La-Mg-Ni-based hydrogen storage alloys with superlattice structures are the new generation anode material for nickel metal hydride(Ni-MH)batteries owing to the advantages of high capacity and exceptional activation pr...La-Mg-Ni-based hydrogen storage alloys with superlattice structures are the new generation anode material for nickel metal hydride(Ni-MH)batteries owing to the advantages of high capacity and exceptional activation properties.However,the cycling stability is not currently satisfactory enough which plagues its application.Herein,a strategy of partially substituting La with the Y element is proposed to boost the capacity durability of La-Mg-Ni-based alloys.Furthermore,phase structure regulation is implemented simultaneously to obtain the A5 B19-type alloy with good crystal stability specifically.It is found that Y promotes the phase formation of the Pr5 Co19-type phase after annealing at 985℃.The alloy containing Y contributes to the superior rate capability resulting from the promoted hydrogen diffusion rate.Notably,Y substitution enables strengthening the anti-pulverization ability of the alloy in terms of increasing the volume match between[A_(2)B_(4)]and[AB5]subunits,and effectively enhances the anti-corrosion ability of the alloy due to high electronegativity,realizing improved long-term cycling stability of the alloy from 74.2%to 78.5%after cycling 300 times.The work is expected to shed light on the composition and structure design of the La-Mg-Ni-based hydrogen storage alloy for Ni-MH batteries.展开更多
MgH_(2) has been extensively studied as one of the most ideal solid hydrogen storage materials.Nevertheless,rapid capacity decay and sluggish hydrogen storage kinetics hamper its practical application.Herein,a Ni/C na...MgH_(2) has been extensively studied as one of the most ideal solid hydrogen storage materials.Nevertheless,rapid capacity decay and sluggish hydrogen storage kinetics hamper its practical application.Herein,a Ni/C nano-catalyst doped MgH_(2)(MgH_(2)–Ni/C)shows an improved hydrogen absorption kinetics with largely reduced activation energy.Particularly,the MgH_(2)–Ni/C displays remarkable cycling stability,which maintains a high capacity of 6.01 wt.%(98.8%of initial capacity)even after 50 full hydrogen ab/desorption cycles,while the undoped MgH_(2) counterpart retains only 85.2%of its initial capacity.Detailed microstructure characterizations clearly reveal that particle sintering/growth accounts primarily for the deterioration of cycling performance of undoped MgH_(2).By comparison,MgH_(2)–Ni/C can maintain a stable particle size with a growing porous structure during long-term cycling,which effectively increases the specific surface of the particles.A novel carbon-induced-porosity stabilization mechanism is proposed,which can stabilize the proportion of rapid hydrogen absorption process,thus dominating the excellent cycling performance of MgH_(2)–Ni/C.This study provides new insights into the cycling stability mechanism of carbon-containing Mg-based hydrogen storage materials,thus promoting their practical applications.展开更多
Hydrogen,as a cheap,clean,and cost-effective secondary energy source,performs an essential role in optimizing today’s energy structure.Magnesium hydride(Mg H_(2))represents an attractive hydrogen carrier for storage ...Hydrogen,as a cheap,clean,and cost-effective secondary energy source,performs an essential role in optimizing today’s energy structure.Magnesium hydride(Mg H_(2))represents an attractive hydrogen carrier for storage and transportation,however,the kinetic behavior and operating temperature remain undesirable.In this work,a dual-phase multi-site alloy(Ms A)anchored on carbon substrates was designed,and its superior catalytic effects on the hydrogen storage properties of MgH_(2) were reported.Mechanism analysis identified that multi-site Fe Ni_(3)/Ni Cu nanoalloys synergistically served as intrinsic drivers for the striking de/hydrogenation performance of the MgH_(2)-Ms A systems.Concretely,the unique multi-metallic site structure attached to the surface of MgH_(2)provided substantial reversible channels and accessible active sites conducive to the adsorption,activation,and nucleation of H atoms.In addition,the coupling system formed by FeNi_(3) and NiCu dual-phase alloys further enhanced the reactivity between Mg/MgH_(2) and H atoms.Hence,the onset dehydrogenation temperature of Mg H_(2)+5 wt%Ms A was reduced to 195℃ and the hydrogen desorption apparent activation energy was reduced to 83.6 k J/mol.5.08 wt%H_(2) could be released at 250℃ in 20 min,reaching a high dehydrogenation rate of 0.254 wt%H_(2)/min,yet that for MgH_(2) at a higher temperature of 335℃ was only 0.145 wt%H_(2)/min.Then,the dehydrogenated Mg H_(2)-Ms A sample could absorb hydrogen from room temperature(30℃)and charge 3.93 wt%H_(2) at 100℃ within20 min under 3.0 MPa H_(2) pressure.Benefiting from carbon substrates,the 5 wt%Ms A doped-MgH_(2) could still maintain 6.36 wt%hydrogen capacity after 20 cycles.In conclusion,this work provides experimental rationale and new insights for the design of efficient catalysts for magnesium-based solid-state hydrogen storage materials.展开更多
Catalytic doping is one of the economic and efficient strategies to optimize the operating temperature and kinetic behavior of magnesium hydride(MgH_(2)).Herein,efficient regulation of electronic and structural rearra...Catalytic doping is one of the economic and efficient strategies to optimize the operating temperature and kinetic behavior of magnesium hydride(MgH_(2)).Herein,efficient regulation of electronic and structural rearrangements in niobium-rich nickel oxides was achieved through precise compositional design and niobium cation functionalized doping,thereby greatly enhancing its intrinsic catalytic activity in hydrogen storage systems.As the niobium concentration increased,the Ni-Nb catalysts transformed into a mixed state of multi-phase nanoparticles(composed of nickel and niobium-rich nickel oxides)with smaller particle size and uniform distribution,thus exposing more nucleation sites and diffusion channels at the MgH_(2)/Mg interface.In