Scanning transmission electron microscopy（STEM） has been shown as powerful tools for material characterization,especially after the appearance of aberration-corrector which greatly enhances the resolution of STEM. H...Scanning transmission electron microscopy（STEM） has been shown as powerful tools for material characterization,especially after the appearance of aberration-corrector which greatly enhances the resolution of STEM. High angle annular dark field（HAADF） and annular bright field（ABF） imaging of the aberration-corrected STEM are widely used due to their high-resolution capabilities and easily interpretable image contrasts. However, HAADF mode of the STEM is still limited in detecting light elements due to the weak electron-scattering power. ABF mode of the STEM could detect light and heavy elements simultaneously, providing unprecedented opportunities for probing unknown structures of materials. Atomiclevel structure investigation of materials has been achieved by means of these imaging modes, which is invaluable in many fields for either improving properties of materials or developing new materials. This paper aims to provide a introduction of HAADF and ABF imaging techniques and reviews their applications in characterization of cathode materials, study of electrochemical reaction mechanisms, and exploring the effective design of lithium-ion batteries（LIBs）. The future prospects of the STEM are also discussed.展开更多
为了研究Mg_(97)Gd_(2)Y_(1)合金中β'相的粗化过程以及相关析出结构的形成和演变机制,使用原子分辨的高角度环形暗场-扫描透射电子显微镜(high angle annular dark field scanning transmission electron microscope,HAADF-STEM)...为了研究Mg_(97)Gd_(2)Y_(1)合金中β'相的粗化过程以及相关析出结构的形成和演变机制,使用原子分辨的高角度环形暗场-扫描透射电子显微镜(high angle annular dark field scanning transmission electron microscope,HAADF-STEM)成像技术表征了合金不同时效阶段形成的析出结构,并结合第一性原理计算的方法分析了它们的稳定性.结果表明,相关的β_(F)'、β_(M)和β″相主要在β'相粗化过程的早期形成,它们的形成与β'相相界面周围存在较高的错配应变场密切相关;随着β'相粗化过程的进行,β_(M)和β″相的尺寸和数量逐渐减少,而由β'与β_(F)'相交替组成的竹节状析出物增多,成为合金基体中主要的析出结构;当错配应变足够大时,β_(F)'相内部出现位错,β相在位错处可以形核,并逐渐长大成为基体中主要的平衡析出结构.展开更多
Atomically dispersed catalysts have attracted attention in energy conversion applications because their efficiency and chemoselectivity for special catalysis are superior to those of traditional catalysts. However, th...Atomically dispersed catalysts have attracted attention in energy conversion applications because their efficiency and chemoselectivity for special catalysis are superior to those of traditional catalysts. However, they have limitations owing to the extremely low metal-loading content on supports, difficulty in the precise control of the metal location and amount as well as low stability at high temperatures. We prepared a highly doped single metal atom hybrid via a single-step thermal pyrolysis of glucose, dicyandiamide, and inorganic metal salts. High-angle annular dark field-scanning transmission electron microscopy （HAADF-STEM） and X-ray absorption fine structure spectroscopy （XAFS） revealed that nitrogen atoms doped into the graphene matrix were pivotal for metal atom stabilization by generating a metal-Nx coordination structure. Due to the strong anchoring effect of the graphene matrix, the metal loading content was over 4 wt.% in the isolated atomic hybrid （the Pt content was as high as 9.26 wt.% in the Pt-doped hybrid）. Furthermore, the single iron-doped hybrid （Fe@N-doped graphene） showed a remarkable electrocatalytic performance for the oxygen reduction reaction. The peak power density was - 199 mW·cm-2 at a current density of 310 mA·cm-2 and superior to that of a commercial Pt/C catalyst when it was used as a cathode catalyst in assembled zinc-air batteries. This work offered a feasible approach to design and fabricate highly doped single metal atoms （SMAs） catalysts for potential energy applications.展开更多
Traditional space group determination methods are all in reciprocal space,which involves ambiguous identification on some space groups which have glide plane and screw axes.The novel strategy herein for space group de...Traditional space group determination methods are all in reciprocal space,which involves ambiguous identification on some space groups which have glide plane and screw axes.The novel strategy herein for space group determination in real space is based on the atom resolution high angle annular dark field(HAADF)technology.Three HAADF images in three specific crystal zone axes are needed at most.The proposed strategy for space group determination is easy and effective.展开更多
The phase transformation of θ’’→θ’ in an Al-5.7 Cu alloy was investigated by aberration-corrected scanning transmission electron microscopy, and the tranformation mode of θ’’→θ’ during aging treatment was ...The phase transformation of θ’’→θ’ in an Al-5.7 Cu alloy was investigated by aberration-corrected scanning transmission electron microscopy, and the tranformation mode of θ’’→θ’ during aging treatment was clarified. In the presence of the θ’ phases, θ’ was found to be formed by in-situ transformation fromθ’’ with the same plate shape, size and broad faces. The transformation starts from multiple sites within the θ’ precipitate and the whole θ’ phase finally forms as the preferential θ’ sections grow and connect with each other. Antiphase domain boundaries are also found in some θ’ precipitates when the disregistry exists between different θ’ sections.展开更多
