锂离子电池电极材料的第一性原理研究进展

文章综述了第一性原理计算在锂离子电池电极材料模拟与设计方面的研究进展.电极材料的研究包括电极材料的电子结构和电子导电性的研究,嵌锂电位、锂离子输运特性、嵌锂过程中局部结构弛豫与相变以及材料表面特性研究等方面,第一性原理计算在上述诸方面的研究都取得了一定的进展.这些理论上的研究成果,可以帮助人们加深对材料性能与机理的理解,同时对材料的设计也具有指导意义.     

锂离子电池相关材料的Raman光谱学研究

锂离子电池是目前综合性能最好的可充电池。本文总结我们实验室用Raman光谱学研究锂离子电池相关材料的一些结果 ,包括聚合物电解质的微结构和离子输运机制 ,低温热解碳负极材料的结构表征和锂离子在其中的嵌入 /脱出机理 ,元素替代引起正极材料LiMn2 O4的结构变化以及在充放电过程中电极 /电解质界面形成的钝化层的性质及其对电池性能的影响     

锂离子电池中的尺寸效应与表界面问题研究

文章介绍了锂离子电池中的尺寸效应与表界面问题的研究.从热力学与动力学方面讨论了小尺寸材料与体材料性质的区别以及作为储能材料的优缺点.从实际考虑,建议发展动力学稳定的纳米结构电极材料.     

纳米储锂材料和锂离子电池

简单综述了锂离子电池的基本原理和发展现状,对中国科学院物理研究所固体离子学课题组在纳米储锂材料方面的研究进展做了介绍.用HRTEM等手段研究了纳米SnO、纳米Si以及纳米SnSb合金在Li入脱嵌过程中结构的变化.着重介绍了一种具有纳米微孔的球形硬碳材料和纳米SnSb合金钉扎的复合负极材料,在高功率密度和高能量密度锂离子电池方面具有广阔应用前景.     

平面复合金属微纳结构的圆二色性研究

圆二色性效应在圆偏振器、光调制器及光电器件等方面具有广泛的应用.为提高平面金属微纳结构的圆二色性,本文设计了由无限长纳米线和G形微纳结构组成的平面复合金属微纳结构,并应用有限元方法研究了该阵列微纳结构的圆二色性特性.数值计算结果显示,在圆偏振光的激发下,G形微纳结构和平面复合金属微纳结构均出现了电偶极子、电四极子和电八极子等共振模式.当G形微纳结构与无限长纳米线连接时,各共振波长均发生红移,并且无限长纳米线增加了不同圆偏振光激发下的局域表面等离激元共振强度,从而使得平面复合微纳结构的圆二色性信号明显增强.此外,还研究了平面复合微纳结构阵列的几何参数对其圆二色性特性的影响.这些结果为提高平面手性微纳结构的圆二色性信号强度提供一定的指导思路和方法.     

石墨烯在锂离子电池负极材料中的应用

正1.引言化石能源日益短缺的危机使得可再生能源和能量存储技术受到广泛关注。基于在能量存储方面的优异表现,锂离子电池被认为是极具发展前景的电化学储能体系之一,其在民用、国防和航空航天等领域显示出强大的应用潜力。锂离子电池又称摇椅电池,其储放能过程如图1所示。锂离子电池的性能主要受到电极材料、电解质和器件组装技术等因素的制约,而正负极材料是决定电池性能的关键所在。现阶段研究的负极材料,依据电极反应的机理来划分,主要有嵌入型、合金反应型以及转换反应型三大类。然而由于三种类型电极材料的固有缺点如理论     

全固态锂离子电池内部热输运研究前沿

本文简要阐述了全固态锂离子电池的特点及其内部热输运研究的意义.介绍并总结了国内外与正极材料、负极材料、固态电解质,以及电极与电解质界面热输运性质相关的实验和理论工作.针对脱嵌锂过程对电极材料热导率的影响机理尚不明确,非晶态转变对电极材料热输运研究的挑战,界面热输运模型与方法不足等问题,系统梳理了全固态锂离子电池内部热输运的重要前沿科学问题.     

