigated as a function of the applied temperature and hydrogen pressure.To the best of our knowledge,it has been possible to prove experimentally the mutual destabilization between LiBH4 and Mg2NiH4.A detailed account of the kinetic and thermodynamic features of the dehydrogenation process is reported here.

Hydrogen desorption kinetics mechanism of Mg-Ni hydride under isothermal and non-isothermal conditions

The Mg-Ni hydride was prepared by hydriding combustion synthesis under a high magnetic field. The dehydriding kinetics of the hydrides was measured under the isothermal and non-isothermal conditions. A model was applied to analyzing the kinetics behavior of Mg-Ni hydride. The calculation results show that the theoretical value and the experimental data can reach a good agreement, especially in the case of non-isothermal dehydriding. The rate-controlling step is the diffusion of hydrogen atoms in the solid solution. The sample prepared under magnetic field of 6 T under the isothermal condition can reach the best performance. The similar tendency was observed under the non-isothermal condition and the reason was discussed.

STRUCTURE OF HYDRIDES IN HIGHLY HYDROGENATED Ti-6Al-4V ALLOY

The microstrueture and various hydrides precipitated in Ti-6A1-4V alloys containing hydrogen 0.16,0.58,0.87,1.49 wt-%,respectively,have been studied by means of TEM and X-ray diffraction.The Ti_3Al phase may precipitate when H over 0.58 wt-%.In the same time,the morphology of hydrides gradually changed from rugged sheets to narrow laths as H contents increased.The microstructure of highly H-doped alloys is obviously fine.A mas- sive hydride and the hydride with tetragonal lattice were observed in the specimen containing 1.49 wt-%H.The twin hydrides were found in the alloys with different H contents and the electron diffraction patterns of the twin hydrides can be served as a simple criterion for distin- guishing the cubic and tetragonal structures.

IN-SITU ELECTRON MICROSCOPY STUDY ON PRECIPITATION OF ZIRCONIUM HYDRIDES INDUCED BY STRESS AND STRAIN IN ZIRCALOY-2

The precipitation process of zirconium hydrides induced by stress and strain was investigated by means of electron microscopy in-situ.The precipitating hydrides induced by stress were found to be γ phase with orientation relationship of (110)_γ‖(110)_(αZr),(001)_γ‖ (0001)_(αZr) between γ-hydrides and surrounding matrix.The growth rate of γ-hydrides which was much faster along [110] direction brought them in taper shape.After fracture of y-hydrides,a new one will precipitate at the tip of cracks.This is the essential process of hydrogen-induced delayed cracking in Zircaloy.The precipitating hydrides induced by strain were found to be δ phase with both orientation relationships of(111)_δ‖(0001)_(αZr),(110)_δ‖ (110)_(αZr) or (010)_δ‖(0001)_(αZr),(001)_δ‖(110)_(αZr)between δ-hydride and surrounding matrix.The δ-hydrides become much finer as the strain rate increased.

Possible Evolutionary Models in the Initially Hydride Earth Theory

A modern view of the properties of chemical elements has confirmed the theory of the hot origin of the Earth. The next step in developing this theory was the hypothesis of the initial hydride Earth. In this work, we attempted to find additional evidence for this hypothesis and show additional effects that flow from it. The effect of the physical properties of atoms and ions on their behavior during the formation of the Earth was studied. The maximum contribution to the distribution of elements was made by those elements whose content in the original protoplanets of the disk was the maximum. Correlation dependence is obtained, which allows one to calculate the distribution of elements in the protoplanetary disk. It was shown that hydrogen was the main element in the proto substance located in the zone of the Earth’s formation. In this case, various chemical compounds formed, most represented by hydrogen compounds—hydrides. Since the pressure inside the Earth is 375 GPa, this factor forces the chemical compounds to adopt stoichiometry and structure that would not be available in atmospheric conditions. It is shown that many chemical elements at high pressure in a hydrogen medium form simple hydrides and super hydrides—polyhydrides with high hydrogen content. Pressure leads to a higher density of matter inside the planet. Given the possibility of forming polyhydrides, there is the possibility of binding the initially available hydrogen in an amount that can reach 49.3 mole%. Young Earth could contain about 10.7 mass% of hydrogen in hydrides, polyhydrides, and adsorbed form is almost twice higher than previous estimates. This fact additionally confirms the theory of the original hydride Earth. In hydrides, the occurrence of the phenomenon of superconductivity was discovered. Polyhydrides were shown as potential superconductors with a high critical temperature above 200 K. We, based on these data, hypothesized the presence of superconducting properties in the Earth’s core, which explains the presence of a magnetic field in the Earth, as well as the unevenness and instability of this field and the possibility of migration of the Earth’s poles. The fact that the Earth has a hydroid core causes its change in time due to the instability of hydrides. Arranged several possible models of the destruction of the Earth’s core. The calculations showed that both models give close results. These results give predictions that can be measured. The proposed models also made it possible to estimate the initial size of the Earth. Possible ways of further testing the hypothesis of the initial hydride Earth is shown.

Enhanced dehydrogenation performances and mechanism of LiBH_4/Mg_(17)Al_(12)-hydride composite

Mg17Al12-hydride （abbreviated as MAH） was selected as a destabilization agent to improve de/rehydrogenation properties of LiBH4. 58LiBH4＋Mg17Al12-hydride composite was prepared by ball-milling. It is found that the dehydrogenation of ball-milled LiBH4/MAH composite presents a two-step reaction for hydrogen release. The composite starts desorbing hydrogen at about 300 ℃ and yields 9.8%of hydrogen （mass fraction） below 500 ℃. By adding MAH, the dehydrogenation kinetics of LiBH4 is improved and the dehydrogenation temperature of LiBH4 is also lowered by 20 ℃. High rehydriding capacity of 8.3% was obtained for the dehydrogenated composite in the first cycle at 450 ℃. The XRD analysis shows the formation of MgB2 and AlB2 in the dehydrogenation process, which reduces the thermodynamics stability of LiBH4 system and is beneficial to the reversible hydrogen storage behaviors of LiBH4/MAH composite.

