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.     

集流体塑性变形对锂离子电池双层电极中锂扩散和应力的影响

针对锂离子电池双层电极结构,建立了综合考虑锂扩散、应力、浓度影响的材料属性及集流体弹塑性变形的理论模型.基于所建立的模型,主要研究了在充电过程中集流体可能发生的塑性变形对电极中锂扩散及应力的影响.数值结果表明集流体的塑性变形会减弱其对活性层的约束,这不仅使得集流体和活性层中的应力得到明显缓解,而且还促进了锂在活性层中的扩散,提高了活性层的有效容量.与此同时,研究了集流体的屈服强度和塑性模量这两个参数的影响,结果表明,较小的屈服强度和较小的塑性模量能进一步弱化约束,松弛电极活性层中的应力,并增加其有效充电容量.研究结果为分层电极的结构设计和性能优化提供了一定的参考.     

纳米颗粒的表面效应和电极颗粒间挤压作用对锂离子电池电压迟滞的影响

硅作为锂离子电池电极材料之一,其应力效应尤为突出,进而将影响电池性能.本文建立了电化学反应-扩散-应力全耦合模型,并研究了恒压充放电条件下扩散诱导应力、表面效应和颗粒间挤压作用对电压迟滞的影响.结果发现,应力及其导致的电压迟滞程度与颗粒尺寸相关.在大颗粒(颗粒半径r 100 nm)中,扩散诱导应力是导致电势迟滞效应的主要因素,这将导致电池能量耗散.对于纳米级小颗粒(r 100 nm)而言,表面效应占据主导,表面效应虽然能缓解电压迟滞,同时却会使驱动电化学反应部分的过电势回线下移,造成锂化容量衰减.本文综合考虑了扩散诱导应力和表面效应,得出:半径为10 nm的颗粒将会使电极具备较好的综合性能.此外,对于硅电极而言,颗粒间挤压作用会使应力回线向压应力状态演化,进而导致锂化容量的衰减.计算结果表明,在电极设计中,对孔隙率设定下限值有助于提升电极性能.     

表面效应对纳米线电极屈曲失稳的影响

纳米线电极在充/放电过程中引起电极的屈曲失稳行为可能会对结构造成力学损伤.本文针对纳米线电极结构,建立了包含锂扩散、应力、浓度影响弹性模量的多场耦合理论模型.基于构建的模型,研究了表面效应对纳米线电极屈曲失稳的影响.结果表明表面效应能够提高纳米线电极的抗屈曲性,延迟纳米线电极的临界屈曲时间.同时,表面效应的影响表现出半径尺寸和长细比的依赖性,即随着电极半径尺寸的增大而减小,而随着电极长细比的增大而增大.此外,模型还显示,在有表面效应的条件下,相对于弹性硬化属性的纳米线电极,具有弹性软化属性的电极因为具有更好的抗失稳性而更适宜作为电极材料.研究结果为纳米线电极的力学可靠性设计提供了一定的帮助.     

广义平面应变锂离子电池柱形梯度材料颗粒电极中扩散诱导应力分析

柱形梯度材料是最有潜力的锂离子电池电极之一. 为了研究恒压充电过程中柱形梯度材料颗粒电极下力学机理, 以Li_1.2(Mn_0.62Ni_0.38)_0.8O₂为例, 讨论弹性模量、扩散系数和偏摩尔体积三个重要材料参数对应力场影响. 并推导出非均匀柱形颗粒电极的扩散方程和力学方程. 结果表明, 柱形梯度材料纳米电极, 沿着半径方向Mn 的材料组分升高Ni 的材料组分降低, 其材料结构有利于降低最大径向应力和环向拉应力, 有效地避免电极的力学失效现象. 并根据计算结果, 对梯度材料电极提出材料结构优化建议.     

锂离子动力电池高倍率充放电过程中弛豫行为的仿真

基于电化学热耦合模型研究了动力锂离子电池高倍率充放电过程中的弛豫行为, 分析对比了不同充放电机制对电池弛豫行为的影响. 研究发现: 充放电过程中, 欧姆极化是造成电压骤变的主要原因; 而恒流-恒压的充电模式能够缓慢消除欧姆极化, 避免电池电压的骤变; 利用恒流恒压对电池进行充电能够充进更多的电量, 有利于电池性能的完全发挥; 固相锂离子浓度的弛豫时间比液相锂离子浓度的弛豫时间长, 并且在放电后期, 固相扩散的特征时间与液相扩散特征时间的比值不断增大, 固相扩散造成的极化在整个放电过程不可忽略.     

