Advanced Current Collectors for Alkali Metal Anodes

High-energy-density batteries are in urgent need to solve the ever-increasing energy storage demand for portable electronic devices, electric vehicles, and renewable solar and wind energy systems. Alkali metals, typically lithium(Li), sodium(Na) and potassium(K), are considered as the promising anode materials owing to their low electrochemical potential, low density, and high theoretical gravimetric capacities. However, the problem of dendrite growth of alkali metals during their plating/stripping process will lead to low Coulombic efficiencies, a short lifespan and huge volume expansion, eventually hindering their practical commercialization. To resolve this issue, a very effective approach is engineering the anodes on structured current collectors. This review summarizes the development of the alkali metal batteries and discusses the recent advances in rational design of anode current collectors. First, the challenges and strategies of suppressing alkali-metal dendrite growth are presented. Then the special attention is paid to the novel current collector design for dendrite-free alkali metal anodes. Finally, we give conclusions and perspective on the current challenges and future research directions toward advanced anode current collectors for alkali metal batteries.     

A Novel, Simple and Efficient Synthesis of Ferrocenyl Enones and Alkynols

Propargylic alcohols are versatile precursors to many organic molecules including natural products and pharmaceutical compounds.[1] In our continuing interest in the development of practical methods for synthesis of ferrocene derivatives, we decided to investigate the efficiencies of ferrocenylacetylene addition to aromatic aldehydes under t-BuOKcatalyzed condition.[2] Interestingly, we found that the usually reliable coupling reaction between terminal alkyne of type 1 and aromatic aldehydes of type 2 does not furnish the expected propargylic alcohols, but that the isomeric aryl enones 3are found in high yield and very short reaction time (10～20 min). This provided a promising protocol for preparation of ferrocenyl chalcones in a practical, economical and mild sense compared with the traditional method. To the best of our knowledge, this unusual reaction was first observed for the addition of ferrocenylacetylene to aldehyde in a base-catalyzed manner (Eq. 1).     

Studies on the Stereochemistry of 2-(Nitromethylidene)-Heterocycles

The ¹H-NMR spectra of 2-(nitromethylidene)pyrrolidine ( 7 ), 1-methyl-2-(nitromethylidene)imidazolidind ( 10 ) and 3-(nitromethylidene)tetrahydrothiazine ( 11 ) in CDCl₃ and (CD₃)₂SO indicate that these compounds have the intramolecularly H-bonded structures (Z)- 7 , (E)- 10 and (Z)- 11 while the N-methyl derivative 8 of 7 is (E)-configurated in both solvents. 1-Benzylamino-1-(methyltio)-2-nitroehtylene ( 13 ), an acylic model, has the H-bonded configuration (E)- 13 in CDCl₃ and in (CD₃)₂SO. 2-(Nitromethylidene)thiazolidine ( 3 ) has the (E)-configuration in CDCl₃ but exists in (CD₃)₂SO as a mixture of (Z)- and (E)-isomers with the former predominating. Both species are detected to varying proportions in a mixture of the two solvents. ¹⁵N-NMR spectroscopy of 3 ruled out unambiguously the nitronic acid structure 6 and the nitromethyleimine structure 5 . The N-methyl derivative 4 of 3 is (Z)-configurated in (CD₃)₂SO. Comparison of the olefinic proton shifts of (Z)- 3 and (Z)- 4 with those of analogues and also of 1,1-bis(methylti)-2-nitroethylene ( 12 ) shows decreased conjugation of the lone pair of electrons of the ring N-atom in (Z)- 3 and (Z)- 4 . This is also supported by ¹³C-NMR studies. Plausible explanations for the phenomenon are offered by postulating that the ring N-atoms are pyramidal in (Z)- 3 and (Z)- 4 and planar in other cases or, alternatively, that the conjugated nitroenamine system gets twisted due to steric interaction between the NO₂-group and the ring S-atom. Single-crystal X-ray studies of 3 and 8 show that the former exists in the (Z)-configuration and the latter in (E)-configuration; the ring N-atom in the former has slightly more pyramidal character than in the latter.     

