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
Lead sulfide(PbS),a typical functional semiconductor material,has attracted serious attention due to its great potential in optoelectronics applications.However,controllable growth of PbS single-crystal film still rem...Lead sulfide(PbS),a typical functional semiconductor material,has attracted serious attention due to its great potential in optoelectronics applications.However,controllable growth of PbS single-crystal film still remains a great challenge.Here,we report heteroepitaxial growth of large-scale highly crystalline PbS films on alkali salt(NaCl and KCl)substrates via chemical vapor deposition(CVD).Structural characterizations demonstrate that the as-grown PbS films exhibit an atomically sharp interface with the underlying substrates.The epitaxial relationships between the epilayers and substrates were determined to be PbS(100)//NaCl(100)or KCl(100),PbS[010]//NaCl[010]or KCl[010].Owing to the high solubility of alkali salt,the epitaxial PbS films can be rapidly released from the underlying substrates and transferred to other substrates of interest while maintaining good integrity and crystallinity,the process of which is particularly attractive in the fields of electronics and optoelectronics.Furthermore,photodetectors based on the transferred PbS films were fabricated,exhibiting a high photoresponsivity of 7.5 A/W,a detectivity of 1.44×10^(12)Jones,and a rapid response time of approximately 0.25 s.This work sheds light on the batch production,green transfer,and optoelectronic application of PbS films.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The authors gratefully acknowledge Beijing Advanced Innovation Center for Intelligent Robots and Systems in Beijing Institute of Technology for the use of FIB and TEM.Financial support was provided by the National Natural Science Foundation of China(No.11704389)the Scientific Equipment Development Project and Youth Innovation Promotion Association Project of Chinese Academy of Sciences.
文摘Lead sulfide(PbS),a typical functional semiconductor material,has attracted serious attention due to its great potential in optoelectronics applications.However,controllable growth of PbS single-crystal film still remains a great challenge.Here,we report heteroepitaxial growth of large-scale highly crystalline PbS films on alkali salt(NaCl and KCl)substrates via chemical vapor deposition(CVD).Structural characterizations demonstrate that the as-grown PbS films exhibit an atomically sharp interface with the underlying substrates.The epitaxial relationships between the epilayers and substrates were determined to be PbS(100)//NaCl(100)or KCl(100),PbS[010]//NaCl[010]or KCl[010].Owing to the high solubility of alkali salt,the epitaxial PbS films can be rapidly released from the underlying substrates and transferred to other substrates of interest while maintaining good integrity and crystallinity,the process of which is particularly attractive in the fields of electronics and optoelectronics.Furthermore,photodetectors based on the transferred PbS films were fabricated,exhibiting a high photoresponsivity of 7.5 A/W,a detectivity of 1.44×10^(12)Jones,and a rapid response time of approximately 0.25 s.This work sheds light on the batch production,green transfer,and optoelectronic application of PbS films.
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)。