addition,the additional generation of active Ni-Nb-O mixed phase induced numerous highly topical disordered and distorted crystalline,promoting the transfer and reorganization of H atoms.As a result,a stable and continuous multi-phase/component synergistic catalytic microenvironment could be constructed,exerting remarkable enhancement on MgH_(2)’s hydrogen storage performance.After comparative tests,Ni_(0.7)Nb_(0.3)-doped MgH_(2) presented the optimal low-temperature kinetics with a dehydrogenation activation energy of 78.8 kJ·mol^(−1).The onset dehydrogenation temperature of MgH_(2)+10 wt%Ni_(0.7)Nb_(0.3) was reduced to 198℃ and 6.18 wt%H_(2) could be released at 250℃ within 10 min.In addition,the dehydrogenated MgH_(2)–NiNb composites absorbed 4.87 wt%H_(2) in 10 min at 125℃ and a capacity retention rate was maintained at 6.18 wt%even after 50 reaction cycles.In a word,our work supplies fresh insights for designing novel defective-state multiphase catalysts for hydrogen storage and other energy related field.展开更多
As a highly reactive reaction intermediate,surface gallium hydride(Ga–H)has garnered significant attention due to its critical role in various catalytic reactions.However,the detailed experimental characterization of...As a highly reactive reaction intermediate,surface gallium hydride(Ga–H)has garnered significant attention due to its critical role in various catalytic reactions.However,the detailed experimental characterization of this unique species remains challenging.Recently,we have demonstrated that solid-state NMR can be an effective tool for studying surface Ga–H.In this work,we report a comparative solid-state NMR study on H_(2) activation over different Ga_(2)O_(3) polymorphs,specificallyα-,β-andγ-Ga_(2)O_(3).^(1)H solid-state NMR enabled the identification of Ga–H species formed on all the three samples following high-temperature H_(2) treatment.The characteristic ^(1)H NMR signals of Ga–H species are resolved using J-coupling-based double-resonance NMR methods,revealing highly similar lineshapes of Ga–H for all the Ga_(2)O_(3) samples.This suggests potentially similar surface Ga–H configurations among different Ga_(2)O_(3) polymorphs.In addition,the local hydrogen environments on the oxide surfaces are further explored using two-dimensional(2D)^(1)H–^(1)H homonuclear correlation spectra,revealing multiple spatially proximate Ga–H and Ga–H/–OH pairs on different Ga_(2)O_(3) polymorphs.These findings provide insights into the potential mechanism of H_(2) dissociation.Overall,this work offers new perspectives on the local structure of surface Ga–H on Ga_(2)O_(3),and the analytical approach presented here can be further extended to the study of other Ga-based catalysts and other metal hydride species.展开更多
To modify the stable thermodynamics and poor kinetics of magnesium hydride(MgH_(2))for solid-state hydrogen storage,MIL-100(Fe)was in situ fabricated on the surfaces of TiO_(2)nano-sheets(NS)by a self-assembly method,...To modify the stable thermodynamics and poor kinetics of magnesium hydride(MgH_(2))for solid-state hydrogen storage,MIL-100(Fe)was in situ fabricated on the surfaces of TiO_(2)nano-sheets(NS)by a self-assembly method,and the prepared TiO_(2)NS@MIL-100(Fe)presents an excellent catalytic effect on MgH_(2).The MgH_(2)+7wt.%TiO_(2)NS@MIL-100(Fe)composite can release hydrogen at 200℃,achieving a decrease of 150℃ compared to pure MgH_(2).Besides,the activation energy of dehydrogenation is decreased to 70.62 kJ/mol and 4 wt.%H_(2) can be desorbed within 20 min at a low temperature of 235℃.Under conditions of 100℃ and 3 MPa,MgH_(2)+7wt.%TiO_(2)NS@MIL-100(Fe)absorbs 5 wt.%of H_(2) in 10 min.Surprisingly,6.62 wt.%reversible capacity is maintained after 50 cycles.The modification mechanism is confirmed that the presence of oxygen vacancies and the synergistic effect of multivalent titanium in TiO_(2)NS@MIL-100(Fe)greatly enhance the kinetic and thermodynamic properties of MgH_(2).展开更多
Dibenzyltoluene(DBT)is a prospective liquid organic hydrogen carrier(LOHC)with low cost and high theoretical hydrogen storage capacity(6.2 wt%).However,the wide application of DBT is severely restricted by expensive n...Dibenzyltoluene(DBT)is a prospective liquid organic hydrogen carrier(LOHC)with low cost and high theoretical hydrogen storage capacity(6.2 wt%).However,the wide application of DBT is severely restricted by expensive noble catalysts.In this work,a new Mg-based metal hydride hydrogenation catalyst,which is composed of MgH_(2),Mg_(2)NiH_(4) and LaH_(3) micro-nano-particles.展开更多
Magnesium hydride(MgH_(2))was highly regarded for its substantial hydrogen storage capacity of up to 7.6 wt%,but its commercial application was hindered by the high operating temperatures and slow kinetics.In this stu...Magnesium hydride(MgH_(2))was highly regarded for its substantial hydrogen storage capacity of up to 7.6 wt%,but its commercial application was hindered by the high operating temperatures and slow kinetics.In this study,the successful synthesis of the layered Ti_(2)NbC_(2) has significantly enhanced the hydrogen storage performance of MgH_(2).MgH_(2)+5 wt%Ti_(2)NbC_(2) began to release hydrogen at 190℃ and started to absorb hydrogen at room temperature.At a constant temperature of 275℃,complete hydrogen release was achieved in just 250 s,up to 6.9 wt%.At 150℃,the absorption of hydrogen reached 6.59 wt%within 200 s,and the hydrogen absorption activation energy was reduced to 41.517±3.981 kJ·mol^(−1),significantly improving the kinetic performance.Moreover,the composite material still exhibited excellent cyclic stability after 20 cycles at 275℃.In the process of hydrogen de/absorption of Ti_(2)NbC_(2) with MgH_(2),active substances Nb-H and Ti-H were generated in situ,which effectively weakened the Mg-H bond and acted as efficient“hydrogen pumps”to accelerate the re/dehydrogenation of MgH_(2).The unique layered structure and hydrogen affinity of Ti_(2)NbC_(2) provided an effective transfer channel for hydrogen migration,which was key to the excellent hydrogen storage performance of the MgH_(2)+Ti_(2)NbC_(2).展开更多
