Space-Confined Atomic Clusters Catalyze Superassembly of Silicon Nanodots within Carbon Frameworks for Use in Lithium-Ion Batteries

Incorporating nanoscale Si into a carbon matrix with high dispersity is desirable for the preparation of lithium-ion batteries (LIBs) but remains challenging. A space-confined catalytic strategy is proposed for direct superassembly of Si nanodots within a carbon (Si NDs⊂C) framework by copyrolysis of triphenyltin hydride (TPT) and diphenylsilane (DPS), where Sn atomic clusters created from TPT pyrolysis serve as the catalyst for DPS pyrolysis and Si catalytic growth. The use of Sn atomic cluster catalysts alters the reaction pathway to avoid SiC generation and enable formation of Si NDs with reduced dimensions. A typical Si NDs⊂C framework demonstrates a remarkable comprehensive performance comparable to other Si-based high-performance half LIBs, and higher energy densities compared to commercial full LIBs, as a consequence of the high dispersity of Si NDs with low lithiation stress. Supported by mechanic simulations, this study paves the way for construction of Si/C composites suitable for applications in future energy technologies.     

Stability criteria for positive linear discrete-time systems

Positivity - We prove new characterisations of exponential stability for positive linear discrete-time systems in ordered Banach spaces, in terms of small-gain conditions. Such conditions have...     

完全非相干白光一维光生伏打暗空间孤子

使用白炽灯作光源在LiNbO₃∶Fe晶体内实验观察到一维白光光生伏打暗空间孤 子. 由奇数 和偶数初始条件分别产生了灰孤子和灰孤子对，它们所感应的波导能导向白光和相干光. 用 相干光清楚地探测到它们内部的多模结构. 该实验证明了白光光生伏打暗空间孤子的存在， 并指出了用完全非相干的白光暗孤子控制和导向相干光的可能性. 关键词： 光生伏打效应 自陷 完全非相干孤子 波导     

CsNiCl3晶体的光谱精细结构、零场分裂参量及Jahn-Teller效应

应用不可约张量理论构造了三角对称晶场中3d²/3d⁸态离子的45阶可完全对角化的微扰哈密顿矩阵，研究了CsNiCl₃晶体的光谱精细结构、晶体结构、零场分裂参量、Jahn-Telller效应以及自旋单重态对Ni²⁺离子基态能级的影响，理论与实验相符合.在此基础上，进一步研究了以前工作中被忽略的自旋-自旋耦合作用和Trees修正对CsNiCl₃晶体的光谱精细结构和零场分裂参量的影响，发现有四种机理会影响零场分裂参量：1)自旋-轨道耦合机理，2)自旋-自旋耦合机理；3)自旋-轨道与自旋-自旋联合耦合机理；4)自旋-轨道与Trees修正联合耦合机理，其中自旋-轨道耦合机理是最主要的，其他三种机理也是不可忽略的. 关键词： 基态能级 精细结构 零场分裂 自旋-自旋耦合     

掺入Ni元素的LiCoO2晶体光谱结构及电子顺磁共振g因子

在弱场图像下,利用Racah不可约张量算符方法得到了三角对称3d4/3d6电子组态的210阶可完全对角化的微扰哈密顿矩阵、最近邻点电荷模型晶体结构常量公式和电子顺磁共振g因子公式.研究了LiCoO2晶体和掺入Ni的LiCoO2:Ni晶体中Co3+的基态能级、晶体结构和电子顺磁共振g因子.考虑了LiCoO2晶体和LiCoO2:Ni晶体中自旋单重态和三重态对Co3+基态能级的影响,讨论了LiCoO2晶体和在LiCoO2晶体中掺杂Ni后Co3+局域结构常量大小的变化是引起Co3+的基态能级变化的主要原因,理论和实验都证实了这一点.还计算了掺杂前后的电子顺磁共振g因子,计算结果与实验值符合得较好.     

Influence of organic modifiers on morphology and crystallization of poly(ϵ‐caprolactone)/synthetic clay intercalated nanocomposites

ε‐caprolactone was polymerized in the presence of neat montmorillonite or organomontmorillonites to obtain a variety of poly(ε‐caprolactone) (PCL)‐based systems loaded with 10 wt % of the silicates. The materials were thoroughly investigated by different X‐ray scattering techniques to determine factors affecting structure of the systems. For one of the nanocomposites it was found that varying the temperature in the range corresponding to crystallization of PCL causes reversible changes in the interlayer distance of the organoclay. Extensive experimental and literature studies on this phenomenon provided clues indicating that this effect might be a result of two‐dimensional ordering of PCL chains inside the galleries of the silicate. Small angle X‐ray scattering and wide angle X‐ray scattering investigation of filaments oriented above melting point of PCL revealed that polymer lamellae were oriented perpendicularly to particles of unmodified silicate, while in PCL/organoclay systems they were found parallel to clay tactoids. Calorimetric and microscopic studies shown that clay particles are effective nucleating agents. In the nanocomposites, PCL crystallized 20‐fold faster than in the neat polymer. The crystallization rate in nanocomposites was also significantly higher than in microcomposite. Further research provided an insight how the presence of the filler affects crystalline fraction and spherulitic structure of the polymer matrix in the investigated systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2350–2367, 2007     

Photoreactions of benzonitrile with cyclic enol ethers

Upon irradiation, cyclic enol ethers such as 1-methoxy-cyclopentene (4) mainly add across the cyano group of benzonitrile (1), under formation of 2-azabutadienes of an imidoester type. This is in agreement with the so-called Δ G-correlation which was reported earlier (ref. 5 and 6). 4-Phenyloxazole (9) is formed from 1 and 1,3-dioxole (5) probably by a similar photochemical process followed by electrocyclic ring opening and hydrolysis. The low yield of the latter photoreaction and the almost exergonic electron transfer between 5 and 1 may point to back electron transfer as the main energy wasting process. From 1 and 2,3-dihydrido-furan (2) only the ortho cycloadduct 6 has been isolated in low yields.