Ni-rich layered oxides are one of the most promising cathode materials for Li-ion batteries due to their high energy density.However,the chemomechanical breakdown and capacity degradation associated with the anisotrop...Ni-rich layered oxides are one of the most promising cathode materials for Li-ion batteries due to their high energy density.However,the chemomechanical breakdown and capacity degradation associated with the anisotropic lattice evolution during lithiation/delithiation hinders its practical application.Herein,by utilizing the in situ environmental transmission electron microscopy(ETEM),we provide a real time nanoscale characterization of high temperature solid-state synthesis of LiNi_(0.8)CO_(0.1)Mn_(0.1)O_(2)(NCM811) cathode,and unprecedentedly reveal the strain/stress formation and morphological evolution mechanism of primary/second ary particles,as well as their influence on electrochemical performance.We show that stress inhomogeneity during solid-state synthesis will lead to both primary/secondary particle pulverization and new grain boundary initiation,which are detrimental to cathode cycling stability and rate performance.Aiming to alleviate this multiscale strain during solid-state synthesis,we introduced a calcination scheme that effectively relieves the stress during the synthesis,thus mitigating the primary/secondary particle crack and the detrimental grain boundaries formation,which in turn improves the cathode structural integrity and Li-ion transport kinetics for long-life and high-rate electrochemical performance.This work remarkably advances the fundamental understanding on mechanochemical properties of transition metal oxide cathode with solid-state synthesis and provides a unified guide for optimization the Ni-rich oxide cathode.展开更多
原子尺度原位研究金属纳米颗粒的氧化过程,对理解金属氧化反应机理和合理设计金属纳米材料有重要意义。长期以来,研究人员通过热重分析、X射线衍射、X射线光电子能谱等手段对金属块体材料和薄膜材料的氧化行为和反应机理开展了广泛研究...原子尺度原位研究金属纳米颗粒的氧化过程,对理解金属氧化反应机理和合理设计金属纳米材料有重要意义。长期以来,研究人员通过热重分析、X射线衍射、X射线光电子能谱等手段对金属块体材料和薄膜材料的氧化行为和反应机理开展了广泛研究。但当金属的尺寸缩小到纳米尺度时,其比表面积、电子结构都与块体材料显著不同,从而导致其氧化行为和反应机理也与块体材料产生差异。由于纳米颗粒体积小,氧化速率快,传统方法很难对其微观的氧化机理进行原位研究。受益于环境控制的电子显微镜技术(atmosphere controlled TEM technologies)的发展,人们有机会在原子尺度对金属纳米颗粒的氧化行为进行系统研究,包括柯肯达尔效应、氧化动力学过程等。然而目前对金属纳米颗粒氧化的研究仍然处于初期阶段,其氧化初期的形核过程仍有待揭示,温度、氧气分压、载体作用对金属纳米颗粒氧化的影响仍有待进一步研究。本文主要以近几年利用原位TEM研究金属纳米颗粒氧化的工作为例,简要介绍这些工作在认识金属氧化理论和推进反应机理的理解方面的最新进展,并探讨了未来研究的机遇和挑战。展开更多
The extremely high structural tolerance of ceria to oxygen vacancies(Ov)has made it a desirable catalytic material for the hydrocarbon oxidation to chemicals and pharmaceuticals and the reduction of gaseous pollutants...The extremely high structural tolerance of ceria to oxygen vacancies(Ov)has made it a desirable catalytic material for the hydrocarbon oxidation to chemicals and pharmaceuticals and the reduction of gaseous pollutants.It is proposed that the formation and diffusion of Ov originate from its outstanding reduction property.However,the formation and diffusion process of Ov over the surface of ceria at the atomic level is still unknown.Herein,the structural and valence evolution of CeO_(2)(111)surfaces in reductive,oxidative and vacuum environments from room temperature up to 700℃was studied with in situ aberration-corrected environmental transmission electron microscopy(ETEM)experiments.Ov is found to form under a high vacuum at elevated temperatures;however,the surface can recover to the initial state through the adsorption of oxygen atoms in an oxygen-contained environment.Furthermore,in hydrogen environment,the step-CeO_(2)(111)surface is not stable at elevated temperatures;thus,the steps tend to be eliminated with increasing temperature.Combined with first-principles density function calculations(DFT),it is proposed that O-terminated surfaces would develop in a hypoxic environment due to the dynamic diffusion of Ov from the outer surface to the subsurface.Furthermore,in a reductive environment,H2 facilitates the formation and diffusion of Ov while Ce-terminated surfaces develope.These results reveal dynamic atomic-scale interplay between the nanoceria surface and gas,thereby providing fundamental insights into the Ov-dependent reaction of nano-CeO_(2) during catalytic processes.展开更多
