The composites of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)as-quenched alloy and 3 wt.%M(M=CoS,CoS_(2),MoS_(2))catalyst were prepared by high-speed vibration ball mill.The effects of metal sulfides on the hydrogenation and dehy...The composites of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)as-quenched alloy and 3 wt.%M(M=CoS,CoS_(2),MoS_(2))catalyst were prepared by high-speed vibration ball mill.The effects of metal sulfides on the hydrogenation and dehydrogenation dynamics of alloys were compared.The results show that the as-milled composites contain a large number of amorphous embedded by a small amount of nanocrystals,and there are many point defects.After ball milling,the crystal grain size in the composites containing CoS is relatively larger,followed by CoS_(2)and MoS_(2)again.After hydrogenation,the amorphous phase is crystallized to form Mg_(2)NiH_(4),YH_(3),Pr_(8)H_(18.96),Sm_(3)H_7,Mg,Co or Mo phases,however,Mg_(2)Ni,YH_(2),PrH_(2)and Ni_(3)Y phases appeared after dehydrogenation.The maximum hydrogenation capacity of the composites containing CoS,CoS_(2)and MoS_(2)are 3.939,4.265 and 4.507 wt.%,respectively.The hydrogenation saturation ratio of composite containing MoS_(2)is higher than that of the composites containing CoS and CoS_(2).The dehydrogenation activation energy of the composites containing CoS,CoS_(2)and MoS_(2)is 107.76,68.43 and 63.28 kJ.mol^(-1).H_(2).On the improvement of hydrogen storage performance of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)alloy,the catalytic effect of MoS_(2)sulfide is better than that of CoS_(2)sulfide,and which is better than CoS sulfide.展开更多
Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocompo...Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.展开更多
A designed Mg_(88.7)Ni_(6.3)Y_(5)hydrogen storage alloy containing 14H type LPSO(long-period stacking ordered)and ternary eutectic structure was prepared by regulating the alloy composition and casting.The hydrogen st...A designed Mg_(88.7)Ni_(6.3)Y_(5)hydrogen storage alloy containing 14H type LPSO(long-period stacking ordered)and ternary eutectic structure was prepared by regulating the alloy composition and casting.The hydrogen storage performance of the alloy was improved by adding nano-flower-like TiO_(2)@C catalyst.The decomposition of the LPSO structure during hydrogenation led to the formation of plenty of nanocrystals which provided abundant interphase boundaries and activation sites.The nanoscale TiO_(2)@C catalyst was uniformly dispersed on the surface of alloy particles,and the"hydrogen overflow''effect of TiO_(2)@C accelerated the dissociation and diffusion of hydrogen on the surface of the alloy particles.As a result,the in-situ endogenous nanocrystals of the LPSO structure decomposition and the externally added flower-like TiO_(2)@C catalyst uniformly dispersed on the surface of the nanoparticles played a synergistic catalytic role in improving the hydrogen storage performance of the Mg-based alloy.With the addition of the TiO_(2)@C catalyst,the beginning hydrogen desorption temperature was reduced to 200℃.Furthermore,the saturated hydrogen absorption capacity of the sample was 5.32 wt.%,and it reached 4.25 wt.%H_(2) in 1 min at 200℃and 30 bar.展开更多
Grain growth of magnesium(Mg)and its hydride is one of the main reasons for kinetic and capacity degradation during the hydrogen absorption and desorption cycles.To solve this problem,herein we propose a novel method ...Grain growth of magnesium(Mg)and its hydride is one of the main reasons for kinetic and capacity degradation during the hydrogen absorption and desorption cycles.To solve this problem,herein we propose a novel method involving synergistic effect of inside embedded metals and outside coated graphene to limit the growth of Mg and its hydride grains.The graphene coated Mg-Y-Al alloys were selected as a model system for demonstrating this positive effect where the Mg_(91)Y_(3)Al_(6)alloy