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
In order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys,Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox (x=0,0.1,0.2,0.3,0.4) alloys w...In order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys,Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox (x=0,0.1,0.2,0.3,0.4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied with an X-ray diffractometer (XRD) and a high resolution transmission electronic microscope (HRTEM). An investigation on the thermal stability of the as-spun alloys was carried out with a differential scanning calorimeter (DSC). The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results demonstrate that the substitution of Co for Ni does not alter the major phase of Mg2Ni but results in the formation of secondary phase MgCo2. No amorphous phase is detected in the as-spun Co-free alloy,but a certain amount of amorphous phase is clearly found in the as-spun Co-containing alloys. The substitution of Co for Ni exerts a slight influence on the hydriding kinetics of the as-spun alloy. However,it dramatically enhances the dehydriding kinetics of the as-cast and spun alloys. As Co content (x) increases from 0 to 0.4,the hydrogen desorption capacity increases from 0.19% to 1.39% (mass fraction) in 20 min for the as-cast alloy,and from 0.89% to 2.18% (mass fraction) for the as-spun alloy (30 m/s).展开更多
A partial substitution of Ni by Mn was implemented in order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys. The nanocrystalline and amorphous MgzNi-type Mg2Nil-xMnx （x=0, 0. 1, 0.2, 0.3, ...A partial substitution of Ni by Mn was implemented in order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys. The nanocrystalline and amorphous MgzNi-type Mg2Nil-xMnx （x=0, 0. 1, 0.2, 0.3, 0.4） alloys were synthesized by the melt-spinning technique. The structures of the as-cast and spun alloys were studied by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and high resolution transmission electron microscopy （HRTEM）. The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results show that the as-spun Mn-free alloy holds a typical nanocrystalline structure, whereas the as-spun alloys containing Mn display a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni intensifies the glass forming ability of the Mg2Ni-type alloy. The hydrogen absorption and desorption capacities and kinetics of the alloys increase with increasing the spinning rate, for which the nanocrystalline and amorphous structure produced by the melt spinning is mainly responsible. The substitution of Mn for Ni evidently improves the hydrogen desorption performance. The hydrogen desorption capacities of the as-cast and spun alloys rise with the increase in the percentage of Mn substitution.展开更多
The nanocrystalline Mg2Ni-type electrode alloys with nominal compositions of Mg20Ni10-xCux (x = 0, 1, 2, 3, 4) were synthesized by melt-spinning technique. The microstructures of the alloys were characterized by XRD, ...The nanocrystalline Mg2Ni-type electrode alloys with nominal compositions of Mg20Ni10-xCux (x = 0, 1, 2, 3, 4) were synthesized by melt-spinning technique. The microstructures of the alloys were characterized by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinet-ics of the alloys were measured using an auto-matically controlled Sieverts apparatus. The re- sults show that all the as-spun alloys hold ty- pical nanocrystalline structure. The substitution of Cu for Ni does not change the major phase Mg2Ni but it leads to the formation of the sec-ondary phase Mg2Cu. The hydrogen absorption capacity of the alloys first increases and then decreases with rising Cu content, but the hy-drogen desorption capacity of the alloys mono- tonously grows with increasing Cu content. The melt spinning significantly improves the hydro- genation and dehydrogenation capacities and kinetics of the alloys.展开更多
Mg-based materials are one of the most promising hydrogen storage candidates due to their high hydrogen storage capacity,environmental benignity,and high Clarke number characteristics.However,the limited thermodynamic...Mg-based materials are one of the most promising hydrogen storage candidates due to their high hydrogen storage capacity,environmental benignity,and high Clarke number characteristics.However,the limited thermodynamics and kinetic properties pose major challenges for their engineering applications.Herein,we review the recent progress in improving their thermodynamics and kinetics,with an emphasis on the models and the influence of various parameters in the calculated models.Subsequently,the impact of alloying,composite,and nanocrystallization on both thermodynamics and dynamics are discussed in detail.In particular,the correlation between various modification strategies and the hydrogen capacity,dehydrogenation enthalpy and temperature,hydriding/dehydriding rates are summarized.In addition,the mechanism of hydrogen storage processes of Mg-based materials is discussed from the aspect of classical kinetic theories and microscope hydrogen transferring behavior.This review concludes with an outlook on the remaining challenge issues and prospects.展开更多
