Particulate modification of lithium-ion battery anode materials and electrolytes

Lithium-ion batteries (LIBs) are considered a rechargeable and commercial energy storage device for electronic equipment such as smartphone and electric vehicles. Despite the prospective future of LIBs, unsatisfied electrochemical properties like reversible capacity, cycle ability and coulombic efficiency still hinder their development. High volume expansion rate, uncontrolled Li dendrite growth and unsatisfied solid electrolyte interphase also occur when LIBs are applied in long-time usage. Numerous modification methods such as exploring high-capacity anode/cathode materials, constructing artificial solid electrolyte interphase and improved conductive binders can be adopted to enhance the performances. Among them, particulate modification for LIBs anode and electrolytes is receiving tremendous attraction in the recent work. The method is composed of changing the morphology and particle size of the active materials, also introduce nano-size additives to the main structure. This review emphasizes on introducing and discussing the modification in following aspects: particulate modification on carbon group IVA element anodes, introduction of additives like transition metal oxide nanoparticles into anode and electrolyte materials, dissipate the influence of Li dendrite growth and ameliorate the performances of solid electrolyte interface. This review hopes to be denoted for the future development of LIBs with the comprehensive understanding on the particulate modification.     

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．     

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.     

Si-induced insertion of Li into SiC to form Li-rich SiC twin crystal

The energy density of Li-ion batteries is closely related to the capacity and average voltage of cathode materials. Unfortunately, current cathode materials either have low capacity or voltage, which limits the development of high-energy-density Li-ion batteries. This has given challenge to many attempts to develop new cathode materials with high capacity and voltage. In this study, we find that Li easily inserts into the (111) plane of SiC in the presence of Si, and a well-organized Li-rich SiC twin crystal is formed. Ultraviolet–visible diffuse reflectance spectra and electrochemical test results suggest that this Li-rich SiC twin crystal possesses the band gap energy of 3.5 eV and charging capacity of 1979 mAh/g at the current density of 200 mA/g, making it a promising candidate for the cathode material in high-capacity Li-ion batteries. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy results reveal that Si-induced Li insertion contributes to the changes in the surface species and structure of pristine SiC. These findings suggest that the Li-rich SiC twin crystal raises new possibilities for the development of high-capacity cathode materials and merits further investigation to expand its application scope.     

焊锡接点IMC层的扩散应力

钎焊过程中在焊锡接点中形成的金属间化合物(IMC)对焊锡接点可靠性具有重要影响。在原子扩散效应下,回流焊和等温时效过程中IMC层的生长会在其内部产生应力,其微结构也发生变化,致使IMC层和整个焊点的力学性能下降。本文基于扩散反应机制,研究了由于原子扩散产生的IMC层的扩散应力。首先建立了焊锡接点IMC层生长早期微结构特征的2界面(Cu/Cu6Sn5/Solder)分析模型,然后运用Laplace变换法求解扩散方程得到了Cu原子在IMC层中的浓度分布;采用把原子扩散作用转换为体应变方法,计算了IMC层在形成和生长过程中应力的解析解。结果表明：IMC层中的扩散应力为压应力,最大值位于Cu/IMC界面处,大小与扩散原子浓度密切相关;随着时效时间的增加,扩散应力增大,但最终趋于稳定并沿IMC厚度方向线性变化。     

Stress-mediated lithiation in nanoscale phase transformation electrodes

Development of high-performance phase transformation electrodes in lithium ion batteries requires comprehensive studies on stress-mediated lithiation involving migration of the phase interface. It brings out many counter-intuitive phenomena, especially in nanoscale electrodes, such as the slowing down migration of phase interface, the vanishing of miscibility gap under high charge rate, and the formation of surface crack during lithiation. However,it is still a challenge to simulate the evolution of stress in arbitrarily-shaped nanoscale electrodes, accompanied with phase transformation and concurrent plastic deformation. This article gives a brief review of our efforts devoted to address these issues by developing phase field model and simulation. We demonstrate that the miscibility gap of two-phase state is affected not only by stress but also by surface reaction rate and particle size. In addition, the migration of phase interface slows down due to stress. It reveals that the plastic deformation generates large radial expansion, which is responsible for the transition from surface hoop compression to surface hoop tension that may induce surface crack during lithiation.We hope our effort can make a contribution to the understanding of stress-coupled kinetics in phase transformation electrodes.     

