The atomic pair distribution function（PDF） reveals the interatomic distance in a material directly in real-space. It is a very powerful method to characterize the local structure of materials. With the help of the t...The atomic pair distribution function（PDF） reveals the interatomic distance in a material directly in real-space. It is a very powerful method to characterize the local structure of materials. With the help of the third generation synchrotron facility and spallation neutron source worldwide, the PDF method has developed quickly both experimentally and theoretically in recent years. Recently this method was successfully implemented at the Shanghai Synchrotron Radiation Facility（SSRF）. The data quality is very high and this ensures the applicability of the method to study the subtle structural changes in complex materials. In this article, we introduce in detail this new method and show some experimental data we collected.展开更多
Battery materials are of vital importance in powering a elean and sustainable society.Improving their performance relies on a clear and fundamental understanding of their properties,in particular,structural properties...Battery materials are of vital importance in powering a elean and sustainable society.Improving their performance relies on a clear and fundamental understanding of their properties,in particular,structural properties.Pair distribution function(PDF) analysis,which takes into account both Bragg scattering and diffuse scattering,can probe structures of both crystalline and amorphous phases in battery materials.This review first introduces the principle of PDF,followed by its application in battery materials.It shows that PDF is an effective tool in studying a series of key scientific topics in battery materials.They range from local ordering,nano-phase quantification,anion redox reaction,to lithium storage mechanism,and so on.展开更多
The energy materials performance is intrinsically determined by structures from the average lattice structure to the atom arrangement, valence, and distribution of the containing transition metal(TM) elements. Underst...The energy materials performance is intrinsically determined by structures from the average lattice structure to the atom arrangement, valence, and distribution of the containing transition metal(TM) elements. Understanding the mechanism of the structure transition and atom rearrangement via synthesis or processing is key to expediting the exploration of excellent energy materials. In this work, in situ neutron scattering is employed to reveal the real-time structure evolution, including the TM-O bonds, lattice,TM valence and the migration of the high-voltage spinel cathode LiNi_(0.5)Mn_(1.5)O_(4). The transition-metalmediated spinel destabilization under the annealing at the oxygen-deficient atmosphere is pinpointed.The formation of Mn^(3+) is correlated to the TM migration activation, TM disordered rearrangement in the spinel, and the transition to a layered-rocksalt phase. The further TM interdiffusion and Mn^(3+) reduction are also revealed with multi-stage thermodynamics and kinetics. The mechanisms of phase transition and atom migrations as functions of temperature, time and atmosphere present important guidance on the synthesis in various-valence element containing oxides.展开更多
Based on Maxwell’s constraint counting theory, rigidity percolation in GexSe1-x glasses occurs when the mean coordination number reaches the value of 2.4. This corresponds to Ge0.20Se0.80 glass. At this composition, ...Based on Maxwell’s constraint counting theory, rigidity percolation in GexSe1-x glasses occurs when the mean coordination number reaches the value of 2.4. This corresponds to Ge0.20Se0.80 glass. At this composition, the number of constraints experienced by an atom equals the number of degrees of freedom in three dimensions. Hence, at this composition, the network changes from a floppy phase to a rigid phase, and rigidity starts to percolate. In this work, we use reverse Monte Carlo (RMC) modeling to model the structure of Ge0.20Se0.80 glass by simulating its experimental total atomic pair distribution function (PDF) obtained via high energy synchrotron radiation. A three-dimensional configuration of 2836 atoms was obtained, from which we extracted the partial atomic pair distribution functions associated with Ge-Ge, Ge-Se and Se-Se real space correlations that are hard to extract experimentally from total scattering methods. Bond angle distributions, coordination numbers, mean coordination numbers and the number of floppy modes were also extracted and discussed. More structural insights about network topology at this composition were illustrated. The results indicate that in Ge0.20Se0.80 glass, Ge atoms break up and cross-link the Se chain structure, and form structural units that are four-fold coordinated (the GeSe4 tetrahedra). These tetrahedra form the basic building block and are connected via shared Se atoms or short Se chains. The extent of the intermediate ranged oscillations in real space (as extracted from the width of the first sharp diffraction peak) was found to be around 19.6 ?. The bonding schemes in this glass are consistent with the so-called “8-N” rule and can be interpreted in terms of a chemically ordered network model.展开更多
晶体学只能够给出有关晶体平均原子结构的信息,而结合逆向蒙特卡罗(Reverse Monte Carlo,RMC)模拟的全散射方法将同时包含原子的平均结构和局部尺度上原子间距、键角以及结构多面体的取向和形变等方面的信息,这也是RMC方法一个独特的优...晶体学只能够给出有关晶体平均原子结构的信息,而结合逆向蒙特卡罗(Reverse Monte Carlo,RMC)模拟的全散射方法将同时包含原子的平均结构和局部尺度上原子间距、键角以及结构多面体的取向和形变等方面的信息,这也是RMC方法一个独特的优势.近年来,借助第三代同步辐射加速器和散裂中子源,RMC方法在实验和理论上都有了较快的发展,同时数据质量高,保证了该方法在材料的局域波动和无序的精细结构研究中的适用性.本文从RMC基本原理和分析方法两个方面介绍了无序体系中的逆向蒙特卡罗方法,同时给出了一系列有助于理解的RMC模型实例.最后,对RMC方法的发展进行了展望.近年来我国对大科学装置的投入迅速增长,相信RMC方法搭载第四代高能量光源,必将在我国新材料的设计与开发中发挥重要的作用.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant No.U1232112)the National Key Basic Research Program of China(Grant No.2012CB825700)
文摘The atomic pair distribution function（PDF） reveals the interatomic distance in a material directly in real-space. It is a very powerful method to characterize the local structure of materials. With the help of the third generation synchrotron facility and spallation neutron source worldwide, the PDF method has developed quickly both experimentally and theoretically in recent years. Recently this method was successfully implemented at the Shanghai Synchrotron Radiation Facility（SSRF）. The data quality is very high and this ensures the applicability of the method to study the subtle structural changes in complex materials. In this article, we introduce in detail this new method and show some experimental data we collected.