Catalytic doping of magnesium hydride(MgH_(2))to improve its hydrogen ab/desorption kinetic properties is considered to be an effective and feasible method.In solid-phase catalysis,the extent of contact between the ca...Catalytic doping of magnesium hydride(MgH_(2))to improve its hydrogen ab/desorption kinetic properties is considered to be an effective and feasible method.In solid-phase catalysis,the extent of contact between the catalyst and the substrate determines the catalytic reaction in a great sense.With large specific surface area and abundant active sites,two-dimensional(2D)nanomaterials are promising catalysts for MgH_(2)via providing numerous pathways for the diffusion and dissociation of hydrogen.In this regard,2D NiMn-based layered double hydroxide and layered metallic oxide(LMO)are designed and introduced into MgH_(2)to improve its hydrogen storage properties.Simultaneous enhancement in interfacial contact,desorption temperature and kinetics are achieved.The MgH_(2)+9wt%Ni3Mn-LMO composites begin to discharge hydrogen at only 190℃and 6.10wt%H_(2)could be charged in 600 s at 150℃.The activation energy for de/hydrogenation is reduced by 42.43%and 46.56%,respectively,compared to pure MgH_(2).Even at a low operating temperature of 235℃,the modified system was still able to release 4.44wt%H_(2)in an hour,which has rarely been reported in previous studies.Microstructure observations and density functional theory calculations revealed that first,the hydrogen pumping effect of Mg_(2)Ni/Mg_(2)NiH_(4) promotes the adsorption and desorption of hydrogen molecules on the surface of MgH_(2),second,MnOx drew electrons from Mg_(2)Ni,producing a new Density of State structure with a lower d-bond center.This unique change further strengthens the Mg_(2)Ni/Mg_(2)NiH_(4) pump effect on MgH_(2).Our work indicates that the application of 2D metal-based catalysts is a feasible and promising approach towards MgH_(2)for solid-state hydrogen storage to meet technical and scientific requirements.展开更多
Rare earth-Mg-Ni-based superlattice structure alloys have garnered recognition as promising materials for hydrogen storage.However,their application is impeded by suboptimal cycling longevity.The novel AB_(4)-type all...Rare earth-Mg-Ni-based superlattice structure alloys have garnered recognition as promising materials for hydrogen storage.However,their application is impeded by suboptimal cycling longevity.The novel AB_(4)-type alloy emerges as an attractive candidate,distinguished by its good structure stability,high rate capability,and long-term durability.Herein,we designed an AB_(4)-type La_(0.6)0Sm_(0.22)Mg_(0.18)Ni_(4.09)Al_(0.09)Mn_(0.10)alloy that manifests superior electrochemical performance.The obtained AB_(4)-type single-phase alloy delivers a high discharge capacity of 375.2 mAh·g^(-1)and features outstanding discharge ability at high rates,maintaining 121 mAh·g^(-1)even at a discharge rate of 6C.The excellent high-rate discharge performance can be attributed to its fast charge transfer and hydrogen diffusion kinetics.Moreover,the AB_(4)-type alloy maintains a capacity retention of 84.5%after 200 cycles and retains 55.7%of its capacity retention even after 500 cycles.This work provides a good alternative to hydrogen storage alloy with high power and long cycling durability performance for nickel metal hydride batteries.展开更多
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...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.展开更多
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...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.展开更多
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) addi...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.展开更多
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...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.展开更多
MgH_(2),albeit with slow desorption kinetics,has been extensively studied as one of the most ideal solid hydrogen storage materials.Adding such catalyst as Ni can improve the desorption kinetics of MgH_(2),whereas the...MgH_(2),albeit with slow desorption kinetics,has been extensively studied as one of the most ideal solid hydrogen storage materials.Adding such catalyst as Ni can improve the desorption kinetics of MgH_(2),whereas the catalytic role has been attributed to different substances such as Ni,Mg_(2)Ni,Mg_(2)NiH0.3,and Mg_(2)NiH4.In the present study,Ni nanoparticles(Ni-NPs)supported on mesoporous carbon(Ni@C)have been synthesized to improve the hydrogen desorption kinetics of MgH_(2).The utilization of Ni@C largely decreases the dehydrogenation activation energy from 176.9 to 79.3 kJ mol^(−1) and the peak temperature of dehydrogenation from 375.5 to 235℃.The mechanism of Ni catalyst is well examined by advanced aberration-corrected environmental transmission electron microscopy and/or x-ray diffraction.During the first dehydrogenation,detailed microstructural studies reveal that the decomposition of MgH_(2)is initially triggered by the Ni-NPs,which is the rate-limiting step.Subsequently,the generated Mg reacts rapidly with Ni-NPs to form Mg_(2)Ni,which further promotes the dehydrogenation of residual MgH_(2).In the following dehydrogenation cycle,Mg_(2)NiH4 can rapidly decompose into Mg_(2)Ni,which continuously promotes the decomposition of MgH_(2).Our study not only elucidates the mechanism of Ni catalyst but also helps design and assemble catalysts with improved dehydriding kinetics of MgH_(2).展开更多
