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.     

具有表面效应的球形纳米电极颗粒中的反应-扩散-力学全耦合分析

表面效应在纳米电极颗粒中占有主导地位,论文首先建立了锂离子电池充放电过程中考虑表面效应的反应-扩散-力学全耦合模型;然后对比了有无表面效应对锂离子浓度、径向应力和环向应力的影响;最后探讨了反应系数和尺寸效应对浓度和扩散诱导应力的影响.数值结果表明表面效应随着充电时间的增加逐渐减小直至充电结束趋于稳定;表面压效应对本模型的浓度无影响但抑制了扩散诱导应力的增加;较慢的化学反应和较小的纳米电极颗粒尺寸可抑制电极应力的增加.     

Melting heat transfer in Cu-water and Ag-water nanofluids flow with homogeneous-heterogeneous reactions

This article addresses melting heat transfer in magnetohydrodynamics(MHD)nanofluid flows by a rotating disk. The analysis is performed in Cu-water and Ag-water nanofluids. Thermal radiation, viscous dissipation, and chemical reactions impacts are added in the nanofluid model. Appropriate transformations lead to the nondimensionalized boundary layer equations. Series solutions for the resulting equations are computed.The role of pertinent parameters on the velocity, temperature, and concentration is analyzed in the outputs. It is revealed that the larger melting parameter enhances the velocity profile while the temperature profile decreases. The surface drag force and heat transfer rate are computed under the influence of pertinent parameters. Furthermore, the homogeneous reaction parameter serves to decrease the surface concentration.     

Nanoparticle coagulation in a planar jet via moment method

Large eddy simulations of nanoparticle coagulation in an incompressible pla- nar jet were performed.The particle is described using a moment method to approximate the particle general dynamics equations.The time-averaged results based on 3000 time steps for every case were obtained to explore the influence of the Schmidt number and the Damkohler number on the nanoparticle dynamics.The results show that the changes of Schmidt number have the influence on the number concentration of nanoparticles only when the particle diameter is less than 1 nm for the fixed gas parameters.The number concentration of particles for small particles decreases more rapidly along the flow di- rection,and the nanoparticles with larger Schmidt number have a narrower distribution along the transverse direction.The smaller nanoparticles coagulate and disperse easily, grow rapidly hence show a stronger polydispersity.The smaller coagulation time scale can enhance the particle collision and coagulation.Frequented collision and coagulation bring a great increase in particle size.The larger the Damkohler number is,the higher the particle polydispersity is.     

Unsteady Boundary Layer on a Blunt Body in a Hypersonic Flow of Non-Uniform Dusty Gas

The unsteady heat transfer at the stagnation point on a blunt body traveling at hypersonic velocity through a layer of nonuniform dusty gas with low-inertia particles (not deposited on the body surface) is investigated. Using the matched asymptotic expansion method, the equations of the two-phase unsteady boundary layer near the symmetry axis of the body are derived with account for the polydispersity of the particles. The structure of the unsteady boundary layer and the variation of the friction and heat transfer coefficients at the stagnation point are studied numerically. Layered nonuniformities of the particle concentration and size are considered, the limits of variation of the thermal and mechanicals loads are found, and the effect of the dust polydispersity on the heat transfer is investigated.     

Experimental and computational studies on flow behavior of gas-solid fluidized bed with disparately sized binary particles

This paper presents experimental and computational studies on the flow behavior of a gas-solid fluidized bed with disparately sized binary particle mixtures. The mixing/segregation behavior and segregation efficiency of the small and large particles are investigated experimentally.Particle composition and operating conditions that influence the fluidization behavior of mixing/segregation are examined. Based on the granular kinetics theory, a multi-fluid CFD model has been developed and verified against the experimental results. The simulation results are in reasonable agreement with experimental data. The results showed that the smaller particles are found near the bed surface while the larger particles tend to settle down to the bed bottom in turbulent fluidized bed. However, complete segregation of the binary particles does not occur in the gas velocity range of 0.695--0.904 m/s. Segregation efficiency increases with increasing gas velocity and mean residence time of the binary particles, but decreases with increasing the small particle concentration. The calculated results also show that the small particles move downward in the wall region and upward in the core. Due to the effect of large particles on the movement of small particles, the small particles present a more turbulent velocity profile in the dense phase than that in the dilute phase.     