Eighteen as-cast binary Mg-Ni, Mg-Mm and ternary Mg-Ni-Mm and Mg-Ni-TM （TM=transition metals （Cu, Zn, Mn and Co）; Mm = mischmetal containing Ce, La, Nd and Pr） alloys were hydrided by an electrochemical process to...Eighteen as-cast binary Mg-Ni, Mg-Mm and ternary Mg-Ni-Mm and Mg-Ni-TM （TM=transition metals （Cu, Zn, Mn and Co）; Mm = mischmetal containing Ce, La, Nd and Pr） alloys were hydrided by an electrochemical process to determine the alloys with the most potential for electrochemical hydrogen storage. The alloys were hydrided in a 6 mol/L KOH solution at 80 °C for 480 min and at 100 A/m2. To assess the electrochemical hydriding performance of alloys, maximum hydrogen concentrations, hydrogen penetration depths and total mass of absorbed hydrogen in the alloys were measured by glow discharge spectrometry. In addition, the structures and phase compositions of the alloys both before and after hydriding were studied by optical and scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction. It was determined that the highest total amount of hydrogen was absorbed by the Mg-25Ni-12Mm and Mg-26Ni （mass fraction, %） alloys. The maximum hydrogen concentrations in the Mg-25Ni-12Mm and Mg-26Ni alloys were 1.0% and 1.6%, respectively. The main hydriding product was the binary MgH2 hydride, and the ternary Mg2NiH4 hydride was also detected in the Mg-25Ni-12Mm alloy. The electrochemical hydriding parameters achieved are discussed in relation to the structures of alloys, alloying elements and hydriding mechanisms.展开更多
The process of mechanically assisted hydriding and subsequent thermal dehydriding was proposed to produce nanocrystalline Mg and Mg alloy powders using pure Mg and Mg-5.5%Zn-0.6%Zr(mass fraction)(ZK60 Mg) alloy as the...The process of mechanically assisted hydriding and subsequent thermal dehydriding was proposed to produce nanocrystalline Mg and Mg alloy powders using pure Mg and Mg-5.5%Zn-0.6%Zr(mass fraction)(ZK60 Mg) alloy as the starting materal.The hydriding was achieved by room-temperature reaction milling in hydrogen.The dehydriding was carried out by vacuum annealing of the as-milled powders.The microstructure and morphology of both the as-milled and subsequently dehydrided powders were characterized by X-ray diffraction analysis(XRD) ,transmission electron microscopy(TEM) ,and scanning electron microscopy(SEM) ,respectively.The results show that,by reaction milling in hydrogen,both Mg and ZK60 Mg alloy can be fully hydrided to form nanocrystalline MgH2 with an average grain size of 10 nm.After subsequent thermal dehydriding at 300℃,the MgH2 can be turned into Mg again,and the newly formed Mg grains are nanocrystallines,with an average grain size of 25 nm.展开更多
A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigated by means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The...A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigated by means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showed that the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis without any activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp (0.1 MPa)=-3026/T+5.814 (523 K≤T≤623 K) for hydriding and Igp (0.1 MPa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1-a)]3/2 = kt and the apparent activation energy for the nucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31kJ/(mol.H2) and 59.9±2.99kJ/(mol.H2)respectively.展开更多
The effects of chloride salts(NaCl,MgCl2and NH4Cl)on the hydrolysis kinetics of MgH2prepared by hydridingcombustion synthesis and mechanical milling(HCS+MM)were discussed.X-ray diffraction(XRD)analyses show that high-...The effects of chloride salts(NaCl,MgCl2and NH4Cl)on the hydrolysis kinetics of MgH2prepared by hydridingcombustion synthesis and mechanical milling(HCS+MM)were discussed.X-ray diffraction(XRD)analyses show that high-purityMgH2was successfully prepared by HCS.Hydrolysis performance test results indicate that the chloride salt added during the millingprocess is favorable to the initial reaction rate and hydrogen generation yield within60min.A MgH2?10%NH4Cl composite exhibitsthe best performance with the hydrogen generation yield of1311mL/g and a conversion rate of85.69%in60min at roomtemperature.It is suggested that the chloride salts not only play as grinding aids in the milling process,but also create fresh surface ofreactive materials,favoring the hydrolysis reaction.展开更多