The lattice distortion effect and cocktail effect of high-entropy oxides(HEOs)will dominate the catalytic effect of the materials,in order to study the influence of the constituent elements of HEOs on the lattice dist...The lattice distortion effect and cocktail effect of high-entropy oxides(HEOs)will dominate the catalytic effect of the materials,in order to study the influence of the constituent elements of HEOs on the lattice distortion effect and cocktail effect,through elemental manipulation of Cr,Cu,and La,high entropy oxides(HEOs)catalyst CrMnFeCoNiO(Cr_(1:1)),CuMnFeCoNiO(Cu_(1:1)),and LaMnFeCoNiO(La_(1:1))were effectively synthesized by the facile co-precipitation approach.With a size of about 10 nm,Cr_(1:1)presented significant modification impacts on enhancing the hydrogen storage capability of MgH_(2).Specifically,MgH_(2)was able to release hydrogen at 200℃with the addition of Cr_(1:1),MgH_(2)+10 wt%Cr_(1:1)showed prompt rate of dehydrogenation which could release 5.56 wt%H_(2)in 20 min at 250℃,and the activation energy of MgH_(2)was lowered to 69.77±3.75 k J·mol^(-1)by adding Cr_(1:1).According to the Chou model fitting,the exceptional kinetic performance of the composite was attributable to a rate-controlling step changed from low-speed surface penetration to high-speed diffusion.Furthermore,MgH_(2)+10wt%Cr_(1:1)was capable of absorbing hydrogen at ambient temperature and the composite could uptake 6 wt%H_(2)within 8 min at the temperature of 150℃.Due to the high entropy effects of HEOs,Cr_(1:1)possessed superior stability,which guarantees the robust cycling qualities of MgH_(2)+10 wt%Cr_(1:1).Meanwhile,microstructure analysis revealed that the active sites with numerous heterogeneous structures were uniformly dispersed on surfaces,exhibiting superior catalytic effects on improving the hydrogen storage performance of MgH_(2).展开更多
Garnet-type solid-state batteries(SSBs)are considered to be one of the most promising candidates to realize next-generation lithium metal batteries with high energy density and safety.However,the dendrite-induced shor...Garnet-type solid-state batteries(SSBs)are considered to be one of the most promising candidates to realize next-generation lithium metal batteries with high energy density and safety.However,the dendrite-induced short-circuit and the poor interfacial contact impeded the practical application.Herein,interface engineering to achieve low interfacial resistance without high temperature calcination was developed,which Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)was simply coated with complex hydride(Li_(4)(BH_(4))_(3)I(3L1L))in various mass ratios n(Li_(4)(BH_(4))_(3)I)-(100−n)LLZTO(10≤n≤40).The interfacial conductivity increases by more than three orders of magnitude from 8.29×10^(−6)S·cm^(−1)to 1.10×10^(−2)S·cm^(−1).Symmetric Li cells exhibit a high critical current density(CCD)of 4.0 mA·cm^(−2) and an excellent cycling stability for 200 h at 4.0 mA·cm^(−2).SSBs with polymeric sulfur-polyacrylonitrile(SPAN)cathode achieve a high discharge capacity of 1149 mAh·g^(−1) with a capacity retention of 91%after 100 cycles(0.2 C).This attempt guides a simple yet efficient strategy for obtaining a stable Li/LLZTO interface,which would promote the development of solid-state batteries.展开更多
The exploration of efficient,long-lived and cost-effective transition metal catalysts is highly desirable for the practical hydrogen storage of magnesium hydride(MgH_(2)) in sustainable energy devices.Herein,FeCoNiCrT...The exploration of efficient,long-lived and cost-effective transition metal catalysts is highly desirable for the practical hydrogen storage of magnesium hydride(MgH_(2)) in sustainable energy devices.Herein,FeCoNiCrTi high-entropy alloy(HEA) nanosheets were prepared via a facile wet chemical ball milling strategy and they were introduced into MgH_(2) to boost the hydrogen storage performance.The refined HEA exhibited superior catalytic activity on MgH_(2).In contrast to additive-free MgH_(2),the initial desorption temperature of the constructed MgH_(2)-HEA composite was reduced from 330.0 to 198.5℃ and a remarkable 51% reduction in the dehydrogenation activation energy was achieved.Besides,the MgH_(2)-HEA composite only required one-twentieth time of that consumed by pure MgH_(2) to absorb 5.0 wt% of H_(2) at 225℃.The synergy between the "hydrogen pumping" effect of Mg_2Ni/Mg_2NiH_4 and Mg_2Co/Mg_2CoH_5 couples,as well as the good dispersion of Fe,Cr and Ti on the surface of MgH_(2) contributed to the enhanced de/hydrogenation performance of the MgH_(2)-HEA composites.This study furnishes important steering for the design and fabrication of multiple transition metal catalysts and may push the commercial application of magnesium-based hydrides one step forward.展开更多
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 dis...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).展开更多
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 hav...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.展开更多
基金the financial support by the National Nat-ural Science Foundation of China(Nos.52201282,52071281,52371239)the China Postdoctoral Science Foundation(No.2023M742945)+4 种基金Hebei Provincial Postdoctoral Science Foundation(No.B2023003023)the Science Research Project of Hebei Education Department(No.BJK2022033)the Natural Science Foundation of Hebei Province(No.C2022203003)the Inner Mongolia Science and Technology Major Project(No.2020ZD0012)the Baotou Science and Technology Planning Project(No.XM2022BT09).
文摘La-Mg-Ni-based hydrogen storage alloys with superlattice structures are the new generation anode material for nickel metal hydride(Ni-MH)batteries owing to the advantages of high capacity and exceptional activation properties.However,the cycling stability is not currently satisfactory enough which plagues its application.Herein,a strategy of partially substituting La with the Y element is proposed to boost the capacity durability of La-Mg-Ni-based alloys.Furthermore,phase structure regulation is implemented simultaneously to obtain the A5 B19-type alloy with good crystal stability specifically.It is found that Y promotes the phase formation of the Pr5 Co19-type phase after annealing at 985℃.The alloy containing Y contributes to the superior rate capability resulting from the promoted hydrogen diffusion rate.Notably,Y substitution enables strengthening the anti-pulverization ability of the alloy in terms of increasing the volume match between[A_(2)B_(4)]and[AB5]subunits,and effectively enhances the anti-corrosion ability of the alloy due to high electronegativity,realizing improved long-term cycling stability of the alloy from 74.2%to 78.5%after cycling 300 times.The work is expected to shed light on the composition and structure design of the La-Mg-Ni-based hydrogen storage alloy for Ni-MH batteries.