Recent developments in the chemistry of perhydroindoles and perhydrocinnolines

Recent synthetic routes to the tetrahydro, hexahydro and octahydro derivatives of indoles are reviewed. An interesting one is the formation of 3-amino-4-oxo-4,5,6,7-tetrahydroindoles in the reaction of 2-phenacyl cyclohexane-l,3-diones with 1,1-disubstituted hydrazines. Antifertility, cns depressant and antiinflammatory activities have been encountered for perhydroindoles besides other biological activities. Hexahydrocinnolines are obtained from the reaction of 2-phenacyl (acetonyl) cyclohexanones and cyclohexane-1,3-diones with hydrazines, while octahydrocinnolines are formed from cyclohexanone-2-acetic acids and hydrazines in two steps. 5-oxo-5,6,7,8-hexahydrocinnolines and their oximes undergo anomalous and interesting aromatisation reactions. Some hexahydrocinnolines are cns depressants while octahydrocinnolines are analgesics. More importantly, they are precursors for interesting azamorphinans. Contribution No. 736 from Research centre     

Konstante der potentiellen Energie und mittlere Schwingungsamplituden in einigen XY4-Molekülen und-Ionen tetraedrischer Symmetrie

Zusammenfassung Mit Hilfe der gruppentheoretischen Methode vonWilson wurden die Konstanten der potentiellen Energie für die Tetramethylverbindungen und-ionen der Elemente der 4. und 5. Gruppe, besonders des C, Si, Ge, Sn, Pb, N, As und Sb, sowie auch der Aluminat- und Zinkat-Ionen unter Verwendung eines Valenzkraftfeldes mit 5 Konstanten berechnet. Auf der Grundlage der vonCyvin postulierten Symmetriekoordinaten wurden die Größen der mittleren Amplitudenquadrate und die mittleren Schwingungsamplituden für gebundene und nicht-gebundene Atompaare bei den Temperaturen 298° K und 500° K berechnet. Der geringfügige Einfluß der Schwingungen der Methyl- und Hydroxylgruppen auf die Gerüstschwingungen wurde vernachlässigt, jedoch die nicht-diagonalen Elemente bei der Lösung der Säkulargleichungen in Betracht gezogen.

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Potential energy constants and mean amplitudes of vibration in some XY₄-molecules and-ions with tetrahedral symmetry

Potential energy constants have been evaluated by theWilson's group theoretical method for the tetramethyl compounds and ions of the elements of the fourth and fifth groups, namely, C, Si, Ge, Sn, Pb, N, As, and Sb as well as the aluminate and zincate ions employing a five-constant valence force field. On the basis of the symmetry coordinates postulated byCyvin, the mean-square amplitude quantities and mean amplitudes of vibration for the bonded and nonbonded atom pairs have also been computed at the temperatures 298° K and 500° K. The effect of the vibrations of methyl and hydroxyl groups on the skeletal modes, being small, has been neglected and the off-diagonal element has been taken into account in solving the secular equations.

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Diese Arbeit wurde vom US-Army Research Office, Durham, unter der Nummer AROD-31-124-6864 unterstützt.     

激光通道传输热特性对远场光束质量的影响

 通过仿真计算分析了激光在光束控制系统通道内传输所产生的热效应及其对远场光束质量的影响。激光传播由近轴波方程描述，用快速傅里叶变换技术求解；激光热效应引起的流场密度变化采用完全Navier-Stokes方程计算。计算给出了不同波长、不同吸收系数条件下的远场光斑情况。计算结果表明，在典型的工作条件和状态下，较高能量激光在光束控制系统通道内产生的热效应影响不容忽视，它会明显降低远场目标处的能量集中度，增大光斑的发散。     

cBN晶体的Raman光谱测量

 用R1000激光共聚焦Raman光谱仪研究了高温高压合成棒中的立方氮化硼（cBN）晶体、原材料六方氮化硼（hBN）和催化剂。Raman光谱测量结果表明：伴随cBN晶体生长的散射峰,出现了两条全新的Raman散射峰（约1.088 cm^-1和约1.368 cm^-1）。该散射峰所对应的物质可能是在高温高压条件下hBN向cBN转变时生成的不完全产物——BN的一种新相。这一结果将有助于进一步讨论cBN的生长机理。     

悬线式物镜力矩器中频段共振理论及实验分析

悬线式物镜力矩器是高密度光盘系统中关键部件——光学头的可执行机构,其运动特性决定着光学头的读盘能力。在光学头研制、生产及测试中发现某些力矩器频率特性曲线的线性工作区内出现共振,它会导致光学头的读碟能力下降。通过对力矩器可动部建模、ansys仿真及实验分析,得出力矩器可动部的质心和力心不重合将导致其在中频段内发生扭转共振。实验结论对悬线式物镜力矩器设计、评价和生产都有重要的指导意义。     

负P表示非经典光场的Wehrl熵和Shannon熵

研究了负P表示非经典光场的Wehrl熵和Shannon熵与场参数m和平均光子数(-n)的关系,结果显示,负P表示的非经典光场的Wehrl熵随着场参数m和平均光子数的增大而减小,当(-n)增大到一定程度时Wehrl熵趋向于一个不变的常数.用数值计算的方法研究了负P表示光场的Shannon熵与平均光子数(-n)的关系,结果表明,Shannon熵随着场参数m和平均光子数(-n)的增大而增大.同时发现,Wehrl熵随光场总噪声的增大而减小,Shannon熵随力学量起伏的减小而减小.