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
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 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
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
Ultrasonic treatment has great contributions on modifying the morphology,dimension and distribution of constituent phases during solidification,which serve as dominate factors influencing the hydrogen storage performa...Ultrasonic treatment has great contributions on modifying the morphology,dimension and distribution of constituent phases during solidification,which serve as dominate factors influencing the hydrogen storage performance of Mg-based alloys.In this research,ultrasonic treatment is utilized as a novel method to enhance the de-/hydriding properties of Mg-2Ni(at.%)alloy.Due to ultrasonic treatment,the microstructure of as-cast alloy is significantly refined and homogenized.Ascribing to the increased eutectic boundaries and shortened distance insideα-Mg for hydrogen atoms diffusion,the hydrogen uptake capacities and isothermal de-/hydriding rates improve effectively,especially at lower temperature.The peak desorption temperature reduces from 392.99°C to 345.56°C,and the dehydriding activation energy decreases from 101.93 k J mol^(-1)to 88.65 k J mol^(-1).Weakened hysteresis of plateau pressures and slightly optimized thermodynamics are determined from the pressure-composition isotherms.Owing to the refined primary Mg,a larger amount of hydrogen with the higher hydriding proportion is absorbed in the first stage when hydrides nucleate in eutectic region and grow on primary Mg periphery subsequently before MgH2colonies impinging,resulting in the enhancement of hydrogenation rates and capacities.展开更多
Mg-based materials have been intensively studied for hydrogen storage applications due to their high energy density up to 2600 Wh/kg or 3700 Wh/L.However,the Mg-based materials with poor kinetics and the necessity for...Mg-based materials have been intensively studied for hydrogen storage applications due to their high energy density up to 2600 Wh/kg or 3700 Wh/L.However,the Mg-based materials with poor kinetics and the necessity for a high temperature to achieve 0.1 MPa hydrogen equilibrium pressure limit the applications in the onboard storage in Fuel cell vehicles(FCVs).Over the past decades,many methods have been applied to improve the hydriding/dehydriding(H/D)kinetics of Mg/MgH 2 by forming amorphous or nanosized particles,adding catalysts and employing external energy field,etc.However,which method is more effective and the intrinsic mechanism they work are widely differing versions.The hydrogenation and dehydrogenation behaviors of Mg-based alloys analyzing by kinetic models is an efficient way to reveal the H/D kinetic mechanism.However,some recently proposed models with physical meaning and simple analysis method are not known intimately by researchers.Therefore,this review focuses on the enhancement method of kinetics in Mg-based hydrogen storage materials and introduces the new kinetic models.展开更多
In order to optimize the dehydriding process for producing nanocrystalline Mg alloy powders by hydriding-dehydriding treatment,nano-structured as-hydrided Mg-3%Al-1%Zn(AZ31 Mg)(mass fraction)alloy powders were thermal...In order to optimize the dehydriding process for producing nanocrystalline Mg alloy powders by hydriding-dehydriding treatment,nano-structured as-hydrided Mg-3%Al-1%Zn(AZ31 Mg)(mass fraction)alloy powders were thermally dehydrided at various temperatures from 275 to 375℃.The kinetics of hydrogen desorption was examined by hydrogen discharge measurement during dehydriding.The microstructure of the as-hydrided and the subsequently fully dehydrided alloy powders was investigated by X-ray diffraction analysis(XRD)and transmission electron microscopy(TEM),respectively.Both the desorption kinetics and the grain size of the alloy after complete dehydriding were found to be strongly dependent on the processing temperature.The higher the temperature,the faster the desorption,and the more significant the grain growth.When the desorption temperature was raised from 300 to 375℃,the time to achieve complete dehydriding was shortened from 190 to 20 min,and the average grain size increased correspondingly from 20 to 58 nm.展开更多
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 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 ℃.
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.