应力对锂离子电池中空碳包覆硅负极电化学性能的影响

针对锂离子电池硅及其复合电极材料,采用Cahn-Hilliard型扩散方程与有限变形理论全耦合的电化学-力模型来描述其在循环锂化过程中的扩散和力学相关性问题,构造高效的数值算法,在商用有限元软件平台上实现对该理论的数值求解.在此基础上,研究了硅电极恒流锂化和脱锂过程,基于界面反应动力学,得到电压响应曲线,计算结果整体趋势与实验结果吻合较好,同时预测的应力响应也与实验结果一致,验证了本方法的有效性.其次,研究了中空碳包覆硅负极锂化过程中的电化学与力学行为,计算结果表明,锂化期间中空碳包覆硅负极应力水平明显低于实心硅负极,随锂化的进行,应力差值越来越大,锂化结束时应力值降低约27%,这种应力的缓解提高了整个电极内化学势水平,使得锂离子浓度水平显著提高,更易达到完全锂化状态.同时,数值研究表明应力水平的缓解延缓了中空碳包覆硅负极的容量衰减(容量提升74%),充分显示出该电极良好的电化学性能.本研究揭示了应力对硅复合电极容量影响的作用机制,为将连续介质电化学-力耦合理论应用于实验预测提供了途径并为电极材料设计提供了理论依据.     

微纳复合结构表面稳定润湿状态及转型过程的热力学分析

自然界中的微纳复合结构超疏水表面由于其独特的润湿性质引起了人们的广泛关注, 大量实验研究表明了仿生人工微纳复合结构表面润湿性能的优越性, 然而液滴在微纳复合结构表面的润湿状态和转型过程的理论研究还并不完善. 本文首先用热力学方法分析了液滴在微纳复合结构表面可能存在的所有状态(四种稳定润湿状态和五种亚稳态到稳定态转型中的过渡态), 推导出了相应的能量表达式及表观接触角方程; 基于最小能量原理, 确定液滴在微纳复合结构表面的稳定状态, 较以往模型相比, 能够更好的预测已有的实验结果; 其次研究了微纳结构尺寸对稳定润湿状态和亚稳态到稳定态转型过程的影响; 最后提出了微纳复合结构表面设计原则, 即确定“超疏水稳定区”尺寸范围, 为超疏水表面的制备提供理论依据.     

离子束刻蚀辅助飞秒激光加工制备碳化硅微光学元件

为了解决飞秒激光加工硬质材料所带来的表面质量差的问题,提出了离子束刻蚀与飞秒激光复合加工技术.利用飞秒激光加工技术在碳化硅表面制备微纳结构图形,然后通过离子束刻蚀技术对碳化硅微纳结构进行刻蚀,以调控结构的线宽和深度,使结构表面粗糙度由约106nm降低到11.8nm.研究表明,利用该技术制备的碳化硅菲涅尔波带片展现出良好的聚焦和成像效果.     

A Mixed-Transfer-Matrix Method for Simulating Normal Conductor/Perfect Insulator/Perfect Conductor Random Networks

We develop a mixed-transfer-matrix approach for computing the macroscopic conductivity of a three-constituent normal conductor/perfect insulator/perfect conductor random network. This is applied to two-dimensional and three-dimensional samples at a percolation threshold. Such networks are simulated in order to test whether a diluted percolating network of normal conducting bonds remains in the same universality class of critical behavior when a finite fraction of those bonds have been replaced by perfectly conducting bonds. Also tested by such simulations is whether a percolating mixture of normal and perfectly conducting bonds remains in the same universality class of critical behavior when a finite fraction of the normal bonds are replaced by perfectly insulating bonds. These questions are crucial for some recently published exact results which connect the macroscopic electrical and elastic responses of percolating networks.     

离子导体载流子输运与存储的界面调控

离子导电材料既可以是载流子主要为离子的纯离子导体,也可以是载流子同时包括离子和电子的混合离子导体.这两类材料是电化学能量转换与储存、化学传感以及选择性透过膜等器件的关键材料.在这些器件中,均存在电极与电解质、颗粒与颗粒、不同晶粒之间的二维或三维的异质结界面.因此,离子与电子在异质结中的输运性质对器件性能有重要的影响.但...     