was first prepared by rapidly solidified method and then high-pressure milled with 5 wt%graphene upon 5 MPa hydrogen gas for obtaining in-situ formed YAl_(2)and YH_(3)embedded in the MgH_(2)matrix with graphene shell(denoted as MgH_(2)-Y-Al@GR).In comparison to pure MgH_(2),the obtained MgH_(2)-Y-Al@GR composites deliver much better kinetics and more stable cyclic performance.For instance,the MgH_(2)-Y-Al@GR can release about 6.1 wt%H_(2)within 30 min at 300℃ but pure MgH_(2)only desorbs∼1.5 wt%H_(2).The activation energy for desorption of MgH_(2)-Y-Al@GR samples is calculated to be 75.3±9.1 kJ/mol that is much lower than approximately 160 kJ/mol for pure MgH_(2).Moreover,its capacity retention is promoted from∼57%of pure MgH_(2)to∼84%after 50th cycles without obvious particle agglomeration and grain growth.The synergistic effect of outside graphene coating with inside embedded metals which could provide a huge number of active sites for catalysis as well as inhibit the grain growth of Mg and its hydride is believed to be responsible for these.展开更多
The hydrogen absorption/desorption kinetic properties of MgH_(2)can be effectively enhanced by doping specific catalysts.In this work,MOFs-derived NiCu@C nanoparticles(~15 nm)with regular core-shell structure were suc...The hydrogen absorption/desorption kinetic properties of MgH_(2)can be effectively enhanced by doping specific catalysts.In this work,MOFs-derived NiCu@C nanoparticles(~15 nm)with regular core-shell structure were successfully prepared and introduced into MgH_(2)(denoted as MgH_(2)-NiCu@C).The onset and peak temperatures of hydrogen desorption of MgH_(2)-11 wt.%NiCu@C are 175.0℃and282.2℃,respectively.The apparent activation energy of dehydrogenated reaction is 77.2±4.5 kJ/mol for MgH_(2)-11 wt.%NiCu@C,which is lower than half of that of the as-milled MgH_(2).Moreover,MgH_(2)-11 wt.%NiCu@C displays great cyclic stability.The strengthening"hydrogen pumping"effect of reversible solid solutions Mg_(2)Ni(Cu)/Mg_(2)Ni(Cu)H_(4)is proposed to explain the remarkable improvement in hydrogen absorption/desorption kinetic properties of MgH_(2).This work offers a novel perspective for the design of bimetallic nanoparticles and beyond for application in hydrogen storage and other energy related fields.展开更多
MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V...MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V_(2)O_(5) nanosheets(H-V_(2)O_(5))are specifically designed and used as catalysts to improve the hydrogen storage properties of MgH_(2).The as-prepared MgH_(2)-H-V_(2)O_(5) composites exhibit low desorption temperatures(Tonset=185℃)with a hydrogen capacity of 6.54 wt%,fast kinetics(Ea=84.55±1.37 kJ mol^(-1) H_(2) for desorption),and long cycling stability.Impressively,hydrogen absorption can be achieved at a temperature as low as 30℃ with a capacity of 2.38 wt%within 60 min.Moreover,the composites maintain a capacity retention rate of~99%after 100 cycles at 275℃.Experimental studies and theoretical calculations demonstrate that the in-situ formed VH_(2)/V catalysts,unique 2D structure of H-V_(2)O_(5) nanosheets,and abundant oxygen vacancies positively contribute to the improved hydrogen sorption properties.Notably,the existence of oxygen vacancies plays a double role,which could not only directly accelerate the hydrogen ab/de-sorption rate of MgH_(2),but also indirectly affect the activity of the catalytic phase VH_(2)/V,thereby further boosting the hydrogen storage performance of MgH_(2).This work highlights an oxygen vacancy excited“hydrogen pump”effect of VH_(2)/V on the hydrogen sorption of Mg/MgH_(2).The strategy developed here may pave a new way toward the development of oxygen vacancy-rich transition metal oxides catalyzed hydride systems.展开更多