The MgNi26 alloy was prepared by three different methods of gravity casting (GC), mechanical alloying (MA) and rapid solidification (RS). All samples were electrochemically hydrided in a 6 mol/L KOH solution at 80 ...The MgNi26 alloy was prepared by three different methods of gravity casting (GC), mechanical alloying (MA) and rapid solidification (RS). All samples were electrochemically hydrided in a 6 mol/L KOH solution at 80 °C for 240 min. The structures and phase compositions of the alloys were studied using optical microscopy and scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction. A temperature-programmed desorption technique was used to measure the absorbed hydrogen and study the dehydriding process. The content of hydrogen absorbed by the MgNi26-MA (approximately 1.3%, mass fraction) was 30 times higher than that of the MgNi26-GC. The MgNi26-RS sample absorbed only 0.1% of hydrogen. The lowest temperature for hydrogen evolution was exhibited by the MgNi26-MA. Compared with pure commercial MgH2, the decomposition temperature was reduced by more than 200 °C. The favourable phase and structural composition of the MgNi26-MA sample were the reasons for the best hydriding and dehydriding properties.展开更多
The hydriding of as-cast Mg-5.5%Zn-0.6%Zr(ZK60 Mg)(mass fraction)alloy was achieved by room-temperature reaction milling in hydrogen,with the mechanical energy serving as the driving force for the process.The hydridin...The hydriding of as-cast Mg-5.5%Zn-0.6%Zr(ZK60 Mg)(mass fraction)alloy was achieved by room-temperature reaction milling in hydrogen,with the mechanical energy serving as the driving force for the process.The hydriding progress during milling was examined by hydrogen absorption measurement,and the microstructure change was characterized by X-ray diffraction analysis(XRD),scanning electron microscopy(SEM),and transmission electron microscopy(TEM),respectively.The results show that,by room-temperature reaction milling in hydrogen,the as-cast ZK60 Mg alloy can be fully hydrided to form a nanocrystalline MgH_(2) single-phase microstructure.In particular,the average grain size of the MgH_(2) phase obtained by room-temperature reaction milling in hydrogen for 16.2 h is about 8-10 nm,and the average particle size of the as-milled hydrided powders is 2-3μm.展开更多
In order to improve the hydrogenation and dehydrogenation performances of the Mg2Ni-type alloys, Mg was partially substituted by La in the alloy, and melt spinning technology was used for the preparation of the Mg20-x...In order to improve the hydrogenation and dehydrogenation performances of the Mg2Ni-type alloys, Mg was partially substituted by La in the alloy, and melt spinning technology was used for the preparation of the Mg20-xLaxNi10 （x=0, 2, 4, 6） hydrogen storage alloys. The structures of the alloys were studied by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and high-resolution transmission electron microscopy （HRTEM）. It was found that no amorphous phase formed in the as-spun La-free alloy, but the as-spun alloys containing La held a major amorphous phase. When La content x≤2, the major phase in the as-cast alloys was Mg2Ni phase, but with further increase of La content, the major phase of the as-cast alloys changed into LaNi5＋LaMg3 phase. Thermal stability of the as-spun alloys was studied by differential scanning calorimetry （DSC）, showing that spinning rate was a negligible factor on the crystallization temperature of the amorphous phase. The hydrogen absorption and desorption kinetics of the as-cast and as-spun alloys were measured using an automatically controlled Sieverts apparatus, confirming that the hydrogen absorption and desorption capacities and kinetics of the as-cast alloys clearly increased with rising La content. For La content x=2, the as-spun alloy displayed optimal hydrogen desorption kinetics at 200 ℃.展开更多
The Mg-Ni-based ternary alloys Mg2-xTixNi(x=0,0.2,0.4)and Mg2Ni1-xZrx(x=0,0.2,0.4)were successfully synthesized by mechanical grinding.The phases in the alloys and the hydriding/dehydriding properties of the alloys we...The Mg-Ni-based ternary alloys Mg2-xTixNi(x=0,0.2,0.4)and Mg2Ni1-xZrx(x=0,0.2,0.4)were successfully synthesized by mechanical grinding.The phases in the alloys and the hydriding/dehydriding properties of the alloys were investigated.Mg2Ni and Mg are the main hydrogen absorption phases in the alloys by XRD analysis.Hydriding kinetics curves of the alloys indicate that the hydrogen absorption rate increases after partial substitution of Ti for Mg and Zr for Ni.According to the measurement of pressure-concentration-isotherms and Van't Hoff equation,the relationship between ln p(H2)and 1 000/T was established.It is found that while increasing the content of correspondingly substituted elements at the same temperature,the equilibrium pressure of dehydriding increases,the enthalpy change and the stability of the alloy hydride decrease.展开更多
Hydrogen storage composites Nd2Mg17-50 wt.%Ni-x wt.%CeO2（x=0, 0.5, 1.0, 1.5, 2.0） were obtained by induction-ball milling method. The catalytic effect of CeO_2 on hydriding kinetics of Nd_2Mg17-50 wt.%Ni composite w...Hydrogen storage composites Nd2Mg17-50 wt.%Ni-x wt.%CeO2（x=0, 0.5, 1.0, 1.5, 2.0） were obtained by induction-ball milling method. The catalytic effect of CeO_2 on hydriding kinetics of Nd_2Mg17-50 wt.%Ni composite was investigated. X-ray diffraction（XRD） and high resolution transmission electron microscopy（HRTEM）, selected area electron diffraction（SAED） analyses showed that Nd_2Mg17-50 wt.%Ni alloy had a multiphase structure, consisting of NdMg12, NdMg_2Ni, Mg_2Ni and Ni phases and the addition of catalyst CeO_2 prompted the composites to be partly transformed into amorphous strucutre. The CeO_2 improved the maximum hydrogen capacity of Nd_2Mg17-50 wt.%Ni alloy from 3.192 wt.% to 3.376 wt.%（x=1.0）. What＇s more, the increment of diffusion coefficient D led to the faster hydriding kinetics, which was calculated by Avrami-Erofeev equation. The dehydrogenation temperature reduced from 515.54 to 504.72 K was mainly caused by the decrease of activation energy from 93.28 to 69.36 kJ /mol, which was proved by the Kissinger equation.展开更多