基金supported by the National Natural Science Foundation of China(Nos.22279111,51971195,and 11935004)the Natural Science Foundation of Hebei Province(No.B2020203037)Subsidy for Hebei Key Laboratory of Applied Chemistry after Operation Performance(No.22567616H).
文摘MgH_(2) has been extensively studied as one of the most ideal solid hydrogen storage materials.Nevertheless,rapid capacity decay and sluggish hydrogen storage kinetics hamper its practical application.Herein,a Ni/C nano-catalyst doped MgH_(2)(MgH_(2)–Ni/C)shows an improved hydrogen absorption kinetics with largely reduced activation energy.Particularly,the MgH_(2)–Ni/C displays remarkable cycling stability,which maintains a high capacity of 6.01 wt.%(98.8%of initial capacity)even after 50 full hydrogen ab/desorption cycles,while the undoped MgH_(2) counterpart retains only 85.2%of its initial capacity.Detailed microstructure characterizations clearly reveal that particle sintering/growth accounts primarily for the deterioration of cycling performance of undoped MgH_(2).By comparison,MgH_(2)–Ni/C can maintain a stable particle size with a growing porous structure during long-term cycling,which effectively increases the specific surface of the particles.A novel carbon-induced-porosity stabilization mechanism is proposed,which can stabilize the proportion of rapid hydrogen absorption process,thus dominating the excellent cycling performance of MgH_(2)–Ni/C.This study provides new insights into the cycling stability mechanism of carbon-containing Mg-based hydrogen storage materials,thus promoting their practical applications.
基金financial supports from the National Key R&D Program of China(No.2020YFA0406204)the National Natural Science Foundation of China(No.51801078)。
文摘Hydrogen,as a cheap,clean,and cost-effective secondary energy source,performs an essential role in optimizing today’s energy structure.Magnesium hydride(Mg H_(2))represents an attractive hydrogen carrier for storage and transportation,however,the kinetic behavior and operating temperature remain undesirable.In this work,a dual-phase multi-site alloy(Ms A)anchored on carbon substrates was designed,and its superior catalytic effects on the hydrogen storage properties of MgH_(2) were reported.Mechanism analysis identified that multi-site Fe Ni_(3)/Ni Cu nanoalloys synergistically served as intrinsic drivers for the striking de/hydrogenation performance of the MgH_(2)-Ms A systems.Concretely,the unique multi-metallic site structure attached to the surface of MgH_(2)provided substantial reversible channels and accessible active sites conducive to the adsorption,activation,and nucleation of H atoms.In addition,the coupling system formed by FeNi_(3) and NiCu dual-phase alloys further enhanced the reactivity between Mg/MgH_(2) and H atoms.Hence,the onset dehydrogenation temperature of Mg H_(2)+5 wt%Ms A was reduced to 195℃ and the hydrogen desorption apparent activation energy was reduced to 83.6 k J/mol.5.08 wt%H_(2) could be released at 250℃ in 20 min,reaching a high dehydrogenation rate of 0.254 wt%H_(2)/min,yet that for MgH_(2) at a higher temperature of 335℃ was only 0.145 wt%H_(2)/min.Then,the dehydrogenated Mg H_(2)-Ms A sample could absorb hydrogen from room temperature(30℃)and charge 3.93 wt%H_(2) at 100℃ within20 min under 3.0 MPa H_(2) pressure.Benefiting from carbon substrates,the 5 wt%Ms A doped-MgH_(2) could still maintain 6.36 wt%hydrogen capacity after 20 cycles.In conclusion,this work provides experimental rationale and new insights for the design of efficient catalysts for magnesium-based solid-state hydrogen storage materials.
基金financial supports from the National Key R&D Program of China(2023YFB3809103)the National Natural Science Foundation of China(U23A20128).
文摘Catalytic doping is one of the economic and efficient strategies to optimize the operating temperature and kinetic behavior of magnesium hydride(MgH_(2)).Herein,efficient regulation of electronic and structural rearrangements in niobium-rich nickel oxides was achieved through precise compositional design and niobium cation functionalized doping,thereby greatly enhancing its intrinsic catalytic activity in hydrogen storage systems.As the niobium concentration increased,the Ni-Nb catalysts transformed into a mixed state of multi-phase nanoparticles(composed of nickel and niobium-rich nickel oxides)with smaller particle size and uniform distribution,thus exposing more nucleation sites and diffusion channels at the MgH_(2)/Mg interface.In addition,the additional generation of active Ni-Nb-O mixed phase induced numerous highly topical disordered and distorted crystalline,promoting the transfer and reorganization of H atoms.As a result,a stable and continuous multi-phase/component synergistic catalytic microenvironment could be constructed,exerting remarkable enhancement on MgH_(2)’s hydrogen storage performance.After comparative tests,Ni_(0.7)Nb_(0.3)-doped MgH_(2) presented the optimal low-temperature kinetics with a dehydrogenation activation energy of 78.8 kJ·mol^(−1).The onset dehydrogenation temperature of MgH_(2)+10 wt%Ni_(0.7)Nb_(0.3) was reduced to 198℃ and 6.18 wt%H_(2) could be released at 250℃ within 10 min.In addition,the dehydrogenated MgH_(2)–NiNb composites absorbed 4.87 wt%H_(2) in 10 min at 125℃ and a capacity retention rate was maintained at 6.18 wt%even after 50 reaction cycles.In a word,our work supplies fresh insights for designing novel defective-state multiphase catalysts for hydrogen storage and other energy related field.
