Cation additives can efficiently enhance the total electrochemical capabilities of zinc-ion hybrid capacitors (ZHCs).However their energy storage mechanisms in zinc-based systems are still under debate.Herein,we modul...Cation additives can efficiently enhance the total electrochemical capabilities of zinc-ion hybrid capacitors (ZHCs).However their energy storage mechanisms in zinc-based systems are still under debate.Herein,we modulate the electrolyte and achieve dual-ion storage by adding magnesium ions.And we assemble several Zn//activated carbon devices with different electrolyte concentrations and investigate their electrochemical reaction dynamic behaviors.The zinc-ion capacitor with Mg^(2+)mixed solution delivers 82 mAh·g^(-1)capacity at 1 A·g^(-1) and maintains 91%of the original capacitance after 10000 cycling.It is superior to the other assembled zinc-ion devices in single-component electrolytes.The finding demonstrates that the double-ion storage mechanism enables the superior rate performance and long cycle lifetime of ZHCs.展开更多
LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nan...LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nanoconfinement is effective in achieving low dehydrogenation temperature and favorable reversibility.Besides,graphene can serve as supporting materials for LiBH_(4)catalysts and also destabilize LiBH_(4)via interfacial reaction.However,graphene has never been used alone as a frame material for nanoconfining LiBH_(4).In this study,graphene microflowers with large pore volumes were prepared and used as nanoconfinement framework material for LiBH_(4),and the nanoconfinement effect of graphene was revealed.After loading 70 wt%of LiBH_(4) and mechanically compressed at 350 MPa,8.0 wt% of H2 can be released within 100 min at 320C,corresponding to the highest volumetric hydrogen storage density of 94.9 g H2 L^(-1)ever reported.Thanks to the nanoconfinement of graphene,the rate-limiting step of dehydrogenation of nanoconfined LiBH_(4) was changed and its apparent activation energy of the dehydrogenation(107.3 kJ mol^(-1))was 42%lower than that of pure LiBH_(4).Moreover,the formation of the intermediate Li_(2)B_(12)H_(12) was effectively inhibited,and the stable nanoconfined structure enhanced the reversibility of LiBH_(4).This work widens the understanding of graphene's nanoconfinement effect and provides new insights for developing high-density hydrogen storage materials.展开更多
Hydrogen storage is a key link in hydrogen economy,where solid-state hydrogen storage is considered as the most promising approach because it can meet the requirement of high density and safety.Thereinto,magnesium-bas...Hydrogen storage is a key link in hydrogen economy,where solid-state hydrogen storage is considered as the most promising approach because it can meet the requirement of high density and safety.Thereinto,magnesium-based materials(MgH_(2))are currently deemed as an attractive candidate due to the potentially high hydrogen storage density(7.6 wt%),however,the stable thermodynamics and slow kinetics limit the practical application.In this study,we design a ternary transition metal sulfide FeNi_(2)S_(4)with a hollow balloon structure as a catalyst of MgH_(2)to address the above issues by constructing a MgH_(2)/Mg_(2)NiH_(4)-MgS/Fe system.Notably,the dehydrogenation/hydrogenation of MgH_(2)has been significantly improved due to the synergistic catalysis of active species of Mg_(2)Ni/Mg_(2)NiH_(4),MgS and Fe originated from the MgH_(2)-FeNi_(2)S_(4)composite.The hydrogen absorption capacity of the MgH_(2)-FeNi_(2)S_(4)composite reaches to 4.02 wt%at 373 K for 1 h,a sharp contrast to the milled-MgH_(2)(0.67 wt%).In terms of dehydrogenation process,the initial dehydrogenation temperature of the composite is 80 K lower than that of the milled-MgH_(2),and the dehydrogenation activation energy decreases by 95.7 kJ·mol-1 compared with the milled-MgH_(2)(161.2 kJ·mol^(-1)).This method provides a new strategy for improving the dehydrogenation/hydrogenation performance of the MgH_(2)material.展开更多
氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过...氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。展开更多
基金financially supported by the National Natural Science Foundation of China (No.52172218)。
文摘Cation additives can efficiently enhance the total electrochemical capabilities of zinc-ion hybrid capacitors (ZHCs).However their energy storage mechanisms in zinc-based systems are still under debate.Herein,we modulate the electrolyte and achieve dual-ion storage by adding magnesium ions.And we assemble several Zn//activated carbon devices with different electrolyte concentrations and investigate their electrochemical reaction dynamic behaviors.The zinc-ion capacitor with Mg^(2+)mixed solution delivers 82 mAh·g^(-1)capacity at 1 A·g^(-1) and maintains 91%of the original capacitance after 10000 cycling.It is superior to the other assembled zinc-ion devices in single-component electrolytes.The finding demonstrates that the double-ion storage mechanism enables the superior rate performance and long cycle lifetime of ZHCs.