基于电化学-应力耦合模型的锂离子电池硅/碳核壳结构的模拟与优化

硅基电极材料在应用中的一个主要问题是巨大的体积膨胀,以及由此带来的电极材料破裂、粉化.本文在有限变形假设前提下,基于电化学-力学耦合理论,研究球形Si/C核壳结构在嵌锂过程中的浓度、应力场的演化,并在此基础上讨论了核壳结构的优化设计.计算结果显示:壳层可以很好地保护硅颗粒的膨胀;然而核内产生的较大的径向压缩应力可能导致核壳界面的脱黏,而核壳界面处的切向拉伸应力可能会导致壳层的断裂.进一步为有效提高核壳结构的电化学与力学性能,从而实现锂离子电池更长的循环寿命,考虑了两种结构的优化:1)单层核壳结构; 2)双层核壳结构.结果表明对于单层核壳结构应使用更软的包覆层材料;而双层核壳结构中优化的材料布置方案为内软外硬,对双层核壳结构的硬度分析表明,内层材料的杨氏模量应低于10 GPa,而外层材料的应不高于70 GPa.本文的结论对球形材料颗粒电极的设计及优化具有一定的指导意义.     

轴向载荷下功能梯度材料Timoshenko梁动力屈曲分析

假设功能梯度材料Timoshenko梁各项物性参数只沿厚度方向按幂函数进行连续变化,研究了功能梯度材料Timoshenko梁的动力屈曲。基于一阶剪切理论,采用Hamilton原理推导出轴向载荷作用下,功能梯度材料Timoshenko梁动力屈曲的控制方程。利用里兹法与棣莫弗公式相结合,获得了功能梯度材料Timoshenko梁在夹支-固支边界条件下动力屈曲临界载荷的解析表达式和屈曲解。应用MATLAB编程计算,讨论了功能梯度材料Timoshenko梁的几何尺寸、梯度指数、模态数、材料构成、泊松比以及弹性模量对临界载荷的影响。结果表明:功能梯度材料Timoshenko梁动力屈曲临界载荷随梁长度的增大而减小,随着梯度指数的增大而减小,随模态数的增大而增大,说明冲击载荷越大,高阶模态越容易被激发;随着泊松比和弹性模量的增大而增大,且泊松比的影响较小,而弹性模量的影响较大。由于剪切项的影响,临界载荷-临界长度的关系曲线在加载端变化趋势平缓。随着模态数的增大,梁的屈曲模态越为复杂。     

轴向荷载下功能梯度材料圆柱壳的动力屈曲

基于Donnell壳体理论和经典板壳理论,利用Hamilton变分原理得到轴向荷载作用下材料属性呈幂律分布的功能梯度材料圆柱壳的动力屈曲控制方程。根据圆柱壳周向连续性设出径向位移的函数表达,利用分离变量法求解得到功能梯度材料圆柱壳在轴向荷载作用下的动力屈曲临界荷载的解析表达式和屈曲解。利用MATLAB软件编程计算,讨论了径厚比、梯度指数、环向模态数、轴向模态数等对功能梯度材料圆柱壳动力屈曲临界荷载的影响。结果表明:圆柱壳的临界荷载随临界长度的增加而减小;冲击端为夹支的临界荷载比冲击端为简支的临界荷载大,说明约束条件对临界荷载有较大影响;圆柱壳的临界荷载随着模态数的增加而增大,说明临界荷载越大,高阶模态越易被激发;屈曲模态图随着模态数的增加而复杂化。     

基于电化学-热耦合模型研究隔膜孔隙结构对锂离子电池性能的影响机制

隔膜孔隙结构对锂离子电池性能具有重要的影响,本文提出了可准确描述充放电过程中锂离子电池内部复杂物理化学现象的电化学-热耦合模型,发现该模型较文献中模型的计算结果更接近实验测试数据.利用该模型探讨了隔膜孔隙率与扭曲率分别对锂离子电池性能的影响规律,发现减小孔隙率或增大扭曲率,电池输出电压、最大放电容量和平均输出功率均不断降低,电池表面温度和温升速度均不断升高;当孔隙率减小或扭曲率增大到一定程度时,放电初期电池输出电压均会出现先下降后回升的现象,且孔隙率越小或扭曲率越大,其下降的幅度越大、速度越快,回升所需时间也越长;要确保其不低于截止电压,隔膜扭曲率必须小于临界扭曲率(其下降至最低点刚好等于截止电压时的隔膜扭曲率).综合分析了放电过程中电池内部各电化学参量和产热量的动态分布规律,发现隔膜孔隙率和扭曲率主要影响放电末期电极膜片内部电化学反应以及其他放电时刻电解液中有效Li~+扩散(传导)系数.     

