Pressure-sensitive plasticity of lithiated silicon in Li-ion batteries

Lithiation-induced plasticity is a key factor that enables Si electrodes to maintain long cycle life in Li-ion batteries. We study the plasticity of various lithiated sili-con phases based on first-principles calculations and iden-tify the linear dependence of the equivalent yield stress on the hydrostatic pressure. Such dependence may cause the compression-tension asymmetry in an amorphous Si thin film electrode from a lithiation to delithiation cycle, and leads to subsequent ratcheting of the electrode after cyclic lithiation. We propose a yield criterion of amorphous lithi-ated silicon that includes the effects of the hydrostatic stress and the lithiation reaction. We further examine the micro-scopic mechanism of deformation in lithiated silicon under mechanical load, which is attributed to the flow-defects mediated local bond switching and cavitation. Hydrostatic compression confines the flow defects thus effectively strength-ens the amorphous structure, and vice versa.     

Cracking mechanisms in lithiated silicon thin film electrodes

The massive cracking of silicon thin film electrodes in lithium ion batteries is associated with the colossal volume changes that occur during lithiation and delithiation cycles. However, the underlying cracking mechanism or even whether fracture initiates during lithiation or delithiation is still unknown. Here, we model the stress generation in amorphous silicon thin films during lithium insertion, fully accounting for the effects of finite strains, plastic flow, and pressure-gradients on the diffusion of lithium. Our finite element analyses demonstrate that the fracture of lithiated silicon films occurs by a sequential cracking mechanism which is distinct from fracture induced by residual tension in conventional thin films. During early-stage lithiation, the expansion of the lithium-silicon subsurface layer bends the film near the edges, and generates a high tensile stress zone at a critical distance away within the lithium-free silicon. Fracture initiates at this high tension zone and creates new film edges, which in turn bend and generate high tensile stresses a further critical distance away. Under repeated lithiation and delithiation cycles, this sequential cracking mechanism creates silicon islands of uniform diameter, which scales with the film thickness. The predicted island sizes, as well as the abrupt mitigation of fracture below a critical film thickness due to the diminishing tensile stress zone, is quantitatively in good agreement with experiments.     

In Situ Measurements of Strains in Composite Battery Electrodes during Electrochemical Cycling

The cyclic stress in lithium-ion battery electrodes induced by repeated charge and discharge cycles causes electrode degradation and fracture, resulting in reduced battery performance and lifetime. To investigate electrode mechanics as a function of electrochemical cycling, we utilize digital image correlation (DIC) to measure the strains that develop in lithium-ion battery electrodes during lithiation and delithiation processes. A composite graphite electrode is cycled galvanostatically (with constant current) in a custom battery cell while optical images of the electrode surface are captured in situ. The strain in the electrode is computed using an in-house DIC code. On average, an unconstrained composite graphite electrode expands 1.41 % during lithiation and contracts 1.33 % during delithiation. These strain values compare favorably with predictions based on the elastic properties of the composite electrode and the expansion of graphite-lithium intercalation compounds (G-LICs). The establishment of this experimental protocol will enable future studies of the relationship between electrode mechanics and battery performance.     

Real-Time Stress Measurement in SiO<Subscript>2</Subscript> Thin Films during Electrochemical Lithiation/Delithiation Cycling

Oxide coatings have been shown to improve the cyclic performance of high-energy density electrode materials such as Si. However, no study exists on the mechanical characterization of these oxide coatings. Here, thin film SiO₂ electrodes are cycled under galvanostatic conditions (at C/9 rate) in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1 M LiPF₆ in ethylene carbonate, diethyl carbonate, dimethyl carbonate solution (1:1:1, wt%) as electrolyte. Stress evolution in the SiO₂ thin film electrodes during electrochemical lithiation/delithiation is measured in situ by monitoring the substrate curvature using a multi-beam optical sensing method. Upon lithiation SiO₂ undergoes extensive inelastic deformation, with a peak compressive stress of 3.1 GPa, and upon delithiation the stress became tensile with a peak stress of 0.7 GPa. A simple plane strain finite element model of Si nanotube coated with SiO₂ shell was developed to understand the mechanical response of the core-shell type microstructures under electrochemical cycling; measured stress response was used in the model to represent SiO₂ constitutive behavior while Si was treated as an elastic-plastic material with concentration dependent mechanical properties obtained from the literature. The results reported here provide insights and quantitative understanding as to why the highly brittle SiO₂ coatings are able to sustain significant volume expansion (300%) of Si core without fracture and enhance cyclic performance of Si reported in the literature. Also, the basic mechanical properties presented here are necessary first step for future design and development of durable Si/SiO₂ core shell structures or SiO₂-based electrodes.     

