Potassium-ion batteries(PIBs)are considered promising alternatives to lithium-ion batteries owing to cost-effective potassium resources and a suitable redox potential of-2.93 V(vs.-3.04 V for Li+/Li).However,the explo...Potassium-ion batteries(PIBs)are considered promising alternatives to lithium-ion batteries owing to cost-effective potassium resources and a suitable redox potential of-2.93 V(vs.-3.04 V for Li+/Li).However,the exploration of appro-priate electrode materials with the correct size for reversibly accommodating large K+ions presents a significant challenge.In addition,the reaction mecha-nisms and origins of enhanced performance remain elusive.Here,tetragonal FeSe nanoflakes of different sizes are designed to serve as an anode for PIBs,and their live and atomic-scale potassiation/depotassiation mechanisms are revealed for the first time through in situ high-resolution transmission electron micros-copy.We found that FeSe undergoes two distinct structural evolutions,sequen-tially characterized by intercalation and conversion reactions,and the initial intercalation behavior is size-dependent.Apparent expansion induced by the intercalation of K+ions is observed in small-sized FeSe nanoflakes,whereas unexpected cracks are formed along the direction of ionic diffusion in large-sized nanoflakes.The significant stress generation and crack extension originating from the combined effect of mechanical and electrochemical interactions are elucidated by geometric phase analysis and finite-element analysis.Despite the different intercalation behaviors,the formed products of Fe and K_(2)Se after full potassiation can be converted back into the original FeSe phase upon depotassiation.In particular,small-sized nanoflakes exhibit better cycling perfor-mance with well-maintained structural integrity.This article presents the first successful demonstration of atomic-scale visualization that can reveal size-dependent potassiation dynamics.Moreover,it provides valuable guidelines for optimizing the dimensions of electrode materials for advanced PIBs.展开更多
Harvesting the promising high energy density of advanced electrode materials in lithium-ion batteries is critically dependent on a mechanistic understanding on how the materials function and degrade along with the bat...Harvesting the promising high energy density of advanced electrode materials in lithium-ion batteries is critically dependent on a mechanistic understanding on how the materials function and degrade along with the battery cycling.Here,we tracked phase transformations during(de)lithiation of Sb_(2)Se_(3) single crystals using in situ high-resolution transmission electron microscopy(HRTEM)technique,and revealed electro-chemo-mechanical evolution at the reaction interface.The effect of this electro-chemo-mechanical coupling has a complicated interplay on the lithiation kinetics and causes various types of defects at the reaction front,including dislocation dipoles,antiphase boundaries,and cracks.In return,the formed cracks and related defects build a path for fast diffusion of lithium ions and trigger a highly anisotropic lithiation at the twisted reaction front,giving rise to the formation of presumably "dead" Sb_(2)Se_(3) nanodomains in amorphous Li_(x)Sb_(2)Se_(3).The detailed mechanistic understanding may facilitate the rational design of high-capacity electrode materials for battery applications.展开更多
基金This work was supported by the National Key R&D Program of China(Grant No.2018YFB1304902)the National Natural Science Foundation of China(Grant Nos.12004034,U1813211,22005247,11904372,51502007,52072323,52122211,12174019,and 51972058)+1 种基金the Gen-eral Research Fund of Hong Kong(Project No.11217221)China Postdoctoral Science Foundation Funded Project(Grant No.2021M690386).
文摘Potassium-ion batteries(PIBs)are considered promising alternatives to lithium-ion batteries owing to cost-effective potassium resources and a suitable redox potential of-2.93 V(vs.-3.04 V for Li+/Li).However,the exploration of appro-priate electrode materials with the correct size for reversibly accommodating large K+ions presents a significant challenge.In addition,the reaction mecha-nisms and origins of enhanced performance remain elusive.Here,tetragonal FeSe nanoflakes of different sizes are designed to serve as an anode for PIBs,and their live and atomic-scale potassiation/depotassiation mechanisms are revealed for the first time through in situ high-resolution transmission electron micros-copy.We found that FeSe undergoes two distinct structural evolutions,sequen-tially characterized by intercalation and conversion reactions,and the initial intercalation behavior is size-dependent.Apparent expansion induced by the intercalation of K+ions is observed in small-sized FeSe nanoflakes,whereas unexpected cracks are formed along the direction of ionic diffusion in large-sized nanoflakes.The significant stress generation and crack extension originating from the combined effect of mechanical and electrochemical interactions are elucidated by geometric phase analysis and finite-element analysis.Despite the different intercalation behaviors,the formed products of Fe and K_(2)Se after full potassiation can be converted back into the original FeSe phase upon depotassiation.In particular,small-sized nanoflakes exhibit better cycling perfor-mance with well-maintained structural integrity.This article presents the first successful demonstration of atomic-scale visualization that can reveal size-dependent potassiation dynamics.Moreover,it provides valuable guidelines for optimizing the dimensions of electrode materials for advanced PIBs.
基金supported by the National Key R&D Program of China(2018YFB1304902)the National Natural Science Foundation of China(11904372,U1813211,and 12004034)+2 种基金Beijing Institute of Technology Research Fund Program for Young ScholarsBeijing Institute of Technology Laboratory Research Project(2019BITSYA03)China Postdoctoral Science Foundation Funded Project(2021M690386)。
文摘Harvesting the promising high energy density of advanced electrode materials in lithium-ion batteries is critically dependent on a mechanistic understanding on how the materials function and degrade along with the battery cycling.Here,we tracked phase transformations during(de)lithiation of Sb_(2)Se_(3) single crystals using in situ high-resolution transmission electron microscopy(HRTEM)technique,and revealed electro-chemo-mechanical evolution at the reaction interface.The effect of this electro-chemo-mechanical coupling has a complicated interplay on the lithiation kinetics and causes various types of defects at the reaction front,including dislocation dipoles,antiphase boundaries,and cracks.In return,the formed cracks and related defects build a path for fast diffusion of lithium ions and trigger a highly anisotropic lithiation at the twisted reaction front,giving rise to the formation of presumably "dead" Sb_(2)Se_(3) nanodomains in amorphous Li_(x)Sb_(2)Se_(3).The detailed mechanistic understanding may facilitate the rational design of high-capacity electrode materials for battery applications.