Enhanced rate capability of LiMn0.9Mg0.1PO4 nanoplates by reduced graphene oxide/carbon double coating for Li-ion batteries

The reduced graphene oxide (RGO)/carbon double-coated LiMn_0.9Mg_0.1PO₄ (LMP) nanoplates are introduced as a cathode material for Li-ion batteries with excellent rate capability. The double coating of RGO and carbon simultaneously brings the unique advantages of conformal carbon layer on each particle surface, and soft RGO sheets connecting the nanoplates to each other, thereby provides easy conduction pathways for the whole LMP aggregates. In particular, the simple self-assembly process driven by the electrostatic interactions enables conducting RGO sheets effectively to wrap the carbon-coated LMP, establishing three-dimensional RGO network. The RGO/C/LMP nanocomposites exhibit remarkably enhanced rate capability compared to the only C- or RGO-coated LMP, which is well explained by the reduced charge-transfer resistance achieved from electrochemical impedance spectroscopy.     

锂离子电池中的物理问题及其研究进展

锂离子电池作为一种性能优越的新型可充放电池已经或将要在移动通信、手提式计算机和电动汽车等诸多领域获得广泛的应用 .然而与锂离子电池相关的物理问题却往往被人们忽视 .例如 ,如何从本质上来提高正极材料的体相电子电导率 ,而不是在正极活性物质中添加炭黑之类的电子导电材料 .文章将着重针对与锂离子电池相关的物理问题 ,介绍近年来的主要进展 ,以期待对锂离子电池有更深入的了解 .     

Extensive limit of a non-extensive entanglement entropy

We report wide-range optical investigations on transparent conducting networks made from separated (semiconducting, metallic) and reference (mixed) single-walled carbon nanotubes, complemented by transport measurements. Comparing the intrinsic frequency-dependent conductivity of the nanotubes with that of the networks, we conclude that higher intrinsic conductivity results in better transport properties, indicating that the properties of the nanotubes are at least as much important as the contacts. We find that HNO₃ doping offers a larger improvement in transparent conductive quality than separation. Spontaneous dedoping occurs in all samples but is most effective in films made of doped metallic tubes, where the sheet conductance returns close to its original value within 24 h.     

Comparison of electrochemical performance for zinc anode via various electrolytes and conducting agents in Zn-air secondary batteries

Zn-air batteries have many advantages as energy devices but they show a poor charge-discharge cycle performance. Therefore, this study examined the effects of various types of electrolytes and conducting agents and changed the additive contents to optimize the electrochemical performance of Zn-air secondary batteries. Electrolytes, such as sodium hydroxide (NaOH) and potassium hydroxide (KOH) solutions, and conducting agents, such as super-p, denka black, acetylene black, and ketjen black, were used to increase the electric conductivity. The electrochemical performance of the zinc anode was evaluated from charge-discharge capacities and cycle efficiency. When the capacity was compared according to each electrolyte from one to ten cycles, in contrast, the zinc anode in 6 M KOH showed a higher discharge capacity in the first cycle. Therefore, zinc anode was composed in the 6-M KOH electrolyte and conducting agents were added. The zinc anode included conducting agents with a higher cycle capacity than those without conducting agents, and super-p had a higher first discharge capacity than the others. Therefore, the zinc anode with super-p of 4% shows the highest performance using 6 M KOH in Zn-air secondary batteries.     

Preparation and performance of sulfur–carbon composite based on hollow carbon nanofiber for lithium-sulfur batteries

A unique structured hollow carbon nanofiber–sulfur composite material (HCF–S) was fabricated and characterized in lithium-sulfur batteries. It is found that a part of spherical sulfur particles are located in the voids formed by the intertwined fibers and the others are confined in hollow channel of the HCF. The high conductive and porous HCF favors the construction of stable three-dimensional conducting network and convenient infiltration of the electrolytes into the cathode. The HCF–S cathode exhibits excellent electrochemical performance in the electrolyte with LiNO₃. By contrast, the ionic liquid electrolyte provides insufficient shuttle suppression and weakens ion transport, which leads to poor cycle and rate capability.     