Modeling crack growth during Li insertion in storage particles using a fracture phase field approach

Fracture of storage particles is considered to be one of the major reasons for capacity fade and increasing power loss in many commercial lithium ion batteries. The appearance of fracture and cracks in the particles is commonly ascribed to mechanical stress, which evolves from inhomogeneous swelling and shrinkage of the material when lithium is inserted or extracted. Here, a coupled model of lithium diffusion, mechanical stress and crack growth using a phase field method is applied to investigate how the formation of cracks depends on the size of the particle and the presence or absence of an initial crack, as well as the applied flux at the boundary. The model shows great versatility in that it is free of constraints with respect to particle geometry, dimension or crack path and allows simultaneous observation of the evolution of lithium diffusion and crack growth. In this work, we focus on the insertion process. In particular, we demonstrate the presence of intricate fracture phenomena, such as, crack branching or complete breakage of storage particles within just a single half cycle of lithium insertion, a phenomenon that was only speculated about before.     

柱状电极屈曲或裂纹扩展的临界力学参数研究

柱形结构电极是近年来使用最为广泛的锂电池电极结构之一．本文以硅材料细长柱形电极为例，研究了充电电流大小、电极长径比、初始裂纹长度以及断裂韧性对于电极的屈曲现象和裂纹扩展现象发生时间的影响．计算结果表明，屈曲与裂纹扩展现象出现的先后顺序与充电电流大小无关；具有小的长径比，大的初始裂纹长度以及较小断裂韧性的电极，裂纹扩展比屈曲现象更早发生．对于硅材料，不同长径比的电极具有不同临界断裂韧性值，当材料的断裂韧性小于该临界值，在锂化过程中裂纹扩展会先于屈曲现象发生；该临界断裂韧性值随初始裂纹长度的增加而增加．本文的结论对于电极的结构设计以及材料选取具有一定指导意义．     

Benchmark experiments and characteristic cyclic plasticity deformation

Key issues in cyclic plasticity modeling are discussed based upon representative experimental observations on several commonly used engineering materials. Cyclic plasticity is characterized by the Bauschinger effect, cyclic hardening/softening, strain range effect, nonproporitonal hardening, and strain ratcheting. Additional hardening is identified to associate with ratcheting rate decay. Proper modeling requires a clear distinction among different types of cyclic plasticity behavior. Cyclic hardening/softening sustains dependent on the loading amplitude and loading history. Strain range effect is common for most engineering metallic materials. Often, nonproportional hardening is accompanied by cyclic hardening, as being observed on stainless steels and pure copper. A clarification of the two types of material behavior can be made through benchmark experiments and modeling technique. Ratcheting rate decay is a common observation on a number of materials and it often follows a power law relationship with the number of loading cycles under the constant amplitude stress controlled condition. Benchmark experiments can be used to explore the different cyclic plasticity properties of the materials. Discussions about proper modeling are based on the typical cyclic plasticity phenomena obtained from testing several engineering materials under various uniaxial and multiaxial cyclic loading conditions. Sufficient experimental evidence points to the unambiguous conclusion that none of the hardening phenomena (cyclic hardening/softening, strain range effect, nonproportional hardening, and strain hardening associated with ratcheting rate decay) is isotropic in nature. None of the hardening behavior can be properly modeled with a change in the yield stress.     