La1.5Mg17Ni0.5 hydrogen storage materials were prepared by hydriding combustion synthesis (HCS) and mechanical alloying (MA) method respectively. The experimental results show that the hydrogen absorption properties o...La1.5Mg17Ni0.5 hydrogen storage materials were prepared by hydriding combustion synthesis (HCS) and mechanical alloying (MA) method respectively. The experimental results show that the hydrogen absorption properties of La1.5Mg17Nio.5 prepared by MA are better than that by HCS. La1.5Mg17Nio.5 prepared by MA can absorb 6.73 mass% hydrogen at 523 K within 1 min, and 4.92 mass% hydrogen at 423 K. The improvement of hydriding properties of La1.5Mg17Ni0.5alloy prepared by MA can be ascribed to the formation of nano-crystalline and defects during the mechanical alloying.展开更多
The welding joints of Zircaloy 4 plates obtained by diffusion welding at 800°C under pressure in vacuum were cracked during autoclave tests at 400°C superheated steam after exposure longer than 150 days. T...The welding joints of Zircaloy 4 plates obtained by diffusion welding at 800°C under pressure in vacuum were cracked during autoclave tests at 400°C superheated steam after exposure longer than 150 days. The section of specimens was examined by optical microscopy and the composition at the tips of cracking was analyzed by electron microprobe. The result shows that the combination of oxidation and hydriding induced cracking is responsible for this failure of the welding joints.展开更多
The structure and hydriding performance of La0.6Nd0.4Ni4.8Mn0.2Cux (x = 0 ～ 0.4) alloys were investigated in order to develop suitable materials for metal hydride air conditioner. The effect of Cu addition on the cry...The structure and hydriding performance of La0.6Nd0.4Ni4.8Mn0.2Cux (x = 0 ～ 0.4) alloys were investigated in order to develop suitable materials for metal hydride air conditioner. The effect of Cu addition on the crystal structure,equilibrium pressure, hydrogen capacity and hysteresis as well as hydrogen absorption/desorption kinetics were systematically studied by using the measurement of P-C isotherms, X-ray diffraction and scanning electron microscopy. As the amount of Cu increases, the plateau pressure increases and hydrogen absorption/desorption kinetics is improved, but the effective hydrogen storage capacity decreases. It is shown that variations in the basal plane parameter a can be used as an indication for the plateau pressure changes. With the increase of parameter a, the plateau pressure decreases. For La0.6 Nd0.4Ni4.8Mn0.2Cux(x = 0 ～ 0.4) alloys there is a relationship between the effective hydrogen storage capacities and the ratios of their unit cell parameters c and a. The effective hydrogen storage capacity decreases with increase of a/c.展开更多
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
Novel hydrogen storage materials have propelled progress in hydrogen storage technologies.Magnesium hydride(MgH_(2))is a highly promising candidate.Nevertheless,several drawbacks,including the need for elevated therma...Novel hydrogen storage materials have propelled progress in hydrogen storage technologies.Magnesium hydride(MgH_(2))is a highly promising candidate.Nevertheless,several drawbacks,including the need for elevated thermal conditions,sluggish dehydrogena-tion kinetics,and high thermodynamic stability,limit its practical application.One effective method of addressing these challenges is cata-lyst doping,which effectively boosts the hydrogen storage capability of Mg-based materials.Herein,we review recent advancements in catalyst-doped MgH_(2) composites,with particular focus on multicomponent and high-entropy catalysts.Structure-property relationships and catalytic mechanisms in these doping strategies are also summarized.Finally,based on existing challenges,we discuss future research directions for the development of Mg-based hydrogen storage systems.展开更多
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Project(2006AA05Z132) supported by the National High-tech Research and Development Program of ChinaProjects(50871050, 50961009) supported by the National Natural Science Foundation of China+1 种基金Project(2010ZD05) supported by the Natural Science Foundation of Inner Mongolia, ChinaProject(NJzy08071) supported by the High Education Science Research Program of Inner Mongolia, China