Thermal treatment is a general and efficient way to synthesize intermetallic catalysts and may involve complicated physical processes.So far,the mechanisms leading to the size and composition heterogeneity,as well as ...Thermal treatment is a general and efficient way to synthesize intermetallic catalysts and may involve complicated physical processes.So far,the mechanisms leading to the size and composition heterogeneity,as well as the phase segregation behavior in Pt-Co nanoparticles(NPs)are still not well understood.Via in-situ environmental transmission electron microscopy,the formation dynamics and segregation behaviors of Pt-Co alloyed NPs during the thermal treatment were investigated.It is found that Pt-Co NPs on zeolitic imidazolate frameworks-67-derived nanocarbon(NC)are formed consecutively through both particle migration coalescence and the Ostwald ripening process.The existence of Pt NPs is found to affect the movement of Co NPs during their migration.With the help of theoretical calculations,the correlations between the composition and migration of the Pt and Co during the ripening process were uncovered.These complex alloying processes are revealed as key factors leading to the heterogeneity of the synthesized Pt-Co alloyed NPs.Under oxidation environment,the Pt-Co NPs become surface faceted gradually,which can be attributed to the oxygen facilitated relatively higher segregation rate of Co from the(111)surface.This work advances the fundamental understanding of design,synthesis,and durability of the Pt-based nanocatalysts.展开更多
Direct observation of the dissolution behavior of nanomaterials could provide fundamental insight to understanding their anisotropic properties and stability. The dissolution mechanism in solution and vacuum has been ...Direct observation of the dissolution behavior of nanomaterials could provide fundamental insight to understanding their anisotropic properties and stability. The dissolution mechanism in solution and vacuum has been well documented. However, the gas-involved dissolution and regrowth have seldom been explored and the mechanisms remain elusive. We report herein, an in situ TEM study of the dissolution and regrowth dynamics of MoO2 nanowires under oxygen using environmental transmission electron microscopy (ETEM). For the first time, oscillatory dissolution on the nanowire tip is revealed, and, intriguingly, simultaneous layer-by-layer regrowth on the sidewall facets is observed, leading to a shorter and wider nanowire. Combined with first-principles calculations, we found that electron beam irradiation caused oxygen loss in the tip facets, which resulted in changing the preferential growth facets and drove the morphology reshaping.展开更多
The dynamics of oxidation of cobalt nanoparticles were directly revealed by in situ environmental transmission electron microscopy.Firstly,cobalt nanoparticles were oxidized to polycrystalline cobalt monoxide,then to ...The dynamics of oxidation of cobalt nanoparticles were directly revealed by in situ environmental transmission electron microscopy.Firstly,cobalt nanoparticles were oxidized to polycrystalline cobalt monoxide,then to polycrystalline tricobalt tetroxide,in the presence of oxygen with a low partial pressure.Numerous cavities(or voids) were formed during the oxidation,owing to the Kirkendall effect.Analysis of the oxides growth suggested that the oxidation of cobalt nanoparticles followed a parabolic rate law,which was consistent with diffusion-limited kinetics.In situ transmission electron microscopy allowed potential atomic oxidation pathways to be considered.The outward diffusion of cobalt atoms inside the oxide layer controlled the oxidation,and formed the hollow structure.Irradiation by the electron beam,which destroyed the sealing effect of graphite layer coated on the cobalt surface and resulted in fast oxidation rate,played an important role in activating and promoting the oxidations.These findings further our understanding on the microscopic kinetics of metal nanocrystal oxidation and knowledge of energetic electrons promoting oxidation reaction.展开更多