基金financially supported by the National Key R&D Program of China(No.2021YFA1502803)the National Natural Science Foundation of China(Nos.22325405,22372160,22432005 and 22321002)Dalian Science and Technology Talent Innovation Program(No.2024RG009).
文摘As a highly reactive reaction intermediate,surface gallium hydride(Ga–H)has garnered significant attention due to its critical role in various catalytic reactions.However,the detailed experimental characterization of this unique species remains challenging.Recently,we have demonstrated that solid-state NMR can be an effective tool for studying surface Ga–H.In this work,we report a comparative solid-state NMR study on H_(2) activation over different Ga_(2)O_(3) polymorphs,specificallyα-,β-andγ-Ga_(2)O_(3).^(1)H solid-state NMR enabled the identification of Ga–H species formed on all the three samples following high-temperature H_(2) treatment.The characteristic ^(1)H NMR signals of Ga–H species are resolved using J-coupling-based double-resonance NMR methods,revealing highly similar lineshapes of Ga–H for all the Ga_(2)O_(3) samples.This suggests potentially similar surface Ga–H configurations among different Ga_(2)O_(3) polymorphs.In addition,the local hydrogen environments on the oxide surfaces are further explored using two-dimensional(2D)^(1)H–^(1)H homonuclear correlation spectra,revealing multiple spatially proximate Ga–H and Ga–H/–OH pairs on different Ga_(2)O_(3) polymorphs.These findings provide insights into the potential mechanism of H_(2) dissociation.Overall,this work offers new perspectives on the local structure of surface Ga–H on Ga_(2)O_(3),and the analytical approach presented here can be further extended to the study of other Ga-based catalysts and other metal hydride species.
基金financial support from the National Natural Science Foundation of China(No.51801078).
文摘To modify the stable thermodynamics and poor kinetics of magnesium hydride(MgH_(2))for solid-state hydrogen storage,MIL-100(Fe)was in situ fabricated on the surfaces of TiO_(2)nano-sheets(NS)by a self-assembly method,and the prepared TiO_(2)NS@MIL-100(Fe)presents an excellent catalytic effect on MgH_(2).The MgH_(2)+7wt.%TiO_(2)NS@MIL-100(Fe)composite can release hydrogen at 200℃,achieving a decrease of 150℃ compared to pure MgH_(2).Besides,the activation energy of dehydrogenation is decreased to 70.62 kJ/mol and 4 wt.%H_(2) can be desorbed within 20 min at a low temperature of 235℃.Under conditions of 100℃ and 3 MPa,MgH_(2)+7wt.%TiO_(2)NS@MIL-100(Fe)absorbs 5 wt.%of H_(2) in 10 min.Surprisingly,6.62 wt.%reversible capacity is maintained after 50 cycles.The modification mechanism is confirmed that the presence of oxygen vacancies and the synergistic effect of multivalent titanium in TiO_(2)NS@MIL-100(Fe)greatly enhance the kinetic and thermodynamic properties of MgH_(2).
基金supported by the National Key R&D Program of China(No.2023YFB3809100)the Youth Fund Project of Grinm(No.SKHT10422023060280).
文摘Dibenzyltoluene(DBT)is a prospective liquid organic hydrogen carrier(LOHC)with low cost and high theoretical hydrogen storage capacity(6.2 wt%).However,the wide application of DBT is severely restricted by expensive noble catalysts.In this work,a new Mg-based metal hydride hydrogenation catalyst,which is composed of MgH_(2),Mg_(2)NiH_(4) and LaH_(3) micro-nano-particles.
基金supported by the National Natural Science Foundation of China(No.52201255)the Natural Science Foundation of Jiangsu Province(No.BK20210884)the Innovation and Entrepreneurship Program of Jiangsu Province(No.JSSCBS20211007).
文摘Magnesium hydride(MgH_(2))was highly regarded for its substantial hydrogen storage capacity of up to 7.6 wt%,but its commercial application was hindered by the high operating temperatures and slow kinetics.In this study,the successful synthesis of the layered Ti_(2)NbC_(2) has significantly enhanced the hydrogen storage performance of MgH_(2).MgH_(2)+5 wt%Ti_(2)NbC_(2) began to release hydrogen at 190℃ and started to absorb hydrogen at room temperature.At a constant temperature of 275℃,complete hydrogen release was achieved in just 250 s,up to 6.9 wt%.At 150℃,the absorption of hydrogen reached 6.59 wt%within 200 s,and the hydrogen absorption activation energy was reduced to 41.517±3.981 kJ·mol^(−1),significantly improving the kinetic performance.Moreover,the composite material still exhibited excellent cyclic stability after 20 cycles at 275℃.In the process of hydrogen de/absorption of Ti_(2)NbC_(2) with MgH_(2),active substances Nb-H and Ti-H were generated in situ,which effectively weakened the Mg-H bond and acted as efficient“hydrogen pumps”to accelerate the re/dehydrogenation of MgH_(2).The unique layered structure and hydrogen affinity of Ti_(2)NbC_(2) provided an effective transfer channel for hydrogen migration,which was key to the excellent hydrogen storage performance of the MgH_(2)+Ti_(2)NbC_(2).
基金supports from the National Key R&D Program of China(2020YFA0406204)the National Natural Science Foundation of China(Grant No 51801078).