文摘In order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys,Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox (x=0,0.1,0.2,0.3,0.4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied with an X-ray diffractometer (XRD) and a high resolution transmission electronic microscope (HRTEM). An investigation on the thermal stability of the as-spun alloys was carried out with a differential scanning calorimeter (DSC). The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results demonstrate that the substitution of Co for Ni does not alter the major phase of Mg2Ni but results in the formation of secondary phase MgCo2. No amorphous phase is detected in the as-spun Co-free alloy,but a certain amount of amorphous phase is clearly found in the as-spun Co-containing alloys. The substitution of Co for Ni exerts a slight influence on the hydriding kinetics of the as-spun alloy. However,it dramatically enhances the dehydriding kinetics of the as-cast and spun alloys. As Co content (x) increases from 0 to 0.4,the hydrogen desorption capacity increases from 0.19% to 1.39% (mass fraction) in 20 min for the as-cast alloy,and from 0.89% to 2.18% (mass fraction) for the as-spun alloy (30 m/s).
基金Projects(50871050,50961001) supported by the National Natural Science Foundation of ChinaProject(2010ZD05) supported by the Natural Science Foundation of Inner Mongolia,ChinaProject(NJzy08071) supported by the High Education Science Research Program of Inner Mongolia,China
文摘A partial substitution of Ni by Mn was implemented in order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys. The nanocrystalline and amorphous MgzNi-type Mg2Nil-xMnx （x=0, 0. 1, 0.2, 0.3, 0.4） alloys were synthesized by the melt-spinning technique. The structures of the as-cast and spun alloys were studied by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and high resolution transmission electron microscopy （HRTEM）. The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results show that the as-spun Mn-free alloy holds a typical nanocrystalline structure, whereas the as-spun alloys containing Mn display a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni intensifies the glass forming ability of the Mg2Ni-type alloy. The hydrogen absorption and desorption capacities and kinetics of the alloys increase with increasing the spinning rate, for which the nanocrystalline and amorphous structure produced by the melt spinning is mainly responsible. The substitution of Mn for Ni evidently improves the hydrogen desorption performance. The hydrogen desorption capacities of the as-cast and spun alloys rise with the increase in the percentage of Mn substitution.
文摘The nanocrystalline Mg2Ni-type electrode alloys with nominal compositions of Mg20Ni10-xCux (x = 0, 1, 2, 3, 4) were synthesized by melt-spinning technique. The microstructures of the alloys were characterized by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinet-ics of the alloys were measured using an auto-matically controlled Sieverts apparatus. The re- sults show that all the as-spun alloys hold ty- pical nanocrystalline structure. The substitution of Cu for Ni does not change the major phase Mg2Ni but it leads to the formation of the sec-ondary phase Mg2Cu. The hydrogen absorption capacity of the alloys first increases and then decreases with rising Cu content, but the hy-drogen desorption capacity of the alloys mono- tonously grows with increasing Cu content. The melt spinning significantly improves the hydro- genation and dehydrogenation capacities and kinetics of the alloys.
基金supported by the Chongqing Special Key Project of Technology Innovation and Application Development,China(cstc2019jscx-dxwt B0029)the National Natural Science Foundation of China(51871143)+5 种基金the Science and Technology Committee of Shanghai(19010500400)the Shanghai Rising-Star Program(21QA1403200)Chongqing Research Program of Basic Research and Frontier Technology(No.cstc2019jcyj-msxm X0306)the Start-up Funds of Chongqing University(02110011044171)the Senior Talent Start-up Funds of Jiangsu University(4111310024)the Independent Research Project of State Key Laboratory of Mechanical Transmissions(SKLMT-ZZKT-2021M11)
文摘Mg-based materials are one of the most promising hydrogen storage candidates due to their high hydrogen storage capacity,environmental benignity,and high Clarke number characteristics.However,the limited thermodynamics and kinetic properties pose major challenges for their engineering applications.Herein,we review the recent progress in improving their thermodynamics and kinetics,with an emphasis on the models and the influence of various parameters in the calculated models.Subsequently,the impact of alloying,composite,and nanocrystallization on both thermodynamics and dynamics are discussed in detail.In particular,the correlation between various modification strategies and the hydrogen capacity,dehydrogenation enthalpy and temperature,hydriding/dehydriding rates are summarized.In addition,the mechanism of hydrogen storage processes of Mg-based materials is discussed from the aspect of classical kinetic theories and microscope hydrogen transferring behavior.This review concludes with an outlook on the remaining challenge issues and prospects.
