The polysulfide shuttle effect critically hinders lithium-sulfur(Li-S)battery development,therefore,the design of heterogeneous interface engineering with“adsorption-catalysis”functions for polysulfide conversion ha...The polysulfide shuttle effect critically hinders lithium-sulfur(Li-S)battery development,therefore,the design of heterogeneous interface engineering with“adsorption-catalysis”functions for polysulfide conversion has garnered considerable attention.However,the exploration of the intricate relationship between key electronic properties and catalytic activity at such interfaces remains a challenge.Additionally,a comprehensive understanding of the thermodynamic growth mechanisms for heterostructure materials is lacking.Herein,a Ni-based homologous structure was precisely constructed via thermodynamic control,with a specific focus on optimizing the interface design.The theoretical results show that the heterostructures with adjustable composition realize the appropriate upward shift to the D-band,improving the affinity towards polysulfide,and further reducing the reaction energy barrier.On this basis,the relationship between interface design and the D-band center,as well as catalytic performance,was established.Specifically,M-Ni_(3)Fe/Ni_(3)ZnC_(0.7)accomplishes the electron enrichment at the interface,supporting the further diffusion of polysulfides,and lowering the Li-S bond energy,performing the bidirectional catalytic transformation of polysulfides.As a result,the Li-S batteries with the cathode of M-Ni_(3)Fe/Ni_(3)ZnC_(0.7)/S deliver rate performances of discharge capacity of 514 mA h g^(−1)at 5.0 C.This understanding of the D-band and interfacial design provides a framework for Li-S catalyst optimization.展开更多
Hard carbon(HC)anodes are one of the most promising electrodes for sodium-ion batteries(SIBs)because of their low cost,high reversible specific capacity,and suitable operating voltage.However,the poor fast-charging pr...Hard carbon(HC)anodes are one of the most promising electrodes for sodium-ion batteries(SIBs)because of their low cost,high reversible specific capacity,and suitable operating voltage.However,the poor fast-charging properties of HC limits the broad applicability of SIBs in practical scenarios.This review initially meticulously dissects the underlying sodium storage mechanisms and kinetic behaviors of the HC anode,elucidating the direct correlation with the rate capabilities.Afterward,recent advancements in the field are systematically surveyed,encompassing strategies such as structural modification,interface engineering,morphology regulation,and electrolyte optimization.These methodologies are pivotal in addressing the challenges and unlocking the full potential of HC anodes for high-rate SIB applications.Eventually,by synthesizing the current state-of-theart and delineating prospective research directions.This review aims to promote the development of HC,thereby advancing nextgeneration SIBs with superior energy density,cycle life,high-rate capability,and safety,ultimately facilitating the broader adoption of sodium-based energy storage systems.展开更多
Lithium metal batteries(LMBs)are regarded as highly promising high-energy-density battery technology,primarily due to the ultrahigh theoretical capacity(3860 mAh g-1)and low electrochemical redox potential(-3.04 V vs....Lithium metal batteries(LMBs)are regarded as highly promising high-energy-density battery technology,primarily due to the ultrahigh theoretical capacity(3860 mAh g-1)and low electrochemical redox potential(-3.04 V vs.SHE)of the lithium metal anode.Nevertheless,the inherent flammability of conventional electrolytes poses significant safety challenges,inevitably limiting the practical deployment of LMBs.Triethyl phosphate(TEP)-based electrolytes,which endow the merits of low cost,exceptional thermal stability,and intrinsic nonflammability,have attracted considerable attention.In this review,we first introduce the key challenges associated with TEP-based electrolytes in LMBs.We then provide a comprehensive overview of recent progress in the development of TEP-based electrolytes in LMBs.Furthermore,we discuss modification strategies and propose future research directions for optimizing TEP-based electrolytes in LMBs.This review aims to provide valuable insights and guidance for the design of advanced TEP-based electrolytes,thereby facilitating the development of stable and safe LMBs.展开更多
Sodium-ion batteries(SIBs)have emerged as promising candidate for large-scale energy storage systems,owing to the abundant natural reserves of sodium,low production costs,and similar electrochemical properties to lith...Sodium-ion batteries(SIBs)have emerged as promising candidate for large-scale energy storage systems,owing to the abundant natural reserves of sodium,low production costs,and similar electrochemical properties to lithium-ion batteries.However,the graphite anodes used in commercial lithium-ion batteries cannot be directly applied to sodium-ion batteries.Among various reported anode materials,hard carbon has attracted extensive attention in SIBs because of its excellent sodium storage capability and cost-effectiveness.In this review,we focus on summarizing the recent advances of coal-based hard carbon anode materials for SIBs.We first introduce the common preparation methods of coal-based hard carbon anode materials.In addition,we overview the effective modification strategies(regulation of oxygen-containing groups,hierarchical pore structures engineering,and heteroatom doping)to boost the sodium storage performance of coal-based hard carbon anode materials.Further research directions of coal-based hard carbon anode materials for SIBs are also proposed.This review is expected to significantly promote the commercial application of coal-based hard carbon anodes.展开更多