Consideration of mechanical properties of single-walled carbon nanotubes under various loading conditions

In this article, mechanical properties of single-walled carbon nanotubes (SWCNTs) with various radiuses under tensile, compressive and lateral loads are considered. Stress–strain curve, elastic modulus, tensile, compressive and rotational stiffness, buckling behaviour, and critical axial compressive load and pressure of eight different zigzag and armchair SWCNTs are investigated to figure out the effect of radius and chirality on mechanical properties of nanotubes. Using molecular dynamic simulation (MDS) method, it can be explained that SWCNTs have higher Young’s modulus and tensile stiffness than compressive elastic modulus and compressive stiffness. Critical axial force of zigzag SWCNT is independent from the radius, but that of armchair type rises by increasing of radius, also these two types show different buckling modes.     

Molecular dynamic investigation of mechanical properties of armchair and zigzag double-walled carbon nanotubes under various loading conditions

Using molecular dynamic simulation (MDS), effects of chirality and Van der Waals interaction on Young's modulus, elastic compressive modulus, bending, tensile, and compressive stiffness, and critical axial force of double-walled carbon nanotube (DWCNT) and its inner and outer tubes are considered. Achieving the highest safety factor, mechanical properties have been investigated under applied load on both inner and outer tubes simultaneously and on each one of them separately. Results indicate that as a compressive element, DWCNT is more beneficial than single-walled carbon nanotube (SWCNT) since it carries two times higher compression before buckling. Except critical axial pressure and tensile stiffness, in other parameters zigzag DWCNT shows higher amounts than armchair type. Outer tube has lower strength than inner tube; therefore, most reliable design of nanostructures can be attained if the mechanical properties of outer tube taken as the properties of DWCNT.     

Size-dependent thermal buckling of heated nanowires with ends axially restrained

Nanowires (NWs) are being actively explored for applications as nanoscale building blocks of sensors, actuators and nanoelectromechanical systems (NEMS). Temperature changes can induce an axial force within NWs due to the thermal expansion and may lead to buckling. The thermal buckling behaviors of ends-axially-restrained nanowires, subjected to a uniform temperature rise, are studied based on Bernoulli–Euler beam theory including the surface thermoelastic effects. Besides the surface elastic modulus, the influences of surface thermal expansion coefficient are incorporated into the model presented herein to describe size-dependent thermoelastic behaviors of nanowires. The results show that the critical buckling temperature and postbuckling deflection are significantly affected by surface thermoelastic effects and the influences become more prominent as the thickness of nanowire decreases. The corresponding influences of the slenderness ratio are also discussed. This research is helpful not only in understanding the thermal buckling properties of nanowires but also in designing the nanowire-based sensor and thermal actuator.     

Double-walled carbon nanotube with surrounding elastic medium under axial pressure

In this paper, the buckling behavior and critical axial pressure of double-walled carbon nanotubes (DWCNTs) with surrounding elastic medium are investigated. A double-shell (circular cylindrical shell) model is presented and the effects of surrounding elastic medium on the outer tube and the van der Waals forces between two adjacent tubes are taken into account. The analysis and the numerical solution method are based on the classical theory of plates and shells and the Galerkin method. Equations are derived for the critical axial forces and pressures of DWCNTs; the critical axial forces and pressures are calculated for different axial half sine wavenumbers and circumferential sine wavenumbers and compared with those for single-walled carbon nanotubes (SWCNTs).Results indicate that the critical axial force of a DWCNT is higher than that of an SWCNT, but the critical axial pressure of a DWCNT is lower than the critical axial pressure of a SWCNT. Although the critical axial force of a DWCNT decreases as the axial half sine wavenumbers increase, it rises as the circumferential sine wavenumbers increase.     