基金supported by the Czech Science Foundation(project no.P108/12/G043)
文摘Eighteen as-cast binary Mg-Ni, Mg-Mm and ternary Mg-Ni-Mm and Mg-Ni-TM （TM=transition metals （Cu, Zn, Mn and Co）; Mm = mischmetal containing Ce, La, Nd and Pr） alloys were hydrided by an electrochemical process to determine the alloys with the most potential for electrochemical hydrogen storage. The alloys were hydrided in a 6 mol/L KOH solution at 80 °C for 480 min and at 100 A/m2. To assess the electrochemical hydriding performance of alloys, maximum hydrogen concentrations, hydrogen penetration depths and total mass of absorbed hydrogen in the alloys were measured by glow discharge spectrometry. In addition, the structures and phase compositions of the alloys both before and after hydriding were studied by optical and scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction. It was determined that the highest total amount of hydrogen was absorbed by the Mg-25Ni-12Mm and Mg-26Ni （mass fraction, %） alloys. The maximum hydrogen concentrations in the Mg-25Ni-12Mm and Mg-26Ni alloys were 1.0% and 1.6%, respectively. The main hydriding product was the binary MgH2 hydride, and the ternary Mg2NiH4 hydride was also detected in the Mg-25Ni-12Mm alloy. The electrochemical hydriding parameters achieved are discussed in relation to the structures of alloys, alloying elements and hydriding mechanisms.
基金Project(50574034)supported by the National Natural Science Foundation of ChinaProject(20060213016)supported by Doctoral Education Fund of Ministry of Education of China
文摘The process of mechanically assisted hydriding and subsequent thermal dehydriding was proposed to produce nanocrystalline Mg and Mg alloy powders using pure Mg and Mg-5.5%Zn-0.6%Zr(mass fraction)(ZK60 Mg) alloy as the starting materal.The hydriding was achieved by room-temperature reaction milling in hydrogen.The dehydriding was carried out by vacuum annealing of the as-milled powders.The microstructure and morphology of both the as-milled and subsequently dehydrided powders were characterized by X-ray diffraction analysis(XRD) ,transmission electron microscopy(TEM) ,and scanning electron microscopy(SEM) ,respectively.The results show that,by reaction milling in hydrogen,both Mg and ZK60 Mg alloy can be fully hydrided to form nanocrystalline MgH2 with an average grain size of 10 nm.After subsequent thermal dehydriding at 300℃,the MgH2 can be turned into Mg again,and the newly formed Mg grains are nanocrystallines,with an average grain size of 25 nm.
文摘A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigated by means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showed that the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis without any activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp (0.1 MPa)=-3026/T+5.814 (523 K≤T≤623 K) for hydriding and Igp (0.1 MPa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1-a)]3/2 = kt and the apparent activation energy for the nucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31kJ/(mol.H2) and 59.9±2.99kJ/(mol.H2)respectively.
基金Projects(51571112,51171079,51471087) supported by the National Natural Science Foundation of ChinaProject(13KJA430003) supported by Jiangsu Higher Education Institutions of China+1 种基金Project supported by Qing Lan Project,ChinaProject supported by the Priority Academic Program Development(PAPD) of Jiangsu Higher Education Institutions,China
文摘The effects of chloride salts(NaCl,MgCl2and NH4Cl)on the hydrolysis kinetics of MgH2prepared by hydridingcombustion synthesis and mechanical milling(HCS+MM)were discussed.X-ray diffraction(XRD)analyses show that high-purityMgH2was successfully prepared by HCS.Hydrolysis performance test results indicate that the chloride salt added during the millingprocess is favorable to the initial reaction rate and hydrogen generation yield within60min.A MgH2?10%NH4Cl composite exhibitsthe best performance with the hydrogen generation yield of1311mL/g and a conversion rate of85.69%in60min at roomtemperature.It is suggested that the chloride salts not only play as grinding aids in the milling process,but also create fresh surface ofreactive materials,favoring the hydrolysis reaction.