Hard carbon(HC)anodes in sodium-ion batteries(SIBs)are prized for their high capacity,durability,costefficiency,environmental sustainability,and safety.The metallic ash elements in HCs inevitably affect the overall pe...Hard carbon(HC)anodes in sodium-ion batteries(SIBs)are prized for their high capacity,durability,costefficiency,environmental sustainability,and safety.The metallic ash elements in HCs inevitably affect the overall performance of SIBs,however,the unclear role of metallic ash elements during carbonization and the electrochemical sodium storage process presents challenges for advancing HC design concepts.In this review,the traditional role of metallic ash element realized in the past and the deep understanding by a new sight from the view of intrinsic types in precursor matrix are initially introduced.Subsequently,the effect of catalyzing graphitization degree,constructing pore structure,tuning SEI formation and tailoring defects of the HCs regulated by extrinsic factors introduced through experimental conditions in recent years are comprehensively summarized.Additionally,future development prospects and perspectives on the research about metallic ash element in HC are also briefly outlined.It is believed that this review can deliver noteworthy viewpoints by introducing metallic ash elements,for the continued development of adjusting the microstructure of HCs at the nanoscale to actualize highperformance SIBs.展开更多
Nanoscale Kirkendall effect has been widely used for rationally fabricating high-quality hollow nanocrystals, but often requires the intrinsic diffusion coefficient of out-diffusion materials higher than that of in-di...Nanoscale Kirkendall effect has been widely used for rationally fabricating high-quality hollow nanocrystals, but often requires the intrinsic diffusion coefficient of out-diffusion materials higher than that of in-diffusion components. Here we demonstrate an unexpected Kirkendall effect that occurs in diffusing intrinsically faster Cu atoms into Pd icosahedra, leading to the formation of PdCu alloyed hollow nanocrystals. The control experiment with Pd octahedra replacing icosahedra indicates the critical role of twin boundaries in facilitating such unexpected Kirkendall effect. In addition, geometric phase analysis and density functional theory calculation show that out-diffusion of Pd atoms in the icosahedra is faster than in-diffusion of Cu atoms, particularly through the twin boundaries, upon the strain gradient with an inward distribution from tensile to compressive strains. The unexpected Kirkendall effect is also found in the interdiffusion of Ag and Pd atoms in Pd icosahedra. Our finds break the limitation of the intrinsic diffusion coefficient for the synthesis of hollow nanocrystals through Kirkendall effect and are expected to enormously enrich the family of hollow nanocrystals which have shown great potential in broad areas, such as fine chemical production, energy storage and conversion, and environmental protection. This work also provides a deep understanding in the diffusion behavior of atoms upon the strain gradient.展开更多
For finding the real roots of a polynomial,we propose a clipping algorithmcalled SLEFEclipping and an isolation algorithmcalled SLEFEisolation algorithm.Ateach iterative step,the SLEFEclipping algorithm generates two ...For finding the real roots of a polynomial,we propose a clipping algorithmcalled SLEFEclipping and an isolation algorithmcalled SLEFEisolation algorithm.Ateach iterative step,the SLEFEclipping algorithm generates two broken lines boundingthe given polynomial.Then,a sequence of intervals can be obtained by computing theintersection of the sequence of broken lines with the abscissa axis.The sequence ofthese intervals converges to the root with a convergence rate of 2.Numerical examplesshow that SLEFE clipping requires fewer iterations and less computation time thancurrent algorithms,and the SLEFE isolation algorithm can compute all intervals thatcontain the roots rapidly and accurately.展开更多
基金supported financially by the National Natural Science Foundation of China(52172242,22109135,52371237)the Science&Technology Talents Lifting Project of Hunan Province(2023TJ-Z32)+2 种基金the Hunan Provincial Education Office Foundation of China(20B570,23B0126)the Natural Science Foundation of Hunan Province(2021JJ30659,2022JJ40423)the Postgraduate Scientific Research Innovation Project of Hunan Province(QL20230146).
