Magnesium hydride(MgH_(2))has been widely regarded as a potential hydrogen storage material owing to its high gravimetric and volumetric capacity.Its sluggish kinetics and high activation energy barrier,however,severe...Magnesium hydride(MgH_(2))has been widely regarded as a potential hydrogen storage material owing to its high gravimetric and volumetric capacity.Its sluggish kinetics and high activation energy barrier,however,severely limit its practical application.Transition metal oxides(TMOs)have been extensively used as catalysts to improve the hydrogen storage performance of MgH_(2),but the low-valence transition metal(TM)ions,resulting from the reduction of TMOs accompanied by the formation of inactive Mg O,have been demonstrated to be the most effective components.Herein,we theoretically and experimentally confirm that the doping of low-valence TMs into Mg O could effectively weaken the Mg-H bonds and decrease the energy required for hydrogen desorption from MgH_(2),leading to superior catalytic activity compared to both TMOs and Mg O.In particular,the apparent activation energy for the dehydrogenation of Mg(Nb)O-catalyzed MgH_(2)could be reduced to only 84.1 kJ mol^(-1),and the reversible capacity could reach around 7 wt.%after 5 cycles with a capacity retention of 96%.Detailed theoretical calculations confirm that the remarkable orbital hybridization between Mg(Nb)O and MgH_(2)promotes charge transfer from MgO to the MgH_(2)monomer,resulting in significantly weakened stability of MgH_(2),which could effectively enhance its hydrogen storage performance.展开更多
It is challenging to create cation vacancies in electrode materials for enhancing the performance of rechargeable lithium ion batteries (LIBs). Herein, we utilized a strong alkaline etching method to successfully crea...It is challenging to create cation vacancies in electrode materials for enhancing the performance of rechargeable lithium ion batteries (LIBs). Herein, we utilized a strong alkaline etching method to successfully create Co vacancies at the interface of atomically thin Co_(3−x)O_(4)/graphene@CNT heterostructure for high-energy/power lithium storage. The creation of Co-vacancies in the sample was confirmed by high-resolution scanning transmission electron microscope (HRSTEM), X-ray photoelectron spectroscopy (XPS) and electron energy loss near-edge structures (ELNES). The obtained Co_(3−x)O_(4)/graphene@CNT delivers an ultra-high capacity of 1688.2 mAh g^(−1) at 0.2 C, excellent rate capability of 83.7% capacity retention at 1 C, and an ultralong life up to 1500 cycles with a reversible capacity of 1066.3 mAh g^(−1). Reaction kinetic study suggests a significant contribution from pseudocapacitive storage induced by the Co-vacancies at the Co_(3−x)O_(4)/graphene@CNT interface. Density functional theory confirms that the Co-vacancies could dramatically enhance the Li adsorption and provide an additional pathway with a lower energy barrier for Li diffusion, which results in an intercalation pseudocapacitive behavior and high-capacity/rate energy storage.展开更多
The authors regret that the wrong image of Fig.1 was uploaded in the paper.The correct one should be:We confirm the discrepancy is restricted to the image of Fig.1 only,the underlying data is correct and unchanged.The...The authors regret that the wrong image of Fig.1 was uploaded in the paper.The correct one should be:We confirm the discrepancy is restricted to the image of Fig.1 only,the underlying data is correct and unchanged.The authors would like to apologise for any inconvenience caused.展开更多
基金supported by the National Key R&D Program of China(No.2018YFB1502101)National Science Fund for Distinguished Young Scholars(51625102)+5 种基金National Natural Science Foundation of China(Nos.51874049,51401036,51901045)the Innovation Program of Shanghai Municipal Education Commission(2019–01–07–00–07E00028)the Science and Technology Commission of Shanghai Municipality(17XD1400700)the Changsha Science and Technology Program Project(No.kq1907092)the Science Research Project of Hunan Province Office of Education(No.20A024)the Programs for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning
文摘Magnesium hydride(MgH_(2))has been widely regarded as a potential hydrogen storage material owing to its high gravimetric and volumetric capacity.Its sluggish kinetics and high activation energy barrier,however,severely limit its practical application.Transition metal oxides(TMOs)have been extensively used as catalysts to improve the hydrogen storage performance of MgH_(2),but the low-valence transition metal(TM)ions,resulting from the reduction of TMOs accompanied by the formation of inactive Mg O,have been demonstrated to be the most effective components.Herein,we theoretically and experimentally confirm that the doping of low-valence TMs into Mg O could effectively weaken the Mg-H bonds and decrease the energy required for hydrogen desorption from MgH_(2),leading to superior catalytic activity compared to both TMOs and Mg O.In particular,the apparent activation energy for the dehydrogenation of Mg(Nb)O-catalyzed MgH_(2)could be reduced to only 84.1 kJ mol^(-1),and the reversible capacity could reach around 7 wt.%after 5 cycles with a capacity retention of 96%.Detailed theoretical calculations confirm that the remarkable orbital hybridization between Mg(Nb)O and MgH_(2)promotes charge transfer from MgO to the MgH_(2)monomer,resulting in significantly weakened stability of MgH_(2),which could effectively enhance its hydrogen storage performance.
基金This work was financially supported by the Australian Research Council(ARC)Discovery Projects(DP210103266,DP200100965 and DP200100365)the ARC Discovery Early Career Researcher Award(DE210101102)the Griffith University Postdoctoral Fellowship Scheme(YUDOU 036 Research Internal).
文摘It is challenging to create cation vacancies in electrode materials for enhancing the performance of rechargeable lithium ion batteries (LIBs). Herein, we utilized a strong alkaline etching method to successfully create Co vacancies at the interface of atomically thin Co_(3−x)O_(4)/graphene@CNT heterostructure for high-energy/power lithium storage. The creation of Co-vacancies in the sample was confirmed by high-resolution scanning transmission electron microscope (HRSTEM), X-ray photoelectron spectroscopy (XPS) and electron energy loss near-edge structures (ELNES). The obtained Co_(3−x)O_(4)/graphene@CNT delivers an ultra-high capacity of 1688.2 mAh g^(−1) at 0.2 C, excellent rate capability of 83.7% capacity retention at 1 C, and an ultralong life up to 1500 cycles with a reversible capacity of 1066.3 mAh g^(−1). Reaction kinetic study suggests a significant contribution from pseudocapacitive storage induced by the Co-vacancies at the Co_(3−x)O_(4)/graphene@CNT interface. Density functional theory confirms that the Co-vacancies could dramatically enhance the Li adsorption and provide an additional pathway with a lower energy barrier for Li diffusion, which results in an intercalation pseudocapacitive behavior and high-capacity/rate energy storage.
文摘The authors regret that the wrong image of Fig.1 was uploaded in the paper.The correct one should be:We confirm the discrepancy is restricted to the image of Fig.1 only,the underlying data is correct and unchanged.The authors would like to apologise for any inconvenience caused.