Nucleation behavior of amorphous Si–B–C–N ceramics derived from boron-modified polyvinylsilazane procusors was systematically investigated by transmission electron microscopy(TEM) combined with spatially-resolved e...Nucleation behavior of amorphous Si–B–C–N ceramics derived from boron-modified polyvinylsilazane procusors was systematically investigated by transmission electron microscopy(TEM) combined with spatially-resolved electron energy-loss spectroscopy(EELS) analysis. The ceramics were pyrolyzed at1000℃ followed by further annealing in N2, and SiC nano-crystallites start to emerge at 1200℃ and dominate at 1500℃. Observed by high-angle annular dark-field imaging, bright and dark clusters were revealed as universal nano-structured features in ceramic matrices before and after nucleation, and the growth of cluster size saturated before reaching 5 nm at 1400℃. EELS analysis demonstrated the gradual development of bonding structures successively into SiC, graphetic BNCxand Si3N4 phases, as well as a constant presence of unexpected oxygen in the matrices. Furthermore, EELS profiling revealed the bright SiC clusters and less bright Si3N4-like clusters at 1200–1400℃. Since the amorphous matrix has already phase separated into SiCN and carbon clusters, another phase separation of SiCN into SiC and Si3N4-like clusters might occur by annealing to accompany their nucleation and growth, albeit one crystallized and another remained in amorphous structure. Hinderance of the cluster growth and further crystallization was owing to the formation of BNCxlayers that developed between SiC and Si3N4-like clusters as well as from the excessive oxygen to form the stable SiO2.展开更多
Laves phases,with the topologically close-packed structure and a chemical formula of Ab_(2),constitute the largest single class of intermetallics.Planar defects in Laves phases are widely investigated,especially for s...Laves phases,with the topologically close-packed structure and a chemical formula of Ab_(2),constitute the largest single class of intermetallics.Planar defects in Laves phases are widely investigated,especially for stacking behavior transformations through synchroshear.Here,we report the coexistence of C14,C36 and C15 structures in MgZn_2 precipitates by using atomic resolution scanning transmission electron microscopy,verifying the previously predicted Laves phase transformation sequence of C14→C36→C15 also applies to MgZn_2.One type of stacking fault couple in precipitates has been found to alone reduce the lattice mismatch with matrix,while some other stacking fault couples need to self-accommodate with irregular planar defects(rhombic units and flattened hexagonal units),or with five-fold symmetry structures to relieve the strain concentration.Precipitates thus grow towards an equiaxed or even round morphology,rather than the plate morphology as conventionally believed.Molecular dynamics calculations are performed to support our analysis.These findings reveal the principles governing the concurrent occurrence of various defects in laves structures,acting as an update of the widely accepted perception of random occurrence of defects during crystal growth.展开更多
基金supported by the National Basic Research Program of China(Grant No.2014CB921002)the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB07030200)the National Natural Science Foundation of China(Grant Nos.51522212,51421002,and 51672307)
文摘Scanning transmission electron microscopy（STEM） has been shown as powerful tools for material characterization,especially after the appearance of aberration-corrector which greatly enhances the resolution of STEM. High angle annular dark field（HAADF） and annular bright field（ABF） imaging of the aberration-corrected STEM are widely used due to their high-resolution capabilities and easily interpretable image contrasts. However, HAADF mode of the STEM is still limited in detecting light elements due to the weak electron-scattering power. ABF mode of the STEM could detect light and heavy elements simultaneously, providing unprecedented opportunities for probing unknown structures of materials. Atomiclevel structure investigation of materials has been achieved by means of these imaging modes, which is invaluable in many fields for either improving properties of materials or developing new materials. This paper aims to provide a introduction of HAADF and ABF imaging techniques and reviews their applications in characterization of cathode materials, study of electrochemical reaction mechanisms, and exploring the effective design of lithium-ion batteries（LIBs）. The future prospects of the STEM are also discussed.