A theory and a simulation capability for the growth of a solid electrolyte interphase layer at an anode particle in a Li-ion battery

A major mechanism for electrochemical aging of Li-ion batteries is the growth of a solid electrolyte interphase (SEI) layer on the surface of anode particles, which leads to capacity fade and also results in a rise in cell resistance. We have formulated a continuum theory for the growth of an SEI layer—a theory which accounts for the generation of the attendant growth stresses. The theory has been numerically implemented in a finite-element program. This simulation capability for SEI growth is coupled with our previously published chemo-mechanical simulation capability for intercalation of Li-ions in electrode particles. Using this new combined capability we have simulated the formation and growth of an SEI layer during cyclic lithiation and delithiation of an anode particle, and predicted the evolution of the growth stresses in the SEI layer. The evolution of the stress state within the SEI layer and at the SEI/anode-particle interface for spherical- and spheroidal-shaped graphite particles is studied. This knowledge of the local interfacial stresses provides a good estimate for the propensity of potential delamination of an SEI layer from an anode particle.     

循环加卸载损伤大理岩的动力学特性

利用MTS 815电液伺服岩石实验系统进行上限应力为80%、85%、90%、95%单轴抗压强度的大理岩单轴压缩循环加卸载实验,每种上限应力条件分别设置20、40、60、80次循环。再利用分离式Hopkinson压杆对损伤岩样进行动力学实验。分析了循环加卸载上限应力及循环次数对大理岩塑性应变的影响,揭示了大理岩动态力学参数和破碎吸收能随损伤变量的演化规律。实验结果表明:塑性应变与循环次数呈正相关,且上限应力越大,塑性应变趋于稳定所需的循环次数也会增大;动态单轴抗压强度、动态弹性模量随损伤变量增加呈指数衰减;破碎吸能占比以损伤变量D=0.343为临界点分为两个阶段,D<0.343时,破碎吸能占比稳定在10%左右,数值约为13 J,当D>0.343时破碎吸能占比随损伤变量增加不断增大。研究结果可为岩体工程的设计、施工及支护参数的选取提供参考。     

全固态锂电池界面的机械失效模型综述

全固态锂电池具有高能量密度和高安全性能等优点,有望替代传统锂电池成为下一代可移动储备．然而,全固态结构也给这种新型电池的应用带来全新的挑战,阻碍其商业化的进程,其中很重要的一个挑战就是机械不稳定性．首先,尽管固态电解质具有较高刚度与强度,理论上应该可以阻挡锂枝晶的穿透,但在其使用过程中仍能观察到锂枝晶的生长,这与高刚度电解质可抵制锂枝晶生长的理论相悖．其次,与液态电解质相比,固态电解质刚度大,在电极活性材料充放电时不能始终保持与活性材料的有效接触,可能导致活性颗粒和电解质的界面分层．因此,解释这些现象并提供解决策略对促进全固态锂电池的广泛应用至关重要．本文旨在总结近年来关于全固态锂电池不同界面处机械失效的力化耦合模型,主要包括以下两个方面：(1) 锂金属负极与固态电解质界面处锂枝晶的形成与生长;(2) 活性颗粒锂化/脱锂化引起的界面分层和破裂．本文从理论模型的角度总结了全固态锂离子电池中不同界面上的机械失效行为,旨在为全固态锂离子电池的模型建立与结构优化提供借鉴思路．     

Incremental collapse of thick-walled circular cylinders under steady axial tension and torsion loads and cyclic transient heating

The accumulation of plastic strain over a number of cycles of heating and cooling of the outer surface of a loaded thick-walled circular cylinder is computed. Two types of loadings are considered, viz. pure axial torsion and a combination of torsion and tension. The cylinder material is taken to be isotropic and linear strain-hardening; its yield stress reduces with temperature and with the number of thermal cycles completed. This cyclic softening is shown to produce an incremental collapse or ratcheting behaviour in contrast to the alternating plasticity which occurs when the yield stress on first loading is maintained.     

Shakedown theory for elastic plastic kinematic hardening bodies

Shakedown static and kinematic theorems for elastic–plastic (generally nonlinear) kinematic hardening solids are derived in classical (path-independence) spirit with new constructions. The generally plastic-deformation-history-dependent hardening curve is assumed to be limited by the initial yield stress and ultimate yield strength, and to obey a positive hysteresis postulate for closed plastic cycles, but else can be arbitrary and unspecified. The theorems reveal that the shakedown of structures is not affected by the particular form of the hardening curve, but just by the initial and ultimate yield stresses. While the ultimate yield strength is clearly defined macroscopically and attached to the incremental collapse mode with unbounded plastic deformations, the initial yield stress, which is responsible for the bounded cyclic plasticity collapse mode, should not be taken as the convenient one at a fixed amount of plastic deformation (0.2%), but is suggested to be taken as low as the fatigue limit to preserve the classical load-history-independence spirit of the shakedown theorems. Otherwise, for our pragmatic application purpose, it may be given empirical values between the low fatigue limit and high ultimate yield stresses according to particular loading processes considered, which may range anywhere between the high-cycle and low-cycle ones. The theorems appear as simple as those of Melan and Koiter for perfect plasticity but applied to the much larger class of more realistic kinematic hardening materials.     