Lithiation-enhanced charge transfer and sliding strength at the silicon-graphene interface:A first-principles study

The application of silicon as ultrahigh capacity electrodes in lithium-ion batteries has been limited by a number of mechanical degradation mechanisms including fracture, delamination and plastic ratcheting, as a result of its large volumetric change during lithiation and delithiation. Graphene coating is one feasible technique to mitigate the mechanical degradation of Si anode and improve its conductivity. In this paper, first-principles calculations are performed to study the atomic structure, charge transfer and sliding strength of the interface between lithiated silicon and graphene. Our results show that Li atoms segregate at the(lithiated) Si-graphene interface preferentially, donating electrons to graphene and enhancing the interfacial sliding resistance. Moreover, the interfacial cohesion and sliding strength can be further enhanced by introducing single-vacancy defects into graphene.These findings provide insights that can guide the design of stable and efficient anodes of silicon/graphene hybrids for energy storage applications.     

界面调控对类金刚石碳基薄膜/铜摩擦副摩擦学行为的影响

无氢DLC/金属铜摩擦副体系摩擦系数高且不易调控，调整DLC/金属铜摩擦界面从而降低其摩擦系数是亟待解决的问题. 本研究中通过制备含氢与无氢类金刚石碳基薄膜，采用试验分析与模拟计算结合的方法研究了不同氢含量碳基薄膜与铜配副的摩擦学特性并讨论了氢原子在摩擦界面对改善摩擦学性能所起的作用. 结果表明:摩擦界面的结构特性对于类金刚石碳基薄膜/铜配副体系摩擦学性能有非常重要的影响，氢原子可以通过减小摩擦副之间的黏着从而起到调节摩擦界面的作用. 通过向DLC中掺杂氢等钝化元素可有效调控界面处的相互作用从而调控体系摩擦学性能. 本研究方法为降低DLC/铜摩擦副体系摩擦系数提供参考.      

From coherent to incoherent mismatched interfaces: A generalized continuum formulation of surface stresses

The equilibrium of coherent and incoherent mismatched interfaces is reformulated in the context of continuum mechanics based on the Gibbs dividing surface concept. Two surface stresses are introduced: a coherent surface stress and an incoherent surface stress, as well as a transverse excess strain. The coherent surface stress and the transverse excess strain represent the thermodynamic driving forces of stretching the interface while the incoherent surface stress represents the driving force of stretching one crystal while holding the other fixed and thereby altering the structure of the interface. These three quantities fully characterize the elastic behavior of coherent and incoherent interfaces as a function of the in-plane strain, the transverse stress and the mismatch strain. The isotropic case is developed in detail and particular attention is paid to the case of interfacial thermo-elasticity. This exercise provides an insight on the physical significance of the interfacial elastic constants introduced in the formulation and illustrates the obvious coupling between the interface structure and its associated thermodynamics quantities. Finally, an example based on atomistic simulations of Cu/Cu₂O interfaces is given to demonstrate the relevance of the generalized interfacial formulation and to emphasize the dependence of the interfacial thermodynamic quantities on the incoherency strain with an actual material system.     

Synthesis of layered cathode materials Li[CoxNiyMn1-x-y]O2 from layered double hydroxide precursors

Cathode materials Li[CoxNiyMn1-x-y]O2 for lithium secondary batteries have been prepared by a new route using layered double hydroxides (LDHs) as a precursor. The resulting layered phase with the α-NaFeO2 structure crystallizes in the rhombohedral system, with space group R-3m having an interlayer spacing close to 0.47 nm. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation states of Co, Ni and Mn. The effects of varying the Co/Ni/Mn ratio on both the structure and electrochemical properties of Li[CoxNiyMn1-x-y]O2 have been investigated by X-ray diffraction and electrochemical tests.The products demonstrated a rather stable cycling behavior, with a reversible capacity of 118 mAh/g for the layered material with Co/Ni/Mn = 1/1/1.     