文摘为了研究Mg_(97)Gd_(2)Y_(1)合金中β'相的粗化过程以及相关析出结构的形成和演变机制,使用原子分辨的高角度环形暗场-扫描透射电子显微镜(high angle annular dark field scanning transmission electron microscope,HAADF-STEM)成像技术表征了合金不同时效阶段形成的析出结构,并结合第一性原理计算的方法分析了它们的稳定性.结果表明,相关的β_(F)'、β_(M)和β″相主要在β'相粗化过程的早期形成,它们的形成与β'相相界面周围存在较高的错配应变场密切相关;随着β'相粗化过程的进行,β_(M)和β″相的尺寸和数量逐渐减少,而由β'与β_(F)'相交替组成的竹节状析出物增多,成为合金基体中主要的析出结构;当错配应变足够大时,β_(F)'相内部出现位错,β相在位错处可以形核,并逐渐长大成为基体中主要的平衡析出结构.
基金This work is financially supported partly by Ministry of Science and Technology （MOST） （Nos. 2017YFA0303500 and 2014CB848900）, the National Natural Science Foundation of China （NSFC） （Nos. U1532112, 11574280 and 11605201 ）, CAS Interdisciplinary Innovation Team and CAS Key Research Program of Frontier Sciences （No. QYZDB-SSW-SLH018）. L. S. acknowledges the recruitment program of global experts, the CAS Hundred Talent Program and Key Laboratory of Advanced Energy Materials Chemistry （Ministry of Education） Nankai University. We thank the Shanghai Synchrotron Radiation Facility （14W1, SSRF）, the Beijing Synchrotron Radiation Facility （1W1B and soft-X-ray endstation, BSRF）, the Hefei Synchrotron Radiation Facility （Photoemission, MCD and Catalysis/ Surface Science Endstations, NSRL）, and the USTC Center for Micro and Nanoscale Research and Fabrication for helps in characterizations.
文摘Atomically dispersed catalysts have attracted attention in energy conversion applications because their efficiency and chemoselectivity for special catalysis are superior to those of traditional catalysts. However, they have limitations owing to the extremely low metal-loading content on supports, difficulty in the precise control of the metal location and amount as well as low stability at high temperatures. We prepared a highly doped single metal atom hybrid via a single-step thermal pyrolysis of glucose, dicyandiamide, and inorganic metal salts. High-angle annular dark field-scanning transmission electron microscopy （HAADF-STEM） and X-ray absorption fine structure spectroscopy （XAFS） revealed that nitrogen atoms doped into the graphene matrix were pivotal for metal atom stabilization by generating a metal-Nx coordination structure. Due to the strong anchoring effect of the graphene matrix, the metal loading content was over 4 wt.% in the isolated atomic hybrid （the Pt content was as high as 9.26 wt.% in the Pt-doped hybrid）. Furthermore, the single iron-doped hybrid （Fe@N-doped graphene） showed a remarkable electrocatalytic performance for the oxygen reduction reaction. The peak power density was - 199 mW·cm-2 at a current density of 310 mA·cm-2 and superior to that of a commercial Pt/C catalyst when it was used as a cathode catalyst in assembled zinc-air batteries. This work offered a feasible approach to design and fabricate highly doped single metal atoms （SMAs） catalysts for potential energy applications.