文摘The polysulfide shuttle effect critically hinders lithium-sulfur(Li-S)battery development,therefore,the design of heterogeneous interface engineering with“adsorption-catalysis”functions for polysulfide conversion has garnered considerable attention.However,the exploration of the intricate relationship between key electronic properties and catalytic activity at such interfaces remains a challenge.Additionally,a comprehensive understanding of the thermodynamic growth mechanisms for heterostructure materials is lacking.Herein,a Ni-based homologous structure was precisely constructed via thermodynamic control,with a specific focus on optimizing the interface design.The theoretical results show that the heterostructures with adjustable composition realize the appropriate upward shift to the D-band,improving the affinity towards polysulfide,and further reducing the reaction energy barrier.On this basis,the relationship between interface design and the D-band center,as well as catalytic performance,was established.Specifically,M-Ni_(3)Fe/Ni_(3)ZnC_(0.7)accomplishes the electron enrichment at the interface,supporting the further diffusion of polysulfides,and lowering the Li-S bond energy,performing the bidirectional catalytic transformation of polysulfides.As a result,the Li-S batteries with the cathode of M-Ni_(3)Fe/Ni_(3)ZnC_(0.7)/S deliver rate performances of discharge capacity of 514 mA h g^(−1)at 5.0 C.This understanding of the D-band and interfacial design provides a framework for Li-S catalyst optimization.
基金supported by the National Natural Science Foundation of China(52402302,52250710680)the High-end Foreign Experts Recruitment Plan of China(G2023016009L)+4 种基金the Zhejiang Provincial Natural Science Foundation of China(LQ24E020001)the Key Research and Development Program of Zhejiang Province(2023C01232)the Basic Research Project of Wenzhou City(G2023016)the Science and Technology Plan Project of Wenzhou Municipality(ZG2022032)the Natural Science Foundation of Changsha(kq2402017).
文摘Hard carbon(HC)anodes are one of the most promising electrodes for sodium-ion batteries(SIBs)because of their low cost,high reversible specific capacity,and suitable operating voltage.However,the poor fast-charging properties of HC limits the broad applicability of SIBs in practical scenarios.This review initially meticulously dissects the underlying sodium storage mechanisms and kinetic behaviors of the HC anode,elucidating the direct correlation with the rate capabilities.Afterward,recent advancements in the field are systematically surveyed,encompassing strategies such as structural modification,interface engineering,morphology regulation,and electrolyte optimization.These methodologies are pivotal in addressing the challenges and unlocking the full potential of HC anodes for high-rate SIB applications.Eventually,by synthesizing the current state-of-theart and delineating prospective research directions.This review aims to promote the development of HC,thereby advancing nextgeneration SIBs with superior energy density,cycle life,high-rate capability,and safety,ultimately facilitating the broader adoption of sodium-based energy storage systems.
基金supported by the National Natural Science Foundation of China(52202286,22309002,52250710680,52171217)the Key Research and Development Program of Zhejiang Province(2023C01232,2024C01057)+3 种基金the Natural Science Foundation of Zhejiang Province(LY24B030006)the Science and Technology Plan Project of Wenzhou Municipality(ZG2024055,ZG2022032)the Wenzhou Association for Science and Technology Innovation Program(NLTS2024-013)the Basic Research Project of Wenzhou City(G20220016)。
文摘Lithium metal batteries(LMBs)are regarded as highly promising high-energy-density battery technology,primarily due to the ultrahigh theoretical capacity(3860 mAh g-1)and low electrochemical redox potential(-3.04 V vs.SHE)of the lithium metal anode.Nevertheless,the inherent flammability of conventional electrolytes poses significant safety challenges,inevitably limiting the practical deployment of LMBs.Triethyl phosphate(TEP)-based electrolytes,which endow the merits of low cost,exceptional thermal stability,and intrinsic nonflammability,have attracted considerable attention.In this review,we first introduce the key challenges associated with TEP-based electrolytes in LMBs.We then provide a comprehensive overview of recent progress in the development of TEP-based electrolytes in LMBs.Furthermore,we discuss modification strategies and propose future research directions for optimizing TEP-based electrolytes in LMBs.This review aims to provide valuable insights and guidance for the design of advanced TEP-based electrolytes,thereby facilitating the development of stable and safe LMBs.
基金supported by the Yunnan Major Scientific and Technological Projects(No.202202AG050003)the National Natural Science Foundation of China(Nos.52262034 and 52202286)+4 种基金the Natural Science Foundation of Yunnan Province(No.202401AW070016)Natural Science Foundation of Zhejiang Province(No.LY24B030006)Key Laboratory of Ionic Rare Earth Resources and Environment,Ministry of Natural Resources of the People’s Republic of China(No.2023IRERE206)Science and Technology Plan Project of Wenzhou Municipality(No.ZG2024055)the Project Funding from“Xingdian Talent Support Plan”.