We report the in situ transmission electron microscope (TEM) observation of the catalytic gasification and growth of carbon nanotubes (CNTs). It was found that iron catalysts can consume the CNTs when pumping out the ...We report the in situ transmission electron microscope (TEM) observation of the catalytic gasification and growth of carbon nanotubes (CNTs). It was found that iron catalysts can consume the CNTs when pumping out the precursor gas, acetylene, at the growth temperature, and reinitiate the growth when acetylene is re-introduced. The switching between gasification and growth of CNTs can be repeated many times with the same catalyst. To understand the phenomenon, thermogravimetric analysis (TGA) coupled with mass spectroscopy was used to study the mechanism involved. It was shown that the residual water molecules in the growth chamber of the TEM react with and remove carbon atoms of CNTs as carbon monoxide vapor under the action of the catalyst, when the precursor gas is pumped out. This result contributes to a better understanding of the water-assisted and oxygen-assisted synthesis of CNT arrays, and provides useful clues on how to extend the lifetime and improve the activity of the catalysts.展开更多
基金the funding support from the National Natural Science Foundation of China (Nos. 52022088, 51971245, 51772262, U20A20336, 21935009)the National Key R&D Program of China (No. 2022YFB2404300, 2022YFE0207900)+2 种基金the Natural Science Foundation of Hebei Province (No. F2021203097, B2020203037)the China Postdoctoral Science Foundation (Grant number 2021M702756)the Sichuan Science and Technology Program and Science and Technology Planning Project of Yibin Sanjiang New Area (2022JBGS002, 2022ZYD0125, 23QYCX0034, 2021ZYGY022)。
文摘Ni-rich layered oxides are one of the most promising cathode materials for Li-ion batteries due to their high energy density.However,the chemomechanical breakdown and capacity degradation associated with the anisotropic lattice evolution during lithiation/delithiation hinders its practical application.Herein,by utilizing the in situ environmental transmission electron microscopy(ETEM),we provide a real time nanoscale characterization of high temperature solid-state synthesis of LiNi_(0.8)CO_(0.1)Mn_(0.1)O_(2)(NCM811) cathode,and unprecedentedly reveal the strain/stress formation and morphological evolution mechanism of primary/second ary particles,as well as their influence on electrochemical performance.We show that stress inhomogeneity during solid-state synthesis will lead to both primary/secondary particle pulverization and new grain boundary initiation,which are detrimental to cathode cycling stability and rate performance.Aiming to alleviate this multiscale strain during solid-state synthesis,we introduced a calcination scheme that effectively relieves the stress during the synthesis,thus mitigating the primary/secondary particle crack and the detrimental grain boundaries formation,which in turn improves the cathode structural integrity and Li-ion transport kinetics for long-life and high-rate electrochemical performance.This work remarkably advances the fundamental understanding on mechanochemical properties of transition metal oxide cathode with solid-state synthesis and provides a unified guide for optimization the Ni-rich oxide cathode.