基金supported by the National Natural Science Foundation of China(Nos.11904307 and 52001268)the Natu-ral Science Foundation of Hunan province(Nos.2019JJ50576 and 2021JJ40539)the Foundation of Education Bureau of Hunan Province(No.20C1797).
文摘Traditional space group determination methods are all in reciprocal space,which involves ambiguous identification on some space groups which have glide plane and screw axes.The novel strategy herein for space group determination in real space is based on the atom resolution high angle annular dark field(HAADF)technology.Three HAADF images in three specific crystal zone axes are needed at most.The proposed strategy for space group determination is easy and effective.
基金supported by the National Natural Science Foundation of China (No. 11227403)Cyrus Tang Center for Sensor Materials and Applications
文摘The phase transformation of θ’’→θ’ in an Al-5.7 Cu alloy was investigated by aberration-corrected scanning transmission electron microscopy, and the tranformation mode of θ’’→θ’ during aging treatment was clarified. In the presence of the θ’ phases, θ’ was found to be formed by in-situ transformation fromθ’’ with the same plate shape, size and broad faces. The transformation starts from multiple sites within the θ’ precipitate and the whole θ’ phase finally forms as the preferential θ’ sections grow and connect with each other. Antiphase domain boundaries are also found in some θ’ precipitates when the disregistry exists between different θ’ sections.
基金financially supported by National Natural Science Foundation of China (Grant Nos. 51172255 and 51532006)
文摘Nucleation behavior of amorphous Si–B–C–N ceramics derived from boron-modified polyvinylsilazane procusors was systematically investigated by transmission electron microscopy(TEM) combined with spatially-resolved electron energy-loss spectroscopy(EELS) analysis. The ceramics were pyrolyzed at1000℃ followed by further annealing in N2, and SiC nano-crystallites start to emerge at 1200℃ and dominate at 1500℃. Observed by high-angle annular dark-field imaging, bright and dark clusters were revealed as universal nano-structured features in ceramic matrices before and after nucleation, and the growth of cluster size saturated before reaching 5 nm at 1400℃. EELS analysis demonstrated the gradual development of bonding structures successively into SiC, graphetic BNCxand Si3N4 phases, as well as a constant presence of unexpected oxygen in the matrices. Furthermore, EELS profiling revealed the bright SiC clusters and less bright Si3N4-like clusters at 1200–1400℃. Since the amorphous matrix has already phase separated into SiCN and carbon clusters, another phase separation of SiCN into SiC and Si3N4-like clusters might occur by annealing to accompany their nucleation and growth, albeit one crystallized and another remained in amorphous structure. Hinderance of the cluster growth and further crystallization was owing to the formation of BNCxlayers that developed between SiC and Si3N4-like clusters as well as from the excessive oxygen to form the stable SiO2.
基金supported financially by the National Natural Science Foundation of China(Nos.51820105001,51771234,51531009 and 51790482)the Fundamental Research Funds for the Central Universities(No.GK201803016)。
文摘Laves phases,with the topologically close-packed structure and a chemical formula of Ab_(2),constitute the largest single class of intermetallics.Planar defects in Laves phases are widely investigated,especially for stacking behavior transformations through synchroshear.Here,we report the coexistence of C14,C36 and C15 structures in MgZn_2 precipitates by using atomic resolution scanning transmission electron microscopy,verifying the previously predicted Laves phase transformation sequence of C14→C36→C15 also applies to MgZn_2.One type of stacking fault couple in precipitates has been found to alone reduce the lattice mismatch with matrix,while some other stacking fault couples need to self-accommodate with irregular planar defects(rhombic units and flattened hexagonal units),or with five-fold symmetry structures to relieve the strain concentration.Precipitates thus grow towards an equiaxed or even round morphology,rather than the plate morphology as conventionally believed.Molecular dynamics calculations are performed to support our analysis.These findings reveal the principles governing the concurrent occurrence of various defects in laves structures,acting as an update of the widely accepted perception of random occurrence of defects during crystal growth.