基金supported by National Key Research and Development Program of China(2017YFA0403804)National Natural Science Foundation of China(51825401)
文摘Ultrasonic treatment has great contributions on modifying the morphology,dimension and distribution of constituent phases during solidification,which serve as dominate factors influencing the hydrogen storage performance of Mg-based alloys.In this research,ultrasonic treatment is utilized as a novel method to enhance the de-/hydriding properties of Mg-2Ni(at.%)alloy.Due to ultrasonic treatment,the microstructure of as-cast alloy is significantly refined and homogenized.Ascribing to the increased eutectic boundaries and shortened distance insideα-Mg for hydrogen atoms diffusion,the hydrogen uptake capacities and isothermal de-/hydriding rates improve effectively,especially at lower temperature.The peak desorption temperature reduces from 392.99°C to 345.56°C,and the dehydriding activation energy decreases from 101.93 k J mol^(-1)to 88.65 k J mol^(-1).Weakened hysteresis of plateau pressures and slightly optimized thermodynamics are determined from the pressure-composition isotherms.Owing to the refined primary Mg,a larger amount of hydrogen with the higher hydriding proportion is absorbed in the first stage when hydrides nucleate in eutectic region and grow on primary Mg periphery subsequently before MgH2colonies impinging,resulting in the enhancement of hydrogenation rates and capacities.
基金H.Shao acknowledges the Macao Science and Technol-ogy Development Fund(FDCT)for funding(project no.118/2016/A3 and 0062/2018/A2)and this work was also par-tially supported by a Start-Up Research Fund from the Uni-versity of Macao(SRG2016-00088-FST)+5 种基金Q.Li also thanks the financial support from the National Natural Science Foun-dation of China(51671118)Young Elite Scientists Sponsor-ship Program by CAST(2017QNRC001)the“Chenguang”Program from the Shanghai Municipal Education Commission(17CG42)Science and Technology Committee of Shanghai(16520721800)the Program for Professor of Special Ap-pointment(Eastern Scholar)by Shanghai Municipal Educa-tion Commission(No.TP2015040).。
文摘Mg-based materials have been intensively studied for hydrogen storage applications due to their high energy density up to 2600 Wh/kg or 3700 Wh/L.However,the Mg-based materials with poor kinetics and the necessity for a high temperature to achieve 0.1 MPa hydrogen equilibrium pressure limit the applications in the onboard storage in Fuel cell vehicles(FCVs).Over the past decades,many methods have been applied to improve the hydriding/dehydriding(H/D)kinetics of Mg/MgH 2 by forming amorphous or nanosized particles,adding catalysts and employing external energy field,etc.However,which method is more effective and the intrinsic mechanism they work are widely differing versions.The hydrogenation and dehydrogenation behaviors of Mg-based alloys analyzing by kinetic models is an efficient way to reveal the H/D kinetic mechanism.However,some recently proposed models with physical meaning and simple analysis method are not known intimately by researchers.Therefore,this review focuses on the enhancement method of kinetics in Mg-based hydrogen storage materials and introduces the new kinetic models.
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In order to optimize the dehydriding process for producing nanocrystalline Mg alloy powders by hydriding-dehydriding treatment,nano-structured as-hydrided Mg-3%Al-1%Zn(AZ31 Mg)(mass fraction)alloy powders were thermally dehydrided at various temperatures from 275 to 375℃.The kinetics of hydrogen desorption was examined by hydrogen discharge measurement during dehydriding.The microstructure of the as-hydrided and the subsequently fully dehydrided alloy powders was investigated by X-ray diffraction analysis(XRD)and transmission electron microscopy(TEM),respectively.Both the desorption kinetics and the grain size of the alloy after complete dehydriding were found to be strongly dependent on the processing temperature.The higher the temperature,the faster the desorption,and the more significant the grain growth.When the desorption temperature was raised from 300 to 375℃,the time to achieve complete dehydriding was shortened from 190 to 20 min,and the average grain size increased correspondingly from 20 to 58 nm.