Critical behavior of blind spots in sensor networks

Blind spots in sensor networks, i.e., individual nodes or small groups of nodes isolated from the rest of the network, are of great concern as they may significantly degrade the network's ability to collect and process information. As the operations of many types of sensors in realistic applications rely on short-lifetime power supplies (e.g., batteries), once they are used up ("off"), replacements become necessary ("on"). This off-and-on process can lead to blind spots. An issue of both theoretical and practical interest concerns the dynamical process and the critical behavior associated with the occurrence of blind spots. In particular, there can be various network topologies, and the off-and-on process can be characterized by the probability that a node functions normally, or the occupying probability of a node in the network. The question to be addressed in this paper concerns how the dynamics of blind spots depend on the network topology and on the occupying probability. For regular, random, and mixed networks, we provide theoretical formulas relating the probability of blind spots to the occupying probability, from which the critical point for the occurrence of blind spots can be determined. For scale-free networks, we present a procedure to estimate the critical point. While our theoretical and numerical analyses are presented in the framework of sensor networks, we expect our results to be generally applicable to network partitioning issues in other networks, such as the wireless cellular network, the Internet, or transportation networks, where the issue of blind spots may be of concern.     

点云投影结合轻量化卷积神经网络实现三维成像声呐快速目标分类*

三维成像声呐的成像结果是三维点云,基于点云的三维成像声呐目标分类方法具有网络结构复杂,计算量大的特点,针对这一问题本文提出了一种将三维成像声呐成像结果从三维点云投影至二维图像的方法,并且使用轻量化卷积神经网络实现了三维成像声呐快速目标分类。该方法首先对三维成像声呐波束形成后的波束域数据进行最大值滤波和阈值滤波,降低点云数据维度;接着,依据三维成像声呐的波束方向,将点云投影为深度图和强度图,分别保存点云的位置信息和强度信息;然后,利用深度图和强度图分别作为第一个通道和第二个通道构建混合通道图,将混合通道图作为目标分类网络的输入,从而将三维点云的目标分类问题转换为二维图像的目标分类问题;最后使用MobileNetV2网络实现了三维成像声呐快速目标分类。实验结果表明,通过本文提出的投影方法可以用二维图像分类网络完成三维成像声呐点云的目标分类任务;而且混合通道图比单独的强度图和深度图收敛速度更快,结合目标识别网络可以25fps实时的进行目标分类,在真实数据集上分类精度达到了91.13%。     

Poly-acrylonitrile-based gel-polymer electrolytes for sodium-ion batteries

Research and development activities on sodium-ion batteries are becoming prominent in the past few years. Compared to lithium-based batteries, the sodium-based batteries will be cheaper because of the abundancy of sodium raw materials in the earth’s crust and also in seawater. In the current study, we synthesized and characterized poly-acrylonitrile (PAN)-based gel-polymer electrolytes formed with NaClO₄ and dissolved in ethylene carbonate (EC) and propylene carbonate (PC). By systematically varying the weight ratios of polymer, salt, and the solvents, we obtained an optimum room temperature ionic conductivity of 4.5 mS cm⁻¹ for the composition 11PAN-12NaClO₄-40EC-37PC (wt.%), which is reasonably good for practical applications. This value of conductivity is comparable to a few other Na⁺ ion conducting gel-polymer electrolyte systems studied in the recent past. Variation of ionic conductivity with inverse temperature showed Arrhenius behavior. Activation energies estimated for all the samples showed only a slight variation suggesting that a single activation process which depends on the EC/PC co-solvent governs the ionic mobility in these gel-polymer electrolytes. Thermo-gravimetric analysis (TGA) revealed that there is no noticeable weight loss of these electrolytes up to 100 °C and hence the electrolytes are thermally stable for operating temperatures up to 100 °C.