Experimental and computational studies on flow behavior of gas–solid fluidized bed with disparately sized binary particles

This paper presents experimental and computational studies on the flow behavior of a gas-solid fluidized bed with disparately sized binary particle mixtures. The mixing/segregation behavior and segregation efficiency of the small and large particles are investigated experimentally. Particle composition and operating conditions that influence the fluidization behavior of mixing/segregation are examined. Based on the granular kinetics theory, a multi-fluid CFD model has been developed and verified against the experimental results. The simulation results are in reasonable agreement with experimental data. The results showed that the smaller particles are found near the bed surface while the larger particles tend to settle down to the bed bottom in turbulent fluidized bed. However, complete segregation of the binary particles does not occur in the gas velocity range of 0.695-0.904 m/s. Segregation efficiency increases with increasing gas velocity and mean residence time of the binary particles, but decreases with increasing the small particle concentration. The calculated results also show that the small particles move downward in the wall region and upward in the core. Due to the effect of large particles on the movement of small particles, the small particles present a more turbulent velocity profile in the dense phase than that in the dilute phase.     

Numerical computation of central crack growth in an active particle of electrodes influenced by multiple factors

Mechanical degradation, especially fractures in active particles in an electrode, is a major reason why the capacity of lithium-ion batteries fades. This paper proposes a model that couples Li-ion diffusion, stress evolution, and damage mechanics to simulate the growth of central cracks in cathode particles \((\hbox {LiMn}_{2}\hbox {O}_{4})\) by an extended finite element method by considering the influence of multiple factors. The simulation shows that particles are likely to crack at a high discharge rate, when the particle radius is large, or when the initial central crack is longer. It also shows that the maximum principal tensile stress decreases and cracking becomes more difficult when the influence of crack surface diffusion is considered. The fracturing process occurs according to the following stages: no crack growth, stable crack growth, and unstable crack growth. Changing the charge/discharge strategy before unstable crack growth sets in is beneficial to prevent further capacity fading during electrochemical cycling.     

Global modelling of heat release during initiation and propagation of detonation and deflagration waves in methane-air-particle systems

In the present paper the direct initiation of a self supporting detonation and propagation of a low-speed combustion in methane-air-coal particles mixtures are solved. For particles, a heterogeneous regime of combustion is used, for methane one overall chemical reaction is taken into account: CH + 2O = CO + 2HO. The heat release rate is assumed to be defined as a delay time based on the well-known thermal theory of Frank-Kamenetsky (1967). The proposed model allows one to investigate the influence inert particles or coal dust on the explosion limits of methane-air mixtures. It is shown that the addition of a limited quantity of particles leads to detonation stability. In low speed combustion problems this method allows one to get a good correlation between theoretical and experimental velocities of steady flame propagation in carbon-hydrogen gaseous mixtures. Coal dust influence on gasdynamics of a methane-air mixture combustion is investigated in an unsteady problem by using of the global modelling. It is shown that limited coal dust concentration increases the flame wave intensity in lean methane-air mixtures in contrast to inert particles. In stoichiometric gas mixtures, sand and coal dusts decrease a flame velocity. Far from the ignition point flame, the velocity is largely defined by the dust mass concentration and not by the size of particles. Received 5 July 1997 / Accepted 13 July 1998     

Viscoplastic response of electrode particles in Li-ion batteries driven by insertion of lithium

Constitutive equations are derived for the viscoplastic behavior of a host medium driven by diffusion of guest atoms. With reference to the trapping concept, two states of a guest atom are distinguished: mobile and immobilized (due to alloying with the host matrix). This allows propagation of a sharp interphase to be described between regions rich and poor in guest atoms. The model is applied to study the mechanical response of a spherical electrode particle in a Li-ion battery. Ability of the constitutive equations to capture basic phenomena observed in anode particles under lithiation is demonstrated by numerical simulation.     

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.     

Solution of general dynamic equation for nanoparticles in turbulent flow considering fluctuating coagulation

A new averaged general dynamic equation (GDE) for nanoparticles in the turbulent flow is derived by considering the combined effect of convection, Brownian diffusion, turbulent diffusion, turbulent coagulation, and fluctuating coagulation. The equation is solved with the Taylor-series expansion moment method in a turbulent pipe flow. The experiments are performed. The numerical results of particle size distribution correlate well with the experimental data. The results show that, for a turbulent nanoparticulate flow, a fluctuating coagulation term should be included in the averaged particle GDE. The larger the Schmidt number is and the lower the Reynolds number is, the smaller the value of ratio of particle diameter at the outlet