文摘原子尺度原位研究金属纳米颗粒的氧化过程,对理解金属氧化反应机理和合理设计金属纳米材料有重要意义。长期以来,研究人员通过热重分析、X射线衍射、X射线光电子能谱等手段对金属块体材料和薄膜材料的氧化行为和反应机理开展了广泛研究。但当金属的尺寸缩小到纳米尺度时,其比表面积、电子结构都与块体材料显著不同,从而导致其氧化行为和反应机理也与块体材料产生差异。由于纳米颗粒体积小,氧化速率快,传统方法很难对其微观的氧化机理进行原位研究。受益于环境控制的电子显微镜技术(atmosphere controlled TEM technologies)的发展,人们有机会在原子尺度对金属纳米颗粒的氧化行为进行系统研究,包括柯肯达尔效应、氧化动力学过程等。然而目前对金属纳米颗粒氧化的研究仍然处于初期阶段,其氧化初期的形核过程仍有待揭示,温度、氧气分压、载体作用对金属纳米颗粒氧化的影响仍有待进一步研究。本文主要以近几年利用原位TEM研究金属纳米颗粒氧化的工作为例,简要介绍这些工作在认识金属氧化理论和推进反应机理的理解方面的最新进展,并探讨了未来研究的机遇和挑战。
基金Project supported by the National Key Research and Development Plan(2021YFA1200201)the Natural Science Foundation of China(51872008)+1 种基金the"111"Project under the DB18015 grantBeijing Outstanding Young Scientists Projects(BJJWZYJH01201910005018)。
文摘The extremely high structural tolerance of ceria to oxygen vacancies(Ov)has made it a desirable catalytic material for the hydrocarbon oxidation to chemicals and pharmaceuticals and the reduction of gaseous pollutants.It is proposed that the formation and diffusion of Ov originate from its outstanding reduction property.However,the formation and diffusion process of Ov over the surface of ceria at the atomic level is still unknown.Herein,the structural and valence evolution of CeO_(2)(111)surfaces in reductive,oxidative and vacuum environments from room temperature up to 700℃was studied with in situ aberration-corrected environmental transmission electron microscopy(ETEM)experiments.Ov is found to form under a high vacuum at elevated temperatures;however,the surface can recover to the initial state through the adsorption of oxygen atoms in an oxygen-contained environment.Furthermore,in hydrogen environment,the step-CeO_(2)(111)surface is not stable at elevated temperatures;thus,the steps tend to be eliminated with increasing temperature.Combined with first-principles density function calculations(DFT),it is proposed that O-terminated surfaces would develop in a hypoxic environment due to the dynamic diffusion of Ov from the outer surface to the subsurface.Furthermore,in a reductive environment,H2 facilitates the formation and diffusion of Ov while Ce-terminated surfaces develope.These results reveal dynamic atomic-scale interplay between the nanoceria surface and gas,thereby providing fundamental insights into the Ov-dependent reaction of nano-CeO_(2) during catalytic processes.
基金the National Natural Science Foundation of China(Nos.52072345,U21A20328,22103047,and 12174348)the China Postdoctoral Science Foundation(No.2021T140621)+3 种基金the Natural Science Foundation of Henan Province(No.222300420077)Henan Center for Outstanding Overseas Scientists(No.GZS201903)support from Strategic Priority Research Program(B)(No.XDB33030200)of Chinese Academy of Sciencesperformed at the Center for Functional Nanomaterials,which is a US DOE Office of Science Facility,at Brookhaven National Laboratory under Contract No.DESC0012704.
文摘Thermal treatment is a general and efficient way to synthesize intermetallic catalysts and may involve complicated physical processes.So far,the mechanisms leading to the size and composition heterogeneity,as well as the phase segregation behavior in Pt-Co nanoparticles(NPs)are still not well understood.Via in-situ environmental transmission electron microscopy,the formation dynamics and segregation behaviors of Pt-Co alloyed NPs during the thermal treatment were investigated.It is found that Pt-Co NPs on zeolitic imidazolate frameworks-67-derived nanocarbon(NC)are formed consecutively through both particle migration coalescence and the Ostwald ripening process.The existence of Pt NPs is found to affect the movement of Co NPs during their migration.With the help of theoretical calculations,the correlations between the composition and migration of the Pt and Co during the ripening process were uncovered.These complex alloying processes are revealed as key factors leading to the heterogeneity of the synthesized Pt-Co alloyed NPs.Under oxidation environment,the Pt-Co NPs become surface faceted gradually,which can be attributed to the oxygen facilitated relatively higher segregation rate of Co from the(111)surface.This work advances the fundamental understanding of design,synthesis,and durability of the Pt-based nanocatalysts.