Analysis on diffusion-induced stress for multi-layer spherical core–shell electrodes in Li-ion batteries

Silicon-based carbon composites are believed as promising anodes in the near future due to their outstanding specific capacity and relatively lower volume effect compared to pure silicon anodes. Herein, a multilayer spherical core–shell(MSCS) electrode with a graphite framework prepared with Si@O-MCMB/C nanoparticles is developed, which aims to realize chemically/mechanically stability during the lithiation/delithiation process with high specific capacity. An electrochemical-/mechanical-coupling model for the M-SCS structure is established with various chemical/mechanical boundary conditions.The simulation of finite difference method(FDM) has been conducted based on the proposed coupling model, by which the diffusion-induced stress along both the radial and the circumferential directions is determined. Moreover, factors that influence the diffusion-induced stress of the M-SCS structure have been discussed and analyzed in detail.     

Kink instability of a highly deformable elastic cylinder

When a soft elastic cylinder is bent beyond a critical radius of curvature, a sharp fold in the form of a kink appears catastrophically at its compressed side while the tensile side remains smooth. The critical radius increases linearly with the diameter of the cylinder but remains independent of its material properties such as modulus; the maximum deflection at the location of the kink depends on both the material and geometric properties of the cylinder. The catastrophic dynamics of evolution of the kink depicts propagation of a shear wave from the location of the kink towards the edges signifying that kinking is an elastic response of the material which results in extreme localization of curvature. We have rationalized this phenomenon in the light of the classical Euler's buckling instability in slender elastic rods.     

Tribological system in the boundary friction mode under a periodic external action

A mechanical analog of a tribological system in the boundary friction mode is studied. A thermodynamic model is used to analyze the first-order phase transition between liquidlike and solidlike structures of a lubricant. The time dependences of the friction force, the relative velocity of the interacting surfaces, and the elastic component of the shear stresses appearing in the lubricant are obtained. It is shown that, in the liquidlike state, the shear modulus of the lubricant and the elastic stresses become zero. The intermittent (stick-slip) friction mode detected experimentally is described. It is shown that, as the lubricant temperature increases, the frequency of phase transitions between the lubricant structural states decreases and the total friction force and elastic stress amplitudes lower. When the temperature or the elastic strain exceeds the corresponding critical value, the lubricant melts and a kinetic slip mode in which the elastic component of the friction force is zero takes place.     

A Comprehensive Numerical Investigation on the Mechanical Properties of Hetero-Junction Carbon Nanotubes

A set of forty-three hetero-junction CNTs, made of forty-four homogeneous carbon nanotubes of different chiralities and configurations with all possible hetero-connection types, were numerically simulated, based on the finite element method in a commercial finite element software and their Young's and shear moduli, and critical buckling loads were obtained and evaluated under the tensile, torsional and buckling loads with an assumption of linear elastic deformation and also compared with each other. The comparison of the linear elastic behavior of hetero-junction CNTs and their corresponding fundamental tubes revealed that the size, type of the connection, and the bending angle in the structure of hetero-junction CNTs considerably influences the mechanical properties of these hetero-structures. It was also discovered that the Stone-Wales defect leads to lower elastic and torsional strength of hetero-junction CNTs when compared to homogeneous CNTs. However, the buckling strength of the hetero-junction CNTs was found to lie in the range of the buckling strength of their corresponding fundamental tubes. It was also determined that the shear modulus of hetero-junction carbon nanotubes generally tends to be closer to the shear modulus of their wider fundamental tubes while critical buckling loads of these heterostructures seem to be closer to critical buckling loads of their thinner fundamental tubes. The evaluation of the elastic properties of hetero-junction carbon nanotubes showed that among the hetero-junction models, those with armchair-armchair and zigzag-zigzag kinks have the highest elastic modulus while the models with armchair-zigzag connections show the lowest elastic stiffness. The results from torsion tests also revealed the fact that zigzag-zigzag and armchair-zigzag hetero-junction carbon nanotubes have the highest and the lowest shear modulus, respectively. Finally, it was observed that the highest critical buckling loads belong to armchair-armchair hetero-junction carbon nanotubes and the lowest buckling strength was found with the hetero-junction models with armchair-zigzag connection.     

螺栓材料应力与声速、温度关系的测定

基于应力－超声波速度关系方法已用于螺栓轴向应力的测量。而声速与被测材料的许多物理因素有关，如弹性模量，密度与温度。本文介绍了用于分析超声波速度－应力－温度三者关系的实验与计算方法，并给出了三种金属材料的结果。检测的质量。