Tailoring 1D nanotubes with refined interfacial interactions and optimized adsorption sites presents a highly promising yet challenging strategy for advancing Na/Li-ion batteries(SIBs/LIBs).Herein,the intertwined yard...Tailoring 1D nanotubes with refined interfacial interactions and optimized adsorption sites presents a highly promising yet challenging strategy for advancing Na/Li-ion batteries(SIBs/LIBs).Herein,the intertwined yardlong bean-like Fe_(9)Ni_(9)S_(16)/FeS heterostructures with sulfur vacancies encapsulated in N-doped carbon nanotubes(3 N-Fe_(9)Ni_(9)S_(16)/FeS-3@CNTs)are controllably synthesized through Fe/Ni-catalyzed pyrolysis of dicyandiamide followed by sulfidation strategies.1D nanotubes with robust outer walls and internal cavity structures shorten the diffusion paths of ions/electrons and buffer volume expansion and aggregation of active materials.The Fe_(9)Ni_(9)S_(16)/FeS heterostructure provides a powerful driving force for charge transfer by forming built-in electric fields,optimizing ion adsorption,while the Fe_(9)Ni_(9)S_(16)features a wider interlayer spacing that allows for frequent Na+/Li+insertion and extraction,thereby enhancing the reaction kinetics within the electrode.Driven by these synergistic factors,the 3 N-Fe_(9)Ni_(9)S_(16)/FeS-3@CNTs demonstrates remarkable electrochemical performance,achieving a substantial reversible capacity of up to 682.1mA h g^(−1)for SIBs at 0.1 A g^(−1)and 782.7 mA h g^(−1)for LIBs at 0.5 A g−1,alongside exceptional cycling stability in SIBs,maintaining 78.7%of its capacity after 1500 cycles at 1 A g^(−1)coupling with the ether-based electrolyte.Employing various electrochemical analyses in conjunction with ex-situ characterization techniques and Density Functional Theory(DFT)calculations,the storage mechanisms and phase transition processes are investigated,elucidating the structure-composition-performance relationships.This work paves the way for a new strategy in designing advanced materials with engineered heterostructures and controllable defects for energy conversion and storage devices.展开更多
Sodium titanium phosphate(NaTi_(2)(PO_(4))_(3),NTP)has emerged as a promising electrode material due to its three-dimensional open framework.This study investigates the use of NTP in aqueous dilute Li^(+)/Na^(+)electr...Sodium titanium phosphate(NaTi_(2)(PO_(4))_(3),NTP)has emerged as a promising electrode material due to its three-dimensional open framework.This study investigates the use of NTP in aqueous dilute Li^(+)/Na^(+)electrolytes and extends its application to high-concentration K+electrolytes.X-ray photoelectron spectroscopy,X-ray absorption near-edge structure analysis,and density functional theory calculations revealed that highly electronegative fluorine partially substitutes for oxygen in the NTP lattice,resulting in the formation of Ti-F bonds.The substitution effectively modulates the electronic structure of Ti^(4+),alters the local coordination environment,and influences the redox dynamics.Enhanced long-term cycling stability and rate performance were demonstrated across aqueous sodium-ion,lithium-ion,and potassium-ion half-cells.Among the investigated systems,the aqueous sodium-ion system exhibited the best electrochemical performance,characterized by a single,well-defined charge–discharge plateau,stable cycling behavior with 88.7%capacity retention after 500 cycles at 1 A g^(−1),and an initial specific discharge capacity of 121.7 mAh g^(−1) at 0.2 A g^(−1).The results establish F-doped NTP as a promising candidate for advanced energy storage applications in aqueous alkali metal-ion batteries.展开更多
基金supported by the program of National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT and Future planning(grant number 2022R1A4A1034312,2023R1A2C1007413)by the Commercialization Promotion Agency for R&D Outcomes(COMPA)grant funded by the Korean Government(Ministery of Science and ICT)(RS-2023-00304764)。
文摘Tailoring 1D nanotubes with refined interfacial interactions and optimized adsorption sites presents a highly promising yet challenging strategy for advancing Na/Li-ion batteries(SIBs/LIBs).Herein,the intertwined yardlong bean-like Fe_(9)Ni_(9)S_(16)/FeS heterostructures with sulfur vacancies encapsulated in N-doped carbon nanotubes(3 N-Fe_(9)Ni_(9)S_(16)/FeS-3@CNTs)are controllably synthesized through Fe/Ni-catalyzed pyrolysis of dicyandiamide followed by sulfidation strategies.1D nanotubes with robust outer walls and internal cavity structures shorten the diffusion paths of ions/electrons and buffer volume expansion and aggregation of active materials.The Fe_(9)Ni_(9)S_(16)/FeS heterostructure provides a powerful driving force for charge transfer by forming built-in electric fields,optimizing ion adsorption,while the Fe_(9)Ni_(9)S_(16)features a wider interlayer spacing that allows for frequent Na+/Li+insertion and extraction,thereby enhancing the reaction kinetics within the electrode.Driven by these synergistic factors,the 3 N-Fe_(9)Ni_(9)S_(16)/FeS-3@CNTs demonstrates remarkable electrochemical performance,achieving a substantial reversible capacity of up to 682.1mA h g^(−1)for SIBs at 0.1 A g^(−1)and 782.7 mA h g^(−1)for LIBs at 0.5 A g−1,alongside exceptional cycling stability in SIBs,maintaining 78.7%of its capacity after 1500 cycles at 1 A g^(−1)coupling with the ether-based electrolyte.Employing various electrochemical analyses in conjunction with ex-situ characterization techniques and Density Functional Theory(DFT)calculations,the storage mechanisms and phase transition processes are investigated,elucidating the structure-composition-performance relationships.This work paves the way for a new strategy in designing advanced materials with engineered heterostructures and controllable defects for energy conversion and storage devices.
基金supported by the National Natural Science Foundation of China(52072298,51802261,11675129)the Natural Science Basic Research Plan in Shaanxi Province of China(2025JC-YBQN-758)+1 种基金Scientific Research Program Funded by Shaanxi Provincial Education Department(Program No.23JK0662)the Youth Innovation Team of Shaanxi Universities.
文摘Sodium titanium phosphate(NaTi_(2)(PO_(4))_(3),NTP)has emerged as a promising electrode material due to its three-dimensional open framework.This study investigates the use of NTP in aqueous dilute Li^(+)/Na^(+)electrolytes and extends its application to high-concentration K+electrolytes.X-ray photoelectron spectroscopy,X-ray absorption near-edge structure analysis,and density functional theory calculations revealed that highly electronegative fluorine partially substitutes for oxygen in the NTP lattice,resulting in the formation of Ti-F bonds.The substitution effectively modulates the electronic structure of Ti^(4+),alters the local coordination environment,and influences the redox dynamics.Enhanced long-term cycling stability and rate performance were demonstrated across aqueous sodium-ion,lithium-ion,and potassium-ion half-cells.Among the investigated systems,the aqueous sodium-ion system exhibited the best electrochemical performance,characterized by a single,well-defined charge–discharge plateau,stable cycling behavior with 88.7%capacity retention after 500 cycles at 1 A g^(−1),and an initial specific discharge capacity of 121.7 mAh g^(−1) at 0.2 A g^(−1).The results establish F-doped NTP as a promising candidate for advanced energy storage applications in aqueous alkali metal-ion batteries.