文摘Direct observation of the dissolution behavior of nanomaterials could provide fundamental insight to understanding their anisotropic properties and stability. The dissolution mechanism in solution and vacuum has been well documented. However, the gas-involved dissolution and regrowth have seldom been explored and the mechanisms remain elusive. We report herein, an in situ TEM study of the dissolution and regrowth dynamics of MoO2 nanowires under oxygen using environmental transmission electron microscopy (ETEM). For the first time, oscillatory dissolution on the nanowire tip is revealed, and, intriguingly, simultaneous layer-by-layer regrowth on the sidewall facets is observed, leading to a shorter and wider nanowire. Combined with first-principles calculations, we found that electron beam irradiation caused oxygen loss in the tip facets, which resulted in changing the preferential growth facets and drove the morphology reshaping.
基金supported by the National Natural Science Foundation of China(11227403,11327901,51472215,51222202)the National Basic Research Program of China(2014CB932500,2015CB921004)+1 种基金Cyrus Tang Center for Sensor Materials and Applicationsthe resources of the Center of Electron Microscopy of Zhejiang University(ZJU)
文摘The dynamics of oxidation of cobalt nanoparticles were directly revealed by in situ environmental transmission electron microscopy.Firstly,cobalt nanoparticles were oxidized to polycrystalline cobalt monoxide,then to polycrystalline tricobalt tetroxide,in the presence of oxygen with a low partial pressure.Numerous cavities(or voids) were formed during the oxidation,owing to the Kirkendall effect.Analysis of the oxides growth suggested that the oxidation of cobalt nanoparticles followed a parabolic rate law,which was consistent with diffusion-limited kinetics.In situ transmission electron microscopy allowed potential atomic oxidation pathways to be considered.The outward diffusion of cobalt atoms inside the oxide layer controlled the oxidation,and formed the hollow structure.Irradiation by the electron beam,which destroyed the sealing effect of graphite layer coated on the cobalt surface and resulted in fast oxidation rate,played an important role in activating and promoting the oxidations.These findings further our understanding on the microscopic kinetics of metal nanocrystal oxidation and knowledge of energetic electrons promoting oxidation reaction.
基金Acknowle dgements This work was financially supported by the National Natural Science Foundation of China (NSFC) (Nos. 10704044 and 50825201), Fok Ying Tung Education Foundation (No. 111049), and the National BasicResearch Program of China (No. 2007CB935301). We thank Qingyu Zhao and Xiaoyang Lin for the help in the STA experiments. RS and SWC acknowledge the support from NSF-CBET (#0625340). We gratefully acknowledge the use of facilities within the LeRoy Eyring Center for Solid State Science at Arizona State University.
文摘We report the in situ transmission electron microscope (TEM) observation of the catalytic gasification and growth of carbon nanotubes (CNTs). It was found that iron catalysts can consume the CNTs when pumping out the precursor gas, acetylene, at the growth temperature, and reinitiate the growth when acetylene is re-introduced. The switching between gasification and growth of CNTs can be repeated many times with the same catalyst. To understand the phenomenon, thermogravimetric analysis (TGA) coupled with mass spectroscopy was used to study the mechanism involved. It was shown that the residual water molecules in the growth chamber of the TEM react with and remove carbon atoms of CNTs as carbon monoxide vapor under the action of the catalyst, when the precursor gas is pumped out. This result contributes to a better understanding of the water-assisted and oxygen-assisted synthesis of CNT arrays, and provides useful clues on how to extend the lifetime and improve the activity of the catalysts.