Interface balance laws,phase growth and nucleation conditions for multiphase solids with inhomogeneous surface stress

In this paper, the thermodynamic configurational force associated with a moving interface is used to derive the conditions for phase growth and nucleation in bodies with multiple diffusing species and arbitrary surface stress at the phase interface. First, the mass, momentum and energy balances are derived on the evolving phase interface. The thermodynamic conditions that result from free energy inequality at the interface are derived leading to the analytical form of the configurational force for bodies subject to mechanical loads, heat and multiple diffusing species. The derived second law condition naturally extends the Eshelby energy–momentum tensor to include species diffusion terms. The above second law restriction is then used to derive the condition for the growth of new phases in a body undergoing finite deformation subject to inhomogeneous as well as anisotropic interface stress, and multiple diffusing species. The growth conditions are derived in both current and reference configurations. The statistical temperature-dependent growth velocity is next derived using the Boltzmann distribution. The derived finite deformation form of growth requirement is simplified to obtain the small deformation diffusive void growth condition. Next, a general, finite deformation, arbitrary surface stress form of phase nucleation condition is derived by considering uncertainty in growth of a small nucleus. The probability of nucleation is shown to naturally depend on a theoretical estimate of critical volumetric energy density, which is directly related to the surface stress. The classical nucleation theory is shown to result from a simplified special case of the general criterion. As an application of the developed theory, the classical Blech electromigration experiment is simulated to estimate the critical energy density corresponding to the onset of electromigration voids at Al–TiN interface.     

Effect of prestress on the stability of electrode–electrolyte interfaces during charging in lithium batteries

We formulate a model of the growth of electrode–electrolyte interfaces in lithium batteries in the presence of an elastic prestress. The model accounts for the kinetics of Li⁺ transport through a solid electrolyte and, within the interface, for the kinetics of Li⁺ adsorption by the anode, electrostatics, and the elastic field. We specifically account for the effect of the elastic field through an asymptotic analysis of a nearly flat interface between two semi-infinite elastic bodies. We use the model as a basis for assessing the effect of prestress on the stability of planar growth and the potential of prestress as a means of suppressing the formation of deleterious dendrites. We present a linear stability analysis that results in explicit analytical expressions for the dependence of growth rates, and of the critical unstable wavelength for the interfacial roughening, on the state of prestress and on fundamental parameters such as surface diffusivities, surface energy, deposition kinetics, and elastic moduli. Finally, we examine the model in the light of experimental observations concerned with the effect of applied pressure on a lithium/dioxolane-dimethoxy ethane electrolyte systems. With reasonable choices of parameters and some calibration, the model accounts for the observation that a modest applied pressure indeed results in a substantial reduction in the roughening of the lithium surface during cycling.     

The effect of inhomogeneous plastic deformation on the ductility and fracture behavior of age hardenable aluminum alloys

The role of alloy composition, grain structure, precipitate microstructure, and precipitate dislocation interactions on the plastic deformation characteristics and the resulting fracture behavior of two isotropic Al–Li–Cu–X alloys designated AF/C-458 (1.8 w/o Li) and AF/C-489 (2.1 w/o Li) was examined. Inhomogeneous deformation due to strain localization from the shearing of the δ′ (Al₃Li), θ′ (Al₂Cu), and T₁ (Al₂CuLi) precipitates lead to fine and coarse planar slip for the AF/C-458 and AF/C-489 alloys, respectively. The intensity of this planar slip was predicted through slip intensity calculations using precipitate density measurements, dislocation particle interactions, and grain boundary misorientation-slip continuity statistics. The slip intensity predictions were corroborated through atomic force microscopy (AFM) measured slip height offsets on the polished surface of single aged and 2% plastically strained tensile samples. Our results suggest that the low ductility of AF/C-489 in comparison to AF/C-458 is primarily due to the much larger slip lengths, i.e. grain size, which increased the strain localization and stress concentrations on grain boundaries, thus promoting low-energy intergranular fracture.     