基金the financial support provided by the Natural Science Foundations in Hebei Province(No.E2018201235)Baoding Science and Technology Planning Project(No.2074P019)+2 种基金Higher Education in Hebei Province School Science and Technology Research Project(No.QN2019209)Horizontal project(horizontal 20230048)2022 Hebei Province and Hebei University College Students Innovation and Entrepreneurship Training Program(Nos.2022265 and 2022266)。
文摘The composites of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)as-quenched alloy and 3 wt.%M(M=CoS,CoS_(2),MoS_(2))catalyst were prepared by high-speed vibration ball mill.The effects of metal sulfides on the hydrogenation and dehydrogenation dynamics of alloys were compared.The results show that the as-milled composites contain a large number of amorphous embedded by a small amount of nanocrystals,and there are many point defects.After ball milling,the crystal grain size in the composites containing CoS is relatively larger,followed by CoS_(2)and MoS_(2)again.After hydrogenation,the amorphous phase is crystallized to form Mg_(2)NiH_(4),YH_(3),Pr_(8)H_(18.96),Sm_(3)H_7,Mg,Co or Mo phases,however,Mg_(2)Ni,YH_(2),PrH_(2)and Ni_(3)Y phases appeared after dehydrogenation.The maximum hydrogenation capacity of the composites containing CoS,CoS_(2)and MoS_(2)are 3.939,4.265 and 4.507 wt.%,respectively.The hydrogenation saturation ratio of composite containing MoS_(2)is higher than that of the composites containing CoS and CoS_(2).The dehydrogenation activation energy of the composites containing CoS,CoS_(2)and MoS_(2)is 107.76,68.43 and 63.28 kJ.mol^(-1).H_(2).On the improvement of hydrogen storage performance of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)alloy,the catalytic effect of MoS_(2)sulfide is better than that of CoS_(2)sulfide,and which is better than CoS sulfide.
基金the National Natural Science Foundation of China(Nos.51871125,51761032,52001005 and 51731002)Major Science and Technology Innovation Projects in Shandong Province(No.2019JZZY010320)for financial support of the work.
文摘Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.
基金partially supported by the National Key R&D Program of China(No.2020YFA0406204)the National Natural Science Foundation of China(No.52201265)+1 种基金Shaanxi Province Key Project of Research and Development Plan,China(No.2023-YBGY-294,No.2023KXJ-060)the Doctoral Scientific Research Starting Foundation of Shaanxi University of Science and Technology,China(No.2016GBJ-02)。
文摘A designed Mg_(88.7)Ni_(6.3)Y_(5)hydrogen storage alloy containing 14H type LPSO(long-period stacking ordered)and ternary eutectic structure was prepared by regulating the alloy composition and casting.The hydrogen storage performance of the alloy was improved by adding nano-flower-like TiO_(2)@C catalyst.The decomposition of the LPSO structure during hydrogenation led to the formation of plenty of nanocrystals which provided abundant interphase boundaries and activation sites.The nanoscale TiO_(2)@C catalyst was uniformly dispersed on the surface of alloy particles,and the"hydrogen overflow''effect of TiO_(2)@C accelerated the dissociation and diffusion of hydrogen on the surface of the alloy particles.As a result,the in-situ endogenous nanocrystals of the LPSO structure decomposition and the externally added flower-like TiO_(2)@C catalyst uniformly dispersed on the surface of the nanoparticles played a synergistic catalytic role in improving the hydrogen storage performance of the Mg-based alloy.With the addition of the TiO_(2)@C catalyst,the beginning hydrogen desorption temperature was reduced to 200℃.Furthermore,the saturated hydrogen absorption capacity of the sample was 5.32 wt.%,and it reached 4.25 wt.%H_(2) in 1 min at 200℃and 30 bar.
基金financially supported by the Key Program for International S&T Cooperation Projects of China(No.2017YFE0124300)National Natural Science Foundation of China(No.52171205,51971002 and 52171197)+1 种基金Scientific Research Foundation of Anhui Provincial Education Department(Nos.KJ2020ZD26,KJ2021A0360)Anhui Provincial Natural Science Foundation for Excellent Youth Scholars(No.2108085Y16).