基金the Czech Science Foundation (project No. P108/12/G043) for the financial support of this research
文摘The MgNi26 alloy was prepared by three different methods of gravity casting (GC), mechanical alloying (MA) and rapid solidification (RS). All samples were electrochemically hydrided in a 6 mol/L KOH solution at 80 °C for 240 min. The structures and phase compositions of the alloys were studied using optical microscopy and scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction. A temperature-programmed desorption technique was used to measure the absorbed hydrogen and study the dehydriding process. The content of hydrogen absorbed by the MgNi26-MA (approximately 1.3%, mass fraction) was 30 times higher than that of the MgNi26-GC. The MgNi26-RS sample absorbed only 0.1% of hydrogen. The lowest temperature for hydrogen evolution was exhibited by the MgNi26-MA. Compared with pure commercial MgH2, the decomposition temperature was reduced by more than 200 °C. The favourable phase and structural composition of the MgNi26-MA sample were the reasons for the best hydriding and dehydriding properties.
基金Project(50574034)supported by the National Natural Science Foundation of ChinaProject(20060213016)supported by Doctoral Education Fund of Ministry of Education of China。
文摘The hydriding of as-cast Mg-5.5%Zn-0.6%Zr(ZK60 Mg)(mass fraction)alloy was achieved by room-temperature reaction milling in hydrogen,with the mechanical energy serving as the driving force for the process.The hydriding progress during milling was examined by hydrogen absorption measurement,and the microstructure change was characterized by X-ray diffraction analysis(XRD),scanning electron microscopy(SEM),and transmission electron microscopy(TEM),respectively.The results show that,by room-temperature reaction milling in hydrogen,the as-cast ZK60 Mg alloy can be fully hydrided to form a nanocrystalline MgH_(2) single-phase microstructure.In particular,the average grain size of the MgH_(2) phase obtained by room-temperature reaction milling in hydrogen for 16.2 h is about 8-10 nm,and the average particle size of the as-milled hydrided powders is 2-3μm.
基金supported by 863 Program (2006AA05Z132)the National Natural Science Foundations of China (50871050 and 50701011)+1 种基金Natural Science Foundation of Inner Mongolia, China (200711020703)High Education Science Research Project of Inner Mongolia, China (NJzy08071)
文摘In order to improve the hydrogenation and dehydrogenation performances of the Mg2Ni-type alloys, Mg was partially substituted by La in the alloy, and melt spinning technology was used for the preparation of the Mg20-xLaxNi10 （x=0, 2, 4, 6） hydrogen storage alloys. The structures of the alloys were studied by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and high-resolution transmission electron microscopy （HRTEM）. It was found that no amorphous phase formed in the as-spun La-free alloy, but the as-spun alloys containing La held a major amorphous phase. When La content x≤2, the major phase in the as-cast alloys was Mg2Ni phase, but with further increase of La content, the major phase of the as-cast alloys changed into LaNi5＋LaMg3 phase. Thermal stability of the as-spun alloys was studied by differential scanning calorimetry （DSC）, showing that spinning rate was a negligible factor on the crystallization temperature of the amorphous phase. The hydrogen absorption and desorption kinetics of the as-cast and as-spun alloys were measured using an automatically controlled Sieverts apparatus, confirming that the hydrogen absorption and desorption capacities and kinetics of the as-cast alloys clearly increased with rising La content. For La content x=2, the as-spun alloy displayed optimal hydrogen desorption kinetics at 200 ℃.
基金Project(2006BB4197)supported by Chongqing Natural Science Foundation,China
文摘The Mg-Ni-based ternary alloys Mg2-xTixNi(x=0,0.2,0.4)and Mg2Ni1-xZrx(x=0,0.2,0.4)were successfully synthesized by mechanical grinding.The phases in the alloys and the hydriding/dehydriding properties of the alloys were investigated.Mg2Ni and Mg are the main hydrogen absorption phases in the alloys by XRD analysis.Hydriding kinetics curves of the alloys indicate that the hydrogen absorption rate increases after partial substitution of Ti for Mg and Zr for Ni.According to the measurement of pressure-concentration-isotherms and Van't Hoff equation,the relationship between ln p(H2)and 1 000/T was established.It is found that while increasing the content of correspondingly substituted elements at the same temperature,the equilibrium pressure of dehydriding increases,the enthalpy change and the stability of the alloy hydride decrease.