Modeling of fatigue crack growth from a notch

When a fatigue crack is nucleated and propagates into the vicinity of the notch, the crack growth rate is generally higher than that can be expected by using the stress intensity factor concept. The current study attempted to describe the crack growth at notches quantitatively with a detailed consideration of the cyclic plasticity of the material. An elastic–plastic finite element analysis was conducted to obtain the stress and strain histories of the notched component. A single multiaxial fatigue criterion was used to determine the crack initiation from the notch and the subsequent crack growth. Round compact specimens made of 1070 steel were subjected to Mode I cyclic loading with different R-ratios at room temperature. The approach developed was able to quantitatively capture the crack growth behavior near the notch. When the R-ratio was positive, the crack growth near a notch was mainly influenced by the plasticity created by the notch and the resulted fatigue damage during crack initiation. When the R-ratio was negative, the contact of the cracked surfaces during a part of a loading cycle reduced the cyclic plasticity of the material near the crack tip. The combined effect of notch plasticity and possible contact of cracked surface were responsible for the observed crack growth phenomenon near a notch.     

A constitutive model of cyclic plasticity

This paper addresses a constitutive model of cyclic plasticity with special emphasis on the yield-point phenomena. In order to point out the deformation characteristics of a mild steel, four types of experiments were conducted, i.e. uniaxial tension at several crosshead speeds, cyclic straining, and stress- and strain-controlled ratchetting. A viscoplastic constitutive model of cyclic plasticity is proposed on the premise that the phenomena of sharp yield point and the subsequent abrupt yield drop result from rapid dislocation multiplication and the stress-dependence of dislocation velocity. Besides, cyclic plasticity behavior, such as the Bauschinger effect, cyclic hardening/softening characteristics and ratchet-strain accumulation, is described by some kinematic and isotropic hardening rules. The cyclic stress–strain responses predicted by this model agree well with the corresponding experimental results.     

显式方法精确模拟形状记忆合金循环荷载下的变形行为

本文提出全新的有限弹塑性J2流方程,用来显式、精确地模拟SMAs（形状记忆合金）材料在循环加载-卸载条件下从塑性逐渐转变为伪弹性的变形行为．首先,改进流动法,使得本构方程耦合屈服中心的移动和屈服面的增大,并改进背应力演化方程,使模型可以产生强烈的包辛格效应,从理论上具备模拟SMAs独特变形行为的能力;其次,构造全过程下的统一硬化函数显式表达式,代入本构方程后能得到符合要求的形函数;再次,利用选定的数据点构造统一光滑的上屈服函数,再利用上下屈服应力之间的一种线性关系,推导得到下屈服阶段的形函数;最后,只需要给定一个参数就可以得到单个循环结果,利用拉格朗日插值方法构建参数随循环次数变化的函数,就可以模拟任意循环荷载下的变形行为．通过模型结果和实验数据对比证明新方法的有效性．     

Constitutive modeling of cyclic plasticity deformation of a pure polycrystalline copper

Cyclic plasticity experiments were conducted on a pure polycrystalline copper and the material was found to display significant cyclic hardening and nonproportional hardening. An effort was made to describe the cyclic plasticity behavior of the material. The model is based on the framework using a yield surface together with the Armstrong–Frederick type kinematic hardening rule. No isotropic hardening is considered and the yield stress is assumed to be a constant. The backstress is decomposed into additive parts with each part following the Armstrong–Frederick type hardening rule. A memory surface in the plastic strain space is used to account for the strain range effect. The Tanaka fourth order tensor is used to characterize nonproportional loading. A set of material parameters in the hardening rules are related to the strain memory surface size and they are used to capture the strain range effect and the dependence of cyclic hardening and nonproportional hardening on the loading magnitude. The constitutive model can describe well the transient behavior during cyclic hardening and nonproportional hardening of the polycrystalline copper. Modeling of long-term ratcheting deformation is a difficult task and further investigations are required.     