Atomistically determined phase-field modeling of dislocation dissociation,stacking fault formation,dislocation slip,and reactions in fcc systems

The purpose of the current work is the development of a phase field model for dislocation dissociation, slip and stacking fault formation in single crystals amenable to determination via atomistic or ab initio methods in the spirit of computational material design. The current approach is based in particular on periodic microelasticity (Wang and Jin, 2001, Bulatov and Cai, 2006, Wang and Li, 2010) to model the strongly non-local elastic interaction of dislocation lines via their (residual) strain fields. These strain fields depend in turn on phase fields which are used to parameterize the energy stored in dislocation lines and stacking faults. This energy storage is modeled here with the help of the ”interface” energy concept and model of Cahn and Hilliard (1958) (see also Allen and Cahn, 1979, Wang and Li, 2010). In particular, the “homogeneous” part of this energy is related to the “rigid” (i.e., purely translational) part of the displacement of atoms across the slip plane, while the “gradient” part accounts for energy storage in those regions near the slip plane where atomic displacements deviate from being rigid, e.g., in the dislocation core. Via the attendant global energy scaling, the interface energy model facilitates an atomistic determination of the entire phase field energy as an optimal approximation of the (exact) atomistic energy; no adjustable parameters remain. For simplicity, an interatomic potential and molecular statics are employed for this purpose here; alternatively, ab initio (i.e., DFT-based) methods can be used. To illustrate the current approach, it is applied to determine the phase field free energy for fcc aluminum and copper. The identified models are then applied to modeling of dislocation dissociation, stacking fault formation, glide and dislocation reactions in these materials. As well, the tensile loading of a dislocation loop is considered. In the process, the current thermodynamic picture is compared with the classical mechanical one as based on the Peach-Köhler force.     

Mixed-mode interfacial adhesive strength of a thin film on an anisotropic substrate

The mixed-mode interfacial adhesion strength between a gold (Au) thin film and an anisotropic passivated silicon (Si) substrate is measured using laser-induced stress wave loading. Test specimens are prepared by bonding a fused silica (FS) prism to the back side of a 〈1 0 0〉 Si substrate with a thin silicon nitride (Si_xN_y) passivation layer deposited on the top surface. A high-amplitude stress wave is developed by pulsed laser ablation of a sacrificial absorbing layer on one of the lateral surfaces of the FS prism. Due to the negative non-linear elastic properties of the FS, the compressive stress wave evolves into a decompression shock with fast fall time. Careful selection of the incident angle between the pulse and the FS/Si interface generates a mode-converted shear wave in refraction, subjecting the Si_xN_y/Au thin film interface to dynamic mixed-mode loading, sufficient to cause interfacial fracture. A detailed analysis of the anisotropic wave propagation combined with interferometric measurements of surface displacements enables calculation of the interfacial stresses developed under mixed-mode loading. The mixed-mode interfacial strength is compared to the interfacial strength measured under purely tensile loading.     

SURFACE METALLIZATION OF CENOSPHERES AND PRECIPITATORS BY ELECTROLESS PLATING

This paper reports the use of a colloidal Pd^0 catalysis system to metallize the surface of precipitators separated from coal fly-ash, and metals such as Cu, Ni etc. are deposited on the precipitators surface. Alternatively, according to the characteristic surface of cenospheres, an Ag coating catalysis system is adopted to first deposit Ag on the cenospheres surface, followed, if necessary, by the deposition of other metals such as Cu, Ni, etc. on the Ag coating to produce monolayer and multilayer metal-coated cenospheres. The surface characteristics and the morphologies of the metal coatings are examined in detail with scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) techniques. It can be shown that the quality of metal coatings derived from the Aa coatina catalysis system, is better than that of the colloidal Pd^0 catalysis system.     