基金Project supported by National Natural Science Foundation of China(51161015,51371094)the Natural Science Foundation of Inner Mongolia,China(2013MS0722,2014MS0529)Talent Incubation Funding of School of Materials and Metallurgy(2014CY012)
文摘Hydrogen storage composites Nd2Mg17-50 wt.%Ni-x wt.%CeO2（x=0, 0.5, 1.0, 1.5, 2.0） were obtained by induction-ball milling method. The catalytic effect of CeO_2 on hydriding kinetics of Nd_2Mg17-50 wt.%Ni composite was investigated. X-ray diffraction（XRD） and high resolution transmission electron microscopy（HRTEM）, selected area electron diffraction（SAED） analyses showed that Nd_2Mg17-50 wt.%Ni alloy had a multiphase structure, consisting of NdMg12, NdMg_2Ni, Mg_2Ni and Ni phases and the addition of catalyst CeO_2 prompted the composites to be partly transformed into amorphous strucutre. The CeO_2 improved the maximum hydrogen capacity of Nd_2Mg17-50 wt.%Ni alloy from 3.192 wt.% to 3.376 wt.%（x=1.0）. What＇s more, the increment of diffusion coefficient D led to the faster hydriding kinetics, which was calculated by Avrami-Erofeev equation. The dehydrogenation temperature reduced from 515.54 to 504.72 K was mainly caused by the decrease of activation energy from 93.28 to 69.36 kJ /mol, which was proved by the Kissinger equation.
文摘La1.5Mg17Ni0.5 hydrogen storage materials were prepared by hydriding combustion synthesis (HCS) and mechanical alloying (MA) method respectively. The experimental results show that the hydrogen absorption properties of La1.5Mg17Nio.5 prepared by MA are better than that by HCS. La1.5Mg17Nio.5 prepared by MA can absorb 6.73 mass% hydrogen at 523 K within 1 min, and 4.92 mass% hydrogen at 423 K. The improvement of hydriding properties of La1.5Mg17Ni0.5alloy prepared by MA can be ascribed to the formation of nano-crystalline and defects during the mechanical alloying.
文摘The welding joints of Zircaloy 4 plates obtained by diffusion welding at 800°C under pressure in vacuum were cracked during autoclave tests at 400°C superheated steam after exposure longer than 150 days. The section of specimens was examined by optical microscopy and the composition at the tips of cracking was analyzed by electron microprobe. The result shows that the combination of oxidation and hydriding induced cracking is responsible for this failure of the welding joints.
基金Project supported by the National Natural Science Foundation of China (50276063)
文摘The structure and hydriding performance of La0.6Nd0.4Ni4.8Mn0.2Cux (x = 0 ～ 0.4) alloys were investigated in order to develop suitable materials for metal hydride air conditioner. The effect of Cu addition on the crystal structure,equilibrium pressure, hydrogen capacity and hysteresis as well as hydrogen absorption/desorption kinetics were systematically studied by using the measurement of P-C isotherms, X-ray diffraction and scanning electron microscopy. As the amount of Cu increases, the plateau pressure increases and hydrogen absorption/desorption kinetics is improved, but the effective hydrogen storage capacity decreases. It is shown that variations in the basal plane parameter a can be used as an indication for the plateau pressure changes. With the increase of parameter a, the plateau pressure decreases. For La0.6 Nd0.4Ni4.8Mn0.2Cux(x = 0 ～ 0.4) alloys there is a relationship between the effective hydrogen storage capacities and the ratios of their unit cell parameters c and a. The effective hydrogen storage capacity decreases with increase of a/c.
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financially supported by the National Key Research and Development Program of China (No. 2021YFB4000604)the National Natural Science Foundation of China (No. 52271220)+2 种基金the 111 Project (No. B12015)the Fundamental Research Funds for the Central UniversitiesHaihe Laboratory of Sustainable Chemical Transformations, Guangxi Collaborative Innovation Centre of Structure and Property for New Energy and Materials, Science Research and Technology Development Project of Guilin (No. 20210102-4)
文摘Novel hydrogen storage materials have propelled progress in hydrogen storage technologies.Magnesium hydride(MgH_(2))is a highly promising candidate.Nevertheless,several drawbacks,including the need for elevated thermal conditions,sluggish dehydrogena-tion kinetics,and high thermodynamic stability,limit its practical application.One effective method of addressing these challenges is cata-lyst doping,which effectively boosts the hydrogen storage capability of Mg-based materials.Herein,we review recent advancements in catalyst-doped MgH_(2) composites,with particular focus on multicomponent and high-entropy catalysts.Structure-property relationships and catalytic mechanisms in these doping strategies are also summarized.Finally,based on existing challenges,we discuss future research directions for the development of Mg-based hydrogen storage systems.