文摘Sodium-ion batteries(SIBs)have emerged as promising candidate for large-scale energy storage systems,owing to the abundant natural reserves of sodium,low production costs,and similar electrochemical properties to lithium-ion batteries.However,the graphite anodes used in commercial lithium-ion batteries cannot be directly applied to sodium-ion batteries.Among various reported anode materials,hard carbon has attracted extensive attention in SIBs because of its excellent sodium storage capability and cost-effectiveness.In this review,we focus on summarizing the recent advances of coal-based hard carbon anode materials for SIBs.We first introduce the common preparation methods of coal-based hard carbon anode materials.In addition,we overview the effective modification strategies(regulation of oxygen-containing groups,hierarchical pore structures engineering,and heteroatom doping)to boost the sodium storage performance of coal-based hard carbon anode materials.Further research directions of coal-based hard carbon anode materials for SIBs are also proposed.This review is expected to significantly promote the commercial application of coal-based hard carbon anodes.
基金supported by the National Natural Science Foundation of China(52402302,52250710680)High-end Foreign Experts Recruitment Plan of China(G2023016009L)+3 种基金Zhejiang Provincial Natural Science Foundation of China(LQ24E020001)Key Research and Development Program of Zhejiang Province(2024C01057,2023C01232)Science and Technology Plan Project of Wenzhou Municipality(ZG2022032)The Natural Science Foundation of Changsha(kq2402017).
文摘Hard carbon(HC)anodes in sodium-ion batteries(SIBs)are prized for their high capacity,durability,costefficiency,environmental sustainability,and safety.The metallic ash elements in HCs inevitably affect the overall performance of SIBs,however,the unclear role of metallic ash elements during carbonization and the electrochemical sodium storage process presents challenges for advancing HC design concepts.In this review,the traditional role of metallic ash element realized in the past and the deep understanding by a new sight from the view of intrinsic types in precursor matrix are initially introduced.Subsequently,the effect of catalyzing graphitization degree,constructing pore structure,tuning SEI formation and tailoring defects of the HCs regulated by extrinsic factors introduced through experimental conditions in recent years are comprehensively summarized.Additionally,future development prospects and perspectives on the research about metallic ash element in HC are also briefly outlined.It is believed that this review can deliver noteworthy viewpoints by introducing metallic ash elements,for the continued development of adjusting the microstructure of HCs at the nanoscale to actualize highperformance SIBs.
基金This work was supported by the National Science Foundation of China(Nos.51522103,51871200,and 61721005)and the National Program for Support of Top-Notch Young Professionals.
文摘Nanoscale Kirkendall effect has been widely used for rationally fabricating high-quality hollow nanocrystals, but often requires the intrinsic diffusion coefficient of out-diffusion materials higher than that of in-diffusion components. Here we demonstrate an unexpected Kirkendall effect that occurs in diffusing intrinsically faster Cu atoms into Pd icosahedra, leading to the formation of PdCu alloyed hollow nanocrystals. The control experiment with Pd octahedra replacing icosahedra indicates the critical role of twin boundaries in facilitating such unexpected Kirkendall effect. In addition, geometric phase analysis and density functional theory calculation show that out-diffusion of Pd atoms in the icosahedra is faster than in-diffusion of Cu atoms, particularly through the twin boundaries, upon the strain gradient with an inward distribution from tensile to compressive strains. The unexpected Kirkendall effect is also found in the interdiffusion of Ag and Pd atoms in Pd icosahedra. Our finds break the limitation of the intrinsic diffusion coefficient for the synthesis of hollow nanocrystals through Kirkendall effect and are expected to enormously enrich the family of hollow nanocrystals which have shown great potential in broad areas, such as fine chemical production, energy storage and conversion, and environmental protection. This work also provides a deep understanding in the diffusion behavior of atoms upon the strain gradient.
基金the joint grant by National Natural Science Foundation ofChina(No.11471093)Thanks to the authors of references for the valuable ideas to this paper and thanksto the reviewers for their precious opinions proposed to this paper.
文摘For finding the real roots of a polynomial,we propose a clipping algorithmcalled SLEFEclipping and an isolation algorithmcalled SLEFEisolation algorithm.Ateach iterative step,the SLEFEclipping algorithm generates two broken lines boundingthe given polynomial.Then,a sequence of intervals can be obtained by computing theintersection of the sequence of broken lines with the abscissa axis.The sequence ofthese intervals converges to the root with a convergence rate of 2.Numerical examplesshow that SLEFE clipping requires fewer iterations and less computation time thancurrent algorithms,and the SLEFE isolation algorithm can compute all intervals thatcontain the roots rapidly and accurately.