文摘Battery materials are of vital importance in powering a elean and sustainable society.Improving their performance relies on a clear and fundamental understanding of their properties,in particular,structural properties.Pair distribution function(PDF) analysis,which takes into account both Bragg scattering and diffuse scattering,can probe structures of both crystalline and amorphous phases in battery materials.This review first introduces the principle of PDF,followed by its application in battery materials.It shows that PDF is an effective tool in studying a series of key scientific topics in battery materials.They range from local ordering,nano-phase quantification,anion redox reaction,to lithium storage mechanism,and so on.
基金supported by the Division of Materials Science and Engineering, Office of Basic Energy Sciences, U.S. Department of Energy (DOE)。
文摘The energy materials performance is intrinsically determined by structures from the average lattice structure to the atom arrangement, valence, and distribution of the containing transition metal(TM) elements. Understanding the mechanism of the structure transition and atom rearrangement via synthesis or processing is key to expediting the exploration of excellent energy materials. In this work, in situ neutron scattering is employed to reveal the real-time structure evolution, including the TM-O bonds, lattice,TM valence and the migration of the high-voltage spinel cathode LiNi_(0.5)Mn_(1.5)O_(4). The transition-metalmediated spinel destabilization under the annealing at the oxygen-deficient atmosphere is pinpointed.The formation of Mn^(3+) is correlated to the TM migration activation, TM disordered rearrangement in the spinel, and the transition to a layered-rocksalt phase. The further TM interdiffusion and Mn^(3+) reduction are also revealed with multi-stage thermodynamics and kinetics. The mechanisms of phase transition and atom migrations as functions of temperature, time and atmosphere present important guidance on the synthesis in various-valence element containing oxides.
文摘Based on Maxwell’s constraint counting theory, rigidity percolation in GexSe1-x glasses occurs when the mean coordination number reaches the value of 2.4. This corresponds to Ge0.20Se0.80 glass. At this composition, the number of constraints experienced by an atom equals the number of degrees of freedom in three dimensions. Hence, at this composition, the network changes from a floppy phase to a rigid phase, and rigidity starts to percolate. In this work, we use reverse Monte Carlo (RMC) modeling to model the structure of Ge0.20Se0.80 glass by simulating its experimental total atomic pair distribution function (PDF) obtained via high energy synchrotron radiation. A three-dimensional configuration of 2836 atoms was obtained, from which we extracted the partial atomic pair distribution functions associated with Ge-Ge, Ge-Se and Se-Se real space correlations that are hard to extract experimentally from total scattering methods. Bond angle distributions, coordination numbers, mean coordination numbers and the number of floppy modes were also extracted and discussed. More structural insights about network topology at this composition were illustrated. The results indicate that in Ge0.20Se0.80 glass, Ge atoms break up and cross-link the Se chain structure, and form structural units that are four-fold coordinated (the GeSe4 tetrahedra). These tetrahedra form the basic building block and are connected via shared Se atoms or short Se chains. The extent of the intermediate ranged oscillations in real space (as extracted from the width of the first sharp diffraction peak) was found to be around 19.6 ?. The bonding schemes in this glass are consistent with the so-called “8-N” rule and can be interpreted in terms of a chemically ordered network model.
文摘晶体学只能够给出有关晶体平均原子结构的信息,而结合逆向蒙特卡罗(Reverse Monte Carlo,RMC)模拟的全散射方法将同时包含原子的平均结构和局部尺度上原子间距、键角以及结构多面体的取向和形变等方面的信息,这也是RMC方法一个独特的优势.近年来,借助第三代同步辐射加速器和散裂中子源,RMC方法在实验和理论上都有了较快的发展,同时数据质量高,保证了该方法在材料的局域波动和无序的精细结构研究中的适用性.本文从RMC基本原理和分析方法两个方面介绍了无序体系中的逆向蒙特卡罗方法,同时给出了一系列有助于理解的RMC模型实例.最后,对RMC方法的发展进行了展望.近年来我国对大科学装置的投入迅速增长,相信RMC方法搭载第四代高能量光源,必将在我国新材料的设计与开发中发挥重要的作用.