基金supported by National Key Research and Development Program of China(2021YFB4000602)National Natural Science Foundation of PR China(Nos.52071287,52072342,52271227)+3 种基金National Outstanding Youth Foundation of China(No.52125104)Natural Science Foundation of Zhejiang Province,PR China(No.LZ23E010002)Young Talent Fund of Association for Science and Technology in Shaanxi,China(No.20220456)Young Star Project of Science and Technology of Shaanxi Province(2022KJXX-43).
文摘LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nanoconfinement is effective in achieving low dehydrogenation temperature and favorable reversibility.Besides,graphene can serve as supporting materials for LiBH_(4)catalysts and also destabilize LiBH_(4)via interfacial reaction.However,graphene has never been used alone as a frame material for nanoconfining LiBH_(4).In this study,graphene microflowers with large pore volumes were prepared and used as nanoconfinement framework material for LiBH_(4),and the nanoconfinement effect of graphene was revealed.After loading 70 wt%of LiBH_(4) and mechanically compressed at 350 MPa,8.0 wt% of H2 can be released within 100 min at 320C,corresponding to the highest volumetric hydrogen storage density of 94.9 g H2 L^(-1)ever reported.Thanks to the nanoconfinement of graphene,the rate-limiting step of dehydrogenation of nanoconfined LiBH_(4) was changed and its apparent activation energy of the dehydrogenation(107.3 kJ mol^(-1))was 42%lower than that of pure LiBH_(4).Moreover,the formation of the intermediate Li_(2)B_(12)H_(12) was effectively inhibited,and the stable nanoconfined structure enhanced the reversibility of LiBH_(4).This work widens the understanding of graphene's nanoconfinement effect and provides new insights for developing high-density hydrogen storage materials.
基金This work was supported by the National Natural Science Foundation of China(grant numbers 52071281 and 51971197)the Natural Science Foundation of Hebei Province(grant numbers E2019203161,E2019203414 and E2020203081)Science and Technology Major project of Inner Mongolia(2020ZD0012).
文摘Hydrogen storage is a key link in hydrogen economy,where solid-state hydrogen storage is considered as the most promising approach because it can meet the requirement of high density and safety.Thereinto,magnesium-based materials(MgH_(2))are currently deemed as an attractive candidate due to the potentially high hydrogen storage density(7.6 wt%),however,the stable thermodynamics and slow kinetics limit the practical application.In this study,we design a ternary transition metal sulfide FeNi_(2)S_(4)with a hollow balloon structure as a catalyst of MgH_(2)to address the above issues by constructing a MgH_(2)/Mg_(2)NiH_(4)-MgS/Fe system.Notably,the dehydrogenation/hydrogenation of MgH_(2)has been significantly improved due to the synergistic catalysis of active species of Mg_(2)Ni/Mg_(2)NiH_(4),MgS and Fe originated from the MgH_(2)-FeNi_(2)S_(4)composite.The hydrogen absorption capacity of the MgH_(2)-FeNi_(2)S_(4)composite reaches to 4.02 wt%at 373 K for 1 h,a sharp contrast to the milled-MgH_(2)(0.67 wt%).In terms of dehydrogenation process,the initial dehydrogenation temperature of the composite is 80 K lower than that of the milled-MgH_(2),and the dehydrogenation activation energy decreases by 95.7 kJ·mol-1 compared with the milled-MgH_(2)(161.2 kJ·mol^(-1)).This method provides a new strategy for improving the dehydrogenation/hydrogenation performance of the MgH_(2)material.
文摘氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。