Stabilization of low-valence transition metal towards advanced catalytic effects on the hydrogen storage performance of magnesium hydride

Magnesium hydride(MgH_(2))has been widely regarded as a potential hydrogen storage material owing to its high gravimetric and volumetric capacity.Its sluggish kinetics and high activation energy barrier,however,severely limit its practical application.Transition metal oxides(TMOs)have been extensively used as catalysts to improve the hydrogen storage performance of MgH_(2),but the low-valence transition metal(TM)ions,resulting from the reduction of TMOs accompanied by the formation of inactive Mg O,have been demonstrated to be the most effective components.Herein,we theoretically and experimentally confirm that the doping of low-valence TMs into Mg O could effectively weaken the Mg-H bonds and decrease the energy required for hydrogen desorption from MgH_(2),leading to superior catalytic activity compared to both TMOs and Mg O.In particular,the apparent activation energy for the dehydrogenation of Mg(Nb)O-catalyzed MgH_(2)could be reduced to only 84.1 kJ mol^(-1),and the reversible capacity could reach around 7 wt.%after 5 cycles with a capacity retention of 96%.Detailed theoretical calculations confirm that the remarkable orbital hybridization between Mg(Nb)O and MgH_(2)promotes charge transfer from MgO to the MgH_(2)monomer,resulting in significantly weakened stability of MgH_(2),which could effectively enhance its hydrogen storage performance.

Perspectives and challenges of hydrogen storage in solid-state hydrides

Hydrogen has been widely considered as a clean energy carrier that bridges the energy producers and energy consumers in an efficient and safe way for a sustainable society.Hydrogen can be stored in a gas,liquid and solid states and each method has its unique advantage.Though compressed hydrogen and liquefied hydrogen are mature technologies for industrial applications,appropriate measures are necessary to deal with the issues at high pressure up to around 100 MPa and low temperature at around 20 K.Distinct from those technologies,storing hydrogen in solid-state hydrides can realize a more compact and much safer approach that does not require high hydrogen pressure and cryogenic temperature.In this review,we will provide an overview of the majormaterial groups that are capable of absorbing and desorbing hydrogen reversibly.The main features on hydrogen storage properties of each material group are summarized,together with the discussion of the key issues and the guidance of materials design,aiming at providing insights for new material development as well as industrial applications.

Properties of hydrogen permeation barrier on the surface of zirconium hydride

A hydrogen permeation barrier was manufactured by the in situ reaction of zirconium hydride with oxygen. A reduction in the hydrogen permeation of the oxide films was detected by measuring the mass difference of the zirconium hydride samples after the dehydrogenation experiment. The reaction of zirconium hydride with oxygen occurs only under the condition that the temperature is higher than 673 K in the oxygen partial pressure of 0.1 MPa. The oxide film is composed of two layers, a permeable oxide layer and a dense oxide layer, and the main phase of the oxide film is ZrO2 with baddeleyite structure. The XPS analysis shows that O-H bonds exist in the oxide film, which are helpful for resisting hydrogen diffusion through the oxide film.

Superconductivity of Lanthanum Superhydride Investigated Using the Standard Four-Probe Configuration under High Pressures

Recently,the theoretically predicted lanthanum superhydride,LaH 10±δ,with a clathrate-like structure was successfully synthesized and found to exhibit a record high superconducting transition temperature T c≈250 K at∼170 GPa,opening a new route for room-temperature superconductivity.However,since in situ experiments at megabar pressures are very challenging,few groups have reported the∼250 K superconducting transition in LaH 10±δ.Here,we establish a simpler sample-loading procedure that allows a relatively large sample size for synthesis and a standard four-probe configuration for resistance measurements.Following this procedure,we successfully synthesized LaH 10±δwith dimensions up to 10×20μm^2 by laser heating a thin La flake and ammonia borane at∼1700 K in a symmetric diamond anvil cell under the pressure of 165 GPa.The superconducting transition at T c≈250 K was confirmed through resistance measurements under various magnetic fields.Our method will facilitate explorations of near-room-temperature superconductors among metal superhydrides.

Degradation Behavior of Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

The degradation mechanism of electrochemical performance of sealed type nickel/metal hydride batteries was investigated. The results indicate that the degradation behavior of Ni/MH battery is not only owing to the lack of electrolyte, but also the deterioration of the active materials on the positive and negative electrodes of Ni/MH batteries. Scanning electron micrographs (SEM), X ray diffraction (XRD) and laser granularity analyses are presented. The particle pulverization and oxidation during charge/discharge are identified as the main causes for deterioration of the negative and positive electrode in nickel/metal hydride batteries, as well as the cross section cracking of both anode and cathode.

Unexpected formation of hydrides in heavy rare earth containing magnesium alloys

Mg–RE(Dy,Gd,Y)alloys show promising for being developed as biodegradable medical applications.It is found that the hydride REH_(2) could be formed on the surface of samples during their preparations with water cleaning.The amount of formed hydrides in Mg–RE alloys is affected by the content of RE and heat treatments.It increases with the increment of RE content.On the surface of the alloy with T4 treatment the amount of formed hydride REH_(2) is higher.In contrast,the amount of REH2 is lower on the surfaces of as-cast and T6-treated alloys.Their formation mechanism is attributed to the surface reaction of Mg–RE alloys with water.The part of RE in solid solution in Mg matrix plays an important role in influencing the formation of hydrides.