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
LiFePO4 materials have become increasingly popular as a cathode material due to the many benefits they possess including thermal stability, durability, low cost, and long life span. Nevertheless, to broaden the genera...LiFePO4 materials have become increasingly popular as a cathode material due to the many benefits they possess including thermal stability, durability, low cost, and long life span. Nevertheless, to broaden the general appeal of this material for practical electrochemical applications, it would be useful to develop a relatively mild, reasonably simple synthesis method of this cathode material. Herein, we describe a generalizable, 2-step methodology of sustainably synthesizing LiFePO4 by incorporating a template-based, ambient, surfactantless, seedless, U-tube protocol in order to generate size and morphologically tailored, crystalline, phase-pure nanowires. The purity, composition, crystallinity, and intrinsic quality of these wires were systematically assessed using transmission electron microscopy (TEM), high-resolution TEM (HRTEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), selected area electron diffraction (SAED), energy dispersive analysis of X-rays (EDAX), and high-resolution synchrotron XRD. From these techniques, we were able to determine that there is an absence of any obvious defects present in our wires, supporting the viability of our synthetic approach. Electrochemical analysis was also employed to assess their electrochemical activity. Although our nanowires do not contain any noticeable impurities, we attribute their less than optimal electrochemical rigor to differences in the chemical bonding between our LiFePO4 nanowires and their bulk-like counterparts. Specifically, we demonstrate for the first time experimentally that the Fe-O3 chemical bond plays an important role in determining the overall conductivity of the material, an assertion which is further supported by recent "first-principles" calculations. Nonetheless, our ambient, solution-based synthesis technique is capable of generating highly crystalline and phase-pure energy-storage-relevant nanowires that can be tailored so as to fabricate different sized materials of reproducible, reliable morphology.展开更多
In this study,we mainly focus on the structural morphology and inter-atomic bonding state of tribofilms resulting from a highly-hydrogenated amorphous carbon(a-C:H) film in order to ascertain the underlying mechanisms...In this study,we mainly focus on the structural morphology and inter-atomic bonding state of tribofilms resulting from a highly-hydrogenated amorphous carbon(a-C:H) film in order to ascertain the underlying mechanisms for its superlubric behavior(i.e.,less than 0.01 friction coefficient).Specifically,we achieved superlubricity(i.e.,friction coefficients of down to 0.003) with this film in dry nitrogen and argon atmospheres especially when the tribo-pair is made of an a-C:H coated Si disk sliding against an a-C:H coated steel ball,while the a-C:H coated disk against uncoated ball does not provide superlubricity.We also found that the state of superlubricity is more stable in argon than in nitrogen and the formation of a smooth and uniformly-thick carbonaceous tribofilm appears to be one of the key factors for the realization of such superlubricity.Besides,the interfacial morphology of sliding test pairs and the atomic-scale bond structure of the carbon-based tribofilms also play an important role in the observed superlubric behavior of a-C:H films.Using Raman spectroscopy and high resolution transmission electron microscopy,we have compared the structural differences of the tribofilms produced on bare and a-C:H coated steel balls.For the a-C:H coated ball as mating material which provided superlow friction in argon,structural morphology of the tribofilm was similar or comparable to that of the original a-C:H coating;while for the bare steel ball,the sp^2-bonded C fraction in the tribofilm increased and a fingerprint-like nanocrystalline structure was detected by high resolution transmission electron microscopy(HRTEM).We also calculated the shear stresses for different tribofilms,and established a relationship between the magnitude of the shear stresses and the extent of sp^3-sp^2 phase transformation.展开更多
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.
文摘LiFePO4 materials have become increasingly popular as a cathode material due to the many benefits they possess including thermal stability, durability, low cost, and long life span. Nevertheless, to broaden the general appeal of this material for practical electrochemical applications, it would be useful to develop a relatively mild, reasonably simple synthesis method of this cathode material. Herein, we describe a generalizable, 2-step methodology of sustainably synthesizing LiFePO4 by incorporating a template-based, ambient, surfactantless, seedless, U-tube protocol in order to generate size and morphologically tailored, crystalline, phase-pure nanowires. The purity, composition, crystallinity, and intrinsic quality of these wires were systematically assessed using transmission electron microscopy (TEM), high-resolution TEM (HRTEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), selected area electron diffraction (SAED), energy dispersive analysis of X-rays (EDAX), and high-resolution synchrotron XRD. From these techniques, we were able to determine that there is an absence of any obvious defects present in our wires, supporting the viability of our synthetic approach. Electrochemical analysis was also employed to assess their electrochemical activity. Although our nanowires do not contain any noticeable impurities, we attribute their less than optimal electrochemical rigor to differences in the chemical bonding between our LiFePO4 nanowires and their bulk-like counterparts. Specifically, we demonstrate for the first time experimentally that the Fe-O3 chemical bond plays an important role in determining the overall conductivity of the material, an assertion which is further supported by recent "first-principles" calculations. Nonetheless, our ambient, solution-based synthesis technique is capable of generating highly crystalline and phase-pure energy-storage-relevant nanowires that can be tailored so as to fabricate different sized materials of reproducible, reliable morphology.
基金supported by the National Basic Research Program of China (Grant No.2011CB013404)National Natural Science Foundation of China(Grant Nos.51321092,51527901 and 51375010)
文摘In this study,we mainly focus on the structural morphology and inter-atomic bonding state of tribofilms resulting from a highly-hydrogenated amorphous carbon(a-C:H) film in order to ascertain the underlying mechanisms for its superlubric behavior(i.e.,less than 0.01 friction coefficient).Specifically,we achieved superlubricity(i.e.,friction coefficients of down to 0.003) with this film in dry nitrogen and argon atmospheres especially when the tribo-pair is made of an a-C:H coated Si disk sliding against an a-C:H coated steel ball,while the a-C:H coated disk against uncoated ball does not provide superlubricity.We also found that the state of superlubricity is more stable in argon than in nitrogen and the formation of a smooth and uniformly-thick carbonaceous tribofilm appears to be one of the key factors for the realization of such superlubricity.Besides,the interfacial morphology of sliding test pairs and the atomic-scale bond structure of the carbon-based tribofilms also play an important role in the observed superlubric behavior of a-C:H films.Using Raman spectroscopy and high resolution transmission electron microscopy,we have compared the structural differences of the tribofilms produced on bare and a-C:H coated steel balls.For the a-C:H coated ball as mating material which provided superlow friction in argon,structural morphology of the tribofilm was similar or comparable to that of the original a-C:H coating;while for the bare steel ball,the sp^2-bonded C fraction in the tribofilm increased and a fingerprint-like nanocrystalline structure was detected by high resolution transmission electron microscopy(HRTEM).We also calculated the shear stresses for different tribofilms,and established a relationship between the magnitude of the shear stresses and the extent of sp^3-sp^2 phase transformation.