文摘Grain growth of magnesium(Mg)and its hydride is one of the main reasons for kinetic and capacity degradation during the hydrogen absorption and desorption cycles.To solve this problem,herein we propose a novel method involving synergistic effect of inside embedded metals and outside coated graphene to limit the growth of Mg and its hydride grains.The graphene coated Mg-Y-Al alloys were selected as a model system for demonstrating this positive effect where the Mg_(91)Y_(3)Al_(6)alloy was first prepared by rapidly solidified method and then high-pressure milled with 5 wt%graphene upon 5 MPa hydrogen gas for obtaining in-situ formed YAl_(2)and YH_(3)embedded in the MgH_(2)matrix with graphene shell(denoted as MgH_(2)-Y-Al@GR).In comparison to pure MgH_(2),the obtained MgH_(2)-Y-Al@GR composites deliver much better kinetics and more stable cyclic performance.For instance,the MgH_(2)-Y-Al@GR can release about 6.1 wt%H_(2)within 30 min at 300℃ but pure MgH_(2)only desorbs∼1.5 wt%H_(2).The activation energy for desorption of MgH_(2)-Y-Al@GR samples is calculated to be 75.3±9.1 kJ/mol that is much lower than approximately 160 kJ/mol for pure MgH_(2).Moreover,its capacity retention is promoted from∼57%of pure MgH_(2)to∼84%after 50th cycles without obvious particle agglomeration and grain growth.The synergistic effect of outside graphene coating with inside embedded metals which could provide a huge number of active sites for catalysis as well as inhibit the grain growth of Mg and its hydride is believed to be responsible for these.
基金supported by the National Natural Science Foundation of China(52071177,52171214)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX21_1112,KYCX21_1107)+1 种基金Six Talent Peaks Project in Jiangsu Province(2018,XNY-020)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions。
文摘The hydrogen absorption/desorption kinetic properties of MgH_(2)can be effectively enhanced by doping specific catalysts.In this work,MOFs-derived NiCu@C nanoparticles(~15 nm)with regular core-shell structure were successfully prepared and introduced into MgH_(2)(denoted as MgH_(2)-NiCu@C).The onset and peak temperatures of hydrogen desorption of MgH_(2)-11 wt.%NiCu@C are 175.0℃and282.2℃,respectively.The apparent activation energy of dehydrogenated reaction is 77.2±4.5 kJ/mol for MgH_(2)-11 wt.%NiCu@C,which is lower than half of that of the as-milled MgH_(2).Moreover,MgH_(2)-11 wt.%NiCu@C displays great cyclic stability.The strengthening"hydrogen pumping"effect of reversible solid solutions Mg_(2)Ni(Cu)/Mg_(2)Ni(Cu)H_(4)is proposed to explain the remarkable improvement in hydrogen absorption/desorption kinetic properties of MgH_(2).This work offers a novel perspective for the design of bimetallic nanoparticles and beyond for application in hydrogen storage and other energy related fields.
基金the support from the National Key Research&Development Program(2022YFB3803700)of ChinaNational Natural Science Foundation(No.52171186)the financial support from the Center of Hydrogen Science,Shanghai Jiao Tong University。
文摘MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V_(2)O_(5) nanosheets(H-V_(2)O_(5))are specifically designed and used as catalysts to improve the hydrogen storage properties of MgH_(2).The as-prepared MgH_(2)-H-V_(2)O_(5) composites exhibit low desorption temperatures(Tonset=185℃)with a hydrogen capacity of 6.54 wt%,fast kinetics(Ea=84.55±1.37 kJ mol^(-1) H_(2) for desorption),and long cycling stability.Impressively,hydrogen absorption can be achieved at a temperature as low as 30℃ with a capacity of 2.38 wt%within 60 min.Moreover,the composites maintain a capacity retention rate of~99%after 100 cycles at 275℃.Experimental studies and theoretical calculations demonstrate that the in-situ formed VH_(2)/V catalysts,unique 2D structure of H-V_(2)O_(5) nanosheets,and abundant oxygen vacancies positively contribute to the improved hydrogen sorption properties.Notably,the existence of oxygen vacancies plays a double role,which could not only directly accelerate the hydrogen ab/de-sorption rate of MgH_(2),but also indirectly affect the activity of the catalytic phase VH_(2)/V,thereby further boosting the hydrogen storage performance of MgH_(2).This work highlights an oxygen vacancy excited“hydrogen pump”effect of VH_(2)/V on the hydrogen sorption of Mg/MgH_(2).The strategy developed here may pave a new way toward the development of oxygen vacancy-rich transition metal oxides catalyzed hydride systems.
