Temperature-Dependent Dynamic Properties of LixMn2O4 in Monte Carlo Simulations

Monte Carlo (MC) simulations are used to simulate the voltage profile and the ionic conductivity s of Li ions in LixMn2O4 and its dependence on the lithium concentration x. The open circuit potential shows clearly the two plateaus in the charge/discharge curve, which agrees well with the experimental results. The two plateaus become more and more steep when the temperature is increased. The simulated ionic conductivity shows an M-shaped curve in the plot of ionic conductivity cr versus x when the simulation temperature is low. Interestingly,the minimum valley, which lies at the middle single-phase area near x=0.5, disappears gradually when the temperature increases to 453K.     

固体物理教学中联接正格子和倒格子空间的傅里叶变换过程浅议

在固体物理学课程中,由于涉及到一些高等数学知识,理解联接正格子和倒格子空间的傅里叶变换过程一直是教学难点之一.本文从晶体结构的周期性特征出发,并结合简易的数学推导,对傅里叶变换过程进行了详细的解读,并且对其中的关键步骤给出了凸显物理内涵的解释.     

Effect of the stoichiometry on the electronic structure of the Ni（111）/α-Al2O3（0001） interface： a first-principles investigation

In this paper first-principles calculations of Ni（111）/α-Al2O3（0001） interfaces have been performed, and are compared with the preceding results of the Cu （111）/α-Al2O3（0001） interface [2004 Phil. Mag. Left. 84 425]. The AI- terminated and O-terminated interfaces have quite different adhesion mechanisms, which are similar to the Cu（111）/α Al2O3（0001） interface. For the O-terminated interface, the adhesion is caused by the strong O-2p/Ni-3d orbital hybridization and ionic interactions. On the other hand, the adhesion nature of the Al-terminated interface is the image-like electrostatic and Ni-Al hybridization interactions, the latter is substantial and cannot be neglected. Charge transfer occurs from Al2O3 to Ni, which is opposite to that in the O=terminated interface. The charge transfer direction for the Al-terminated and O-terminated Ni（111）/α-A1203（0001） interfaces is similar to that in the corresponding Cu（111）/α- Al2O3（0001） interface, but there exist the larger charge transfer quantity and consequent stronger adhesion nature, respectively.     

LiFePO4中对位缺陷的第一性原理研究

基于考虑了Fe-3d电子间的库仑作用U和交换作用J的GGA+U方案,应用第一性原理计算方法系统研究了LiFePO₄的对位缺陷,以及对位缺陷的形成对材料的电导率和离子扩散速率的影响.结果表明,Li/Fe交换缺陷是最容易形成的,形成缺陷后的Fe—O键变长,扩宽了Li离子传输通道,有利于Li离子在通道中的扩散,对材料电化学性能的改善起到了一定的作用.     

CeO2的电子结构，光学和晶格动力学性质：第一性原理研究

基于考虑了Ce-4f电子间的库仑作用U和交换作用J的LDA+U方案,应用第一性原理计算系统研究了CeO₂的电子结构,光学和晶格动力学性质.电荷密度和电子局域函数的分布特征表明,CeO₂是属于共价键的绝缘体.介电常数、玻恩有效电荷张量和声子色散曲线的计算值和相应的实验结果符合得比较好. 关键词： 电子结构 光学性质 晶格动力学 第一性原理计算     

定制电解液或隔膜实现锂离子各向异性输运从而抑制枝晶生长：相场模拟研究

电池内部不可控的枝晶生长问题严重地影响着电池的循环性能和安全性能,这对于锂金属电池的实际应用是一个严峻的挑战。尽管已有较多的实验和理论研究工作聚焦于电极间锂离子各向异性输运特性对枝晶形貌的影响,但仍有一些开放性的问题有待进一步研究,例如,如何将枝晶生长的动态演变与电解液性质、电势分布或隔膜多孔结构诱导的锂离子各向异性输运关联起来。我们通过将锂离子在电解液中的扩散系数(DL)表示为二阶张量的形式并进行相场模拟,发现D_yy:D_xx比值的增加,以及电势诱导的电极/电解液界面锂离子快速扩散层均可以降低界面处锂离子浓度梯度和电势梯度,从而减弱枝晶生长的驱动力。我们还发现隔膜基体与y方向之间夹角的增大也会显著促进电解质中的锂离子各向异性输运特性,以利于抑制枝晶生长。籍此本文提出设计D_yy:D_xx=10:1的电解液和基体倾斜角为arctan (0.5)的隔膜用于锂金属电池。该相场研究有望为设计具有抑制枝晶能力的电解质或隔膜提供指导。     

Multi-scale computation methods: Their applications in lithium-ion battery research and development

Based upon advances in theoretical algorithms, modeling and simulations, and computer technologies, the rational design of materials, cells, devices, and packs in the field of lithium-ion batteries is being realized incrementally and will at some point trigger a paradigm revolution by combining calculations and experiments linked by a big shared database,enabling accelerated development of the whole industrial chain. Theory and multi-scale modeling and simulation, as supplements to experimental efforts, can help greatly to close some of the current experimental and technological gaps,as well as predict path-independent properties and help to fundamentally understand path-independent performance in multiple spatial and temporal scales.     

Brief overview of electrochemical potential in lithium ion batteries

The physical fundamentals and influences upon electrode materials' open-circuit voltage(OCV) and the spatial distribution of electrochemical potential in the full cell are briefly reviewed. We hope to illustrate that a better understanding of these scientific problems can help to develop and design high voltage cathodes and interfaces with low Ohmic drop. OCV is one of the main indices to evaluate the performance of lithium ion batteries(LIBs), and the enhancement of OCV shows promise as a way to increase the energy density. Besides, the severe potential drop at the interfaces indicates high resistance there, which is one of the key factors limiting power density.     

浅析电解质中离子输运的微观物理图像

解析离子在电解质中的输运特征所表现出的微观物理图像,对于调控离子传导行为具有重要的指导意义.本文系统总结了离子在液态、有机聚合物和无机固态电解质中的离子输运物理图像及其影响因素,通过分析各种输运物理模型并比较三类电解质中的离子输运机制,提炼出勾勒离子输运物理图像的相关描述因子.输运介质的物理形态从连续流体到柔性载体再到刚性骨架的演变过程中,离子输运图像由各类电解质的固有属性与外部条件共同刻画,其中介质无序性占据主导作用.揭示电解质结构和离子电导率及输运过程等动力学行为之间的科学规律,有利于发展基于离子输运微观物理图像的传导离子动力学性能调控方法.     

相场模型及其在电化学储能材料中的应用

随着计算机技术的快速发展,计算研究在探究材料体系微结构演化方面展示出巨大的优势.作为材料动力学的一种计算研究方法,相场模型不仅可以避免复杂的界面追踪,而且便于处理各类外场因素,因而受到广泛关注.藉此本文介绍了相场模型的理论框架以及目前主流的多元多相系相场模型:Carter模型, Steinbach模型和Chen模型,并从相场变量的解释、耦合热力学数据库的方式、体系自由能密度的构建方式以及演化方程等方面对上述三个模型进行了系统地概括和比较.进一步,聚焦于相场模型在各向异性输运和相分离、弹性和塑性变形、裂纹扩展和断裂、枝晶生长机制等方面的应用,系统展示了相场模型在描述电化学储能材料微结构演化以及改进其性能方面的巨大潜力.最后,从相场模型的理论改进和应用拓展两个方面,讨论并展望了电化学储能材料相场模拟的未来发展方向和亟待解决的关键问题.