Multiaxial ratcheting with advanced kinematic and directional distortional hardening rules

Ratcheting is defined as the accumulation of plastic strains during cyclic plastic loading. Modeling this behavior is extremely difficult because any small error in plastic strain during a single cycle will add to become a large error after many cycles. As is typical with metals, most constitutive models use the associative flow rule which states that the plastic strain increment is in the direction normal to the yield surface. When the associative flow rule is used, it is important to have the shape of the yield surface modeled accurately because small deviations in shape may result in large deviations in the normal to the yield surface and thus the plastic strain increment in multi-axial loading. During cyclic plastic loading these deviations will accumulate and may result in large errors to predicted strains.This paper compares the bi-axial ratcheting simulations of two classes of plasticity models. The first class of models consists of the classical von Mises model with various kinematic hardening (KH) rules. The second class of models introduce directional distortional hardening (DDH) in addition to these various kinematic hardening rules. Directional distortion describes the formation of a region of high curvature on the yield surface approximately in the direction of loading and a region of flattened curvature approximately in the opposite direction. Results indicate that the addition of directional distortional hardening improves ratcheting predictions, particularly under biaxial stress controlled loading, over kinematic hardening alone.     

A chemo-mechanical model coupled with thermal effect on the hollow core–shell electrodes in lithium-ion batteries

Electrode is a key component to remain durability and safety of lithium-ion(Li-ion) batteries. Li-ion insertion/removal and thermal expansion mismatch may induce high stress in electrode during charging and discharging processes. In this paper, we present a continuum model based on COMSOL Multiphysics software, which involves thermal, chemical and mechanical behaviors of electrodes. The results show that,because of diffusion-induced stress and thermal mismatch, the electrode geometry plays an important role in diffusion kinetics of Li-ions. A higher local compressive stress results in a lower Li-ion concentration and thus a lower capacity when a particle is embedded another, which is in agreement with experimental observations.     

Stochastic many-particle model for LFP electrodes

In the framework of non-equilibrium thermodynamics, we derive a new model for many-particle electrodes. The model is applied to \(\text {LiFePO}_{4}\) (LFP) electrodes consisting of many LFP particles of nanometer size. The phase transition from a lithium-poor to a lithium-rich phase within LFP electrodes is controlled by both different particle sizes and surface fluctuations leading to a system of stochastic differential equations. An explicit relation between battery voltage and current controlled by the thermodynamic state variables is derived. This voltage–current relation reveals that in thin LFP electrodes lithium intercalation from the particle surfaces into the LFP particles is the principal rate-limiting process. There are only two constant kinetic parameters in the model describing the intercalation rate and the fluctuation strength, respectively. The model correctly predicts several features of LFP electrodes, viz. the phase transition, the observed voltage plateaus, hysteresis and the rate-limiting capacity. Moreover we study the impact of both the particle size distribution and the active surface area on the voltage–charge characteristics of the electrode. Finally we carefully discuss the phase transition for varying charging/discharging rates.     

Two-way coupled analysis of lithium diffusion and diffusion induced finite elastoplastic bending of bilayer electrodes in lithium-ion batteries

A fully coupling model for the diffusion induced finite elastoplastic bending of bilayer electrodes in lithium-ion batteries is proposed. The effect of the mechanical stress on the lithium diffusion is accounted for by the mechanical part of the chemical potential derived from the Gibbs free energy along with the logarithmic stress and strain. Eight dimensionless parameters, governing the stress-assisted diffusion and the diffusion induced elastoplastic bending, are identified. It is found that the finite plasticity starting from the interface of the bilayer increases the chemical potential gradient and thereby facilitates the lithium diffusion. The full plastic flow makes the abnormal lithium concentration distribution possible, i.e., the concentration at the lithium inlet can be lower than the concentration at the interface (downstream). The increase in the thickness of the active layer during charging is much larger than the eigen-stretch due to lithiation, and this excess thickening is found to be caused by the lithiation induced plastic yield.