文摘Catalytic doping of magnesium hydride(MgH_(2))to improve its hydrogen ab/desorption kinetic properties is considered to be an effective and feasible method.In solid-phase catalysis,the extent of contact between the catalyst and the substrate determines the catalytic reaction in a great sense.With large specific surface area and abundant active sites,two-dimensional(2D)nanomaterials are promising catalysts for MgH_(2)via providing numerous pathways for the diffusion and dissociation of hydrogen.In this regard,2D NiMn-based layered double hydroxide and layered metallic oxide(LMO)are designed and introduced into MgH_(2)to improve its hydrogen storage properties.Simultaneous enhancement in interfacial contact,desorption temperature and kinetics are achieved.The MgH_(2)+9wt%Ni3Mn-LMO composites begin to discharge hydrogen at only 190℃and 6.10wt%H_(2)could be charged in 600 s at 150℃.The activation energy for de/hydrogenation is reduced by 42.43%and 46.56%,respectively,compared to pure MgH_(2).Even at a low operating temperature of 235℃,the modified system was still able to release 4.44wt%H_(2)in an hour,which has rarely been reported in previous studies.Microstructure observations and density functional theory calculations revealed that first,the hydrogen pumping effect of Mg_(2)Ni/Mg_(2)NiH_(4) promotes the adsorption and desorption of hydrogen molecules on the surface of MgH_(2),second,MnOx drew electrons from Mg_(2)Ni,producing a new Density of State structure with a lower d-bond center.This unique change further strengthens the Mg_(2)Ni/Mg_(2)NiH_(4) pump effect on MgH_(2).Our work indicates that the application of 2D metal-based catalysts is a feasible and promising approach towards MgH_(2)for solid-state hydrogen storage to meet technical and scientific requirements.
基金supported by the Natural Science Foundation of China(Nos.52201282 and 52371239)the Natural Science Foundation of Hebei Province(No.E2024203037)+1 种基金the Basic Innovation Research Project in Yanshan University(2022LGZD004)Baotou Science and Technology Planning Project(No.XM2022BT09).
文摘Rare earth-Mg-Ni-based superlattice structure alloys have garnered recognition as promising materials for hydrogen storage.However,their application is impeded by suboptimal cycling longevity.The novel AB_(4)-type alloy emerges as an attractive candidate,distinguished by its good structure stability,high rate capability,and long-term durability.Herein,we designed an AB_(4)-type La_(0.6)0Sm_(0.22)Mg_(0.18)Ni_(4.09)Al_(0.09)Mn_(0.10)alloy that manifests superior electrochemical performance.The obtained AB_(4)-type single-phase alloy delivers a high discharge capacity of 375.2 mAh·g^(-1)and features outstanding discharge ability at high rates,maintaining 121 mAh·g^(-1)even at a discharge rate of 6C.The excellent high-rate discharge performance can be attributed to its fast charge transfer and hydrogen diffusion kinetics.Moreover,the AB_(4)-type alloy maintains a capacity retention of 84.5%after 200 cycles and retains 55.7%of its capacity retention even after 500 cycles.This work provides a good alternative to hydrogen storage alloy with high power and long cycling durability performance for nickel metal hydride batteries.
基金supported by the National Natural Science Foundation of China(Grant Nos.12272001,11972046)the Outstanding Youth Project of Natural Science Foundation of Anhui Province(Grant No.2108085Y02)the Major Project of Anhui University Natural Science Foundation(Grant No.KJ2020ZD30)。
文摘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.
基金supported by National Key Research and Development Program of China(2021YFB4000604)National Natural Science Foundation of China(52271220)111 Project(B12015)and the Fundamental Research Funds for the Central Universities.
文摘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.
基金supported by the projects UIDB/00481/2020 and UIDP/00481/2020-Fundação para a Ciência e a Tecnologia,DOI 10.54499/UIDB/00481/2020(https://doi.org/10.54499/UIDB/00481/2020)and DOI 10.54499/UIDP/00481/2020(https://doi.org/10.54499/UIDP/00481/2020)supported by CENTRO-01-0145-FEDER-022083-Centro Portugal Regional Operational Programme(Centro 2020),under the PORTUGAL 2020 Partnership Agreement,through the European Regional Development Fund(ERDF).This article is a result of the Innovation Pact“NGS-New Generation Storage”(C644936001-00000045)+3 种基金by“NGS”Consortium,co-financed by NextGeneration EU,through the Incentive System“Agendas para a Inovação Empresarial”(“Agendas for Business Innovation”)within the Recovery and Resilience Plan(PRR).D.P acknowledges FCT,Portugal for the financial support with reference CEECIND/04158/2017(https://doi.org/10.54499/CEECIND/04158/2017/CP1459/CT0029)funding from the SMART-ER project,funded by the European Union’s Horizon 2020 research and innovation programme under Grant Agreement#101016888.support granted by the Recovery and Resilience Plan(PRR)and by the Next Generation EU European Funds to Universidade de Aveiro,through the Agenda for Business Innovation“NGS-Next Generation Storage”(Project no 02/C05-i01.01/2022 with the application C644936001-00000045).
文摘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.
基金supported by the National Key R&D Program of China(No.2022YFB3803801)National Natural Science Foundation of China(52071177,21975125 and 52171214)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions.
文摘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.
基金supported by the National Natural Science Foundation of China(Nos.22279111,51971195,and 11935004)the Natural Science Foundation of Hebei Province(No.B2020203037)Subsidy for Hebei Key Laboratory of Applied Chemistry after Operation Performance(No.22567616H).
文摘MgH_(2),albeit with slow desorption kinetics,has been extensively studied as one of the most ideal solid hydrogen storage materials.Adding such catalyst as Ni can improve the desorption kinetics of MgH_(2),whereas the catalytic role has been attributed to different substances such as Ni,Mg_(2)Ni,Mg_(2)NiH0.3,and Mg_(2)NiH4.In the present study,Ni nanoparticles(Ni-NPs)supported on mesoporous carbon(Ni@C)have been synthesized to improve the hydrogen desorption kinetics of MgH_(2).The utilization of Ni@C largely decreases the dehydrogenation activation energy from 176.9 to 79.3 kJ mol^(−1) and the peak temperature of dehydrogenation from 375.5 to 235℃.The mechanism of Ni catalyst is well examined by advanced aberration-corrected environmental transmission electron microscopy and/or x-ray diffraction.During the first dehydrogenation,detailed microstructural studies reveal that the decomposition of MgH_(2)is initially triggered by the Ni-NPs,which is the rate-limiting step.Subsequently,the generated Mg reacts rapidly with Ni-NPs to form Mg_(2)Ni,which further promotes the dehydrogenation of residual MgH_(2).In the following dehydrogenation cycle,Mg_(2)NiH4 can rapidly decompose into Mg_(2)Ni,which continuously promotes the decomposition of MgH_(2).Our study not only elucidates the mechanism of Ni catalyst but also helps design and assemble catalysts with improved dehydriding kinetics of MgH_(2).