Electrorheological Rayleigh-Taylor instability at the interface between a porous layer and thin shell with poorly conducting couple stress fluid

This paper is concerned with the study of the Electrorheological Rayleigh-Taylor instability (ERTI) at the interface between a densely packed saturated poorly conducting couple stress porous layer accelerated by a lighter poorly conducting couple stress fluid in a thin shell in the presence of a transverse electric field and laser radiation. A simple theory based on fully developed flow approximations is used to derive the dispersion relation for the growth rate of ERTI. The cutoff and the maximum wave numbers and the corresponding maximum frequencies are obtained. It is shown that the effects of couple stress parameter and the electric field reduce the growth rate considerably compared to a non-conducting fluid in the absence of an electric field. These are favorable to control the surface instabilities in many practical applications discussed in this paper.     

Atomistic simulation of stress evolution during island growth

We report the results of a series of hybrid molecular dynamics simulations of the growth of islands on a substrate for several different island/substrate interface energies. When the interface energy is small, the islands tend to be thin and broad and the magnitude of the compressive stress-thickness product is relatively large. As the interface energy increases, the islands become taller and thinner and the magnitude of the compressive stress-thickness product decreases. This trend is consistent with experimental observations. The island aspect ratio dependence on interface energy follows from consideration of the equilibrium wetting angle. The effect of interface energy on the stress-thickness product shows that the island shape, surface/interface stresses and island stresses are self-equilibrated. A simple theory is developed that shows that the stress-thickness product is simply proportional to the substrate coverage and the substrate surface stress. The present simulations yield a simple, accurate, validated theory for stress development during the pre-coalescence stage of film growth.     

A Robust <Emphasis Type="Italic">in situ</Emphasis> TEM Experiment for Characterizing the Fracture Toughness of the Interface in Nanoscale Multilayers

A novel in situ transmission electron microscopy (TEM) bending method using a nano-cantilever specimen that includes a naturally sharp pre-crack at the interface between a 500 nm-thick SiN layer and a 200 nm-thick Cu layer on a Si substrate is developed in order to precisely characterize the fracture toughness of the interface in nanoscale multilayers. By fabricating a perpendicular nanoscale notch in the SiN layer close to the horizontal Cu/SiN interface, a sharp pre-crack is successfully introduced at the Cu/SiN interface. In addition, by changing the relative position of the notch with respect to the fixed end of the specimen, both the instant and continuous interface crack propagation behaviors could be in situ observed using TEM. Finite element analysis shows that the crack propagation from the sharp pre-crack is dominated by a singular stress field within a region 100 nm from the crack tip under a mixed-mode state in all specimens. On the other hand, the fracture toughness represented by the critical energy release rate for the start of crack propagation along the Cu/SiN interface in all specimens is determined through a compliance method and shows good agreement with an average value of 7.1 J/m². This indicates the robust reliability and high precision for characterizing the fracture toughness of the interface in nanoscale multilayers.     

微纳米材料及其结构的界面强度的实验研究

介绍了近年来微纳米材料强度实验测试研究方面的最新进展,重点综述了可用于微纳米材料及其结构中界面强度测试的实验系统、测试方法及结果.主要内容包括:测试微纳米薄膜界面端分层裂纹启裂的夹层悬臂梁方法,测试纳米岛/衬底间界面结合强度的改进AFM (atomic force microscopy)方法, 测试裂纹沿界面扩展的预裂纹法,可实现纳米薄膜界面裂纹原位观察的实验测试方法,测试薄膜在疲劳、蠕变条件下界面裂纹扩展的改进4点弯曲法等.除了总结分析测试结果,还讨论了上述实验方法的优缺点和适用范围,并指出了微纳米材料界面强度实验研究方面的一些挑战与难点,最后提出了若干需要继续研究的课题.