基金the financial support from the National Natural Science Foundation of China(Grant No.51801078)。
文摘The lattice distortion effect and cocktail effect of high-entropy oxides(HEOs)will dominate the catalytic effect of the materials,in order to study the influence of the constituent elements of HEOs on the lattice distortion effect and cocktail effect,through elemental manipulation of Cr,Cu,and La,high entropy oxides(HEOs)catalyst CrMnFeCoNiO(Cr_(1:1)),CuMnFeCoNiO(Cu_(1:1)),and LaMnFeCoNiO(La_(1:1))were effectively synthesized by the facile co-precipitation approach.With a size of about 10 nm,Cr_(1:1)presented significant modification impacts on enhancing the hydrogen storage capability of MgH_(2).Specifically,MgH_(2)was able to release hydrogen at 200℃with the addition of Cr_(1:1),MgH_(2)+10 wt%Cr_(1:1)showed prompt rate of dehydrogenation which could release 5.56 wt%H_(2)in 20 min at 250℃,and the activation energy of MgH_(2)was lowered to 69.77±3.75 k J·mol^(-1)by adding Cr_(1:1).According to the Chou model fitting,the exceptional kinetic performance of the composite was attributable to a rate-controlling step changed from low-speed surface penetration to high-speed diffusion.Furthermore,MgH_(2)+10wt%Cr_(1:1)was capable of absorbing hydrogen at ambient temperature and the composite could uptake 6 wt%H_(2)within 8 min at the temperature of 150℃.Due to the high entropy effects of HEOs,Cr_(1:1)possessed superior stability,which guarantees the robust cycling qualities of MgH_(2)+10 wt%Cr_(1:1).Meanwhile,microstructure analysis revealed that the active sites with numerous heterogeneous structures were uniformly dispersed on surfaces,exhibiting superior catalytic effects on improving the hydrogen storage performance of MgH_(2).
基金This study was financially supported by the National Natural Science Foundation of China(Nos.52171180,51802154,and 51971065)the National Science Fund for Distinguished Young Scholars(No.51625102)+3 种基金the Innovation Program of Shanghai Municipal Education Commission(No.2019-01-07-00-07-E00028)the Fundamental Research Funds for the Central Universities(No.NG2022005)the Open Fund for Graduate Innovation Base in Nanjing University of Aeronautics and Astronautics(No.xcxjh20210612)partially supported by the Fundamental Research Funds for the Central Universities,NS2021043.
文摘Garnet-type solid-state batteries(SSBs)are considered to be one of the most promising candidates to realize next-generation lithium metal batteries with high energy density and safety.However,the dendrite-induced short-circuit and the poor interfacial contact impeded the practical application.Herein,interface engineering to achieve low interfacial resistance without high temperature calcination was developed,which Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)was simply coated with complex hydride(Li_(4)(BH_(4))_(3)I(3L1L))in various mass ratios n(Li_(4)(BH_(4))_(3)I)-(100−n)LLZTO(10≤n≤40).The interfacial conductivity increases by more than three orders of magnitude from 8.29×10^(−6)S·cm^(−1)to 1.10×10^(−2)S·cm^(−1).Symmetric Li cells exhibit a high critical current density(CCD)of 4.0 mA·cm^(−2) and an excellent cycling stability for 200 h at 4.0 mA·cm^(−2).SSBs with polymeric sulfur-polyacrylonitrile(SPAN)cathode achieve a high discharge capacity of 1149 mAh·g^(−1) with a capacity retention of 91%after 100 cycles(0.2 C).This attempt guides a simple yet efficient strategy for obtaining a stable Li/LLZTO interface,which would promote the development of solid-state batteries.
基金the financial support from the National Natural Science Foundation of China (Grant No.51801078)。
文摘The exploration of efficient,long-lived and cost-effective transition metal catalysts is highly desirable for the practical hydrogen storage of magnesium hydride(MgH_(2)) in sustainable energy devices.Herein,FeCoNiCrTi high-entropy alloy(HEA) nanosheets were prepared via a facile wet chemical ball milling strategy and they were introduced into MgH_(2) to boost the hydrogen storage performance.The refined HEA exhibited superior catalytic activity on MgH_(2).In contrast to additive-free MgH_(2),the initial desorption temperature of the constructed MgH_(2)-HEA composite was reduced from 330.0 to 198.5℃ and a remarkable 51% reduction in the dehydrogenation activation energy was achieved.Besides,the MgH_(2)-HEA composite only required one-twentieth time of that consumed by pure MgH_(2) to absorb 5.0 wt% of H_(2) at 225℃.The synergy between the "hydrogen pumping" effect of Mg_2Ni/Mg_2NiH_4 and Mg_2Co/Mg_2CoH_5 couples,as well as the good dispersion of Fe,Cr and Ti on the surface of MgH_(2) contributed to the enhanced de/hydrogenation performance of the MgH_(2)-HEA composites.This study furnishes important steering for the design and fabrication of multiple transition metal catalysts and may push the commercial application of magnesium-based hydrides one step forward.
基金Project supported by the Joint Fund of the National Natural Science Foundation of China–“Ye Qisun”Science Fund(Grant No.U2341251)。
文摘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).
基金Project supported by the National Natural Science Foundation of China (Grant Nos.U2230401,U1930401,and 12004048)the National Key Research and Development Program of China (Grant No.2021YFB3501503)+1 种基金the Science Challenge Project (Grant No.TZ2018002)the Foundation of LCP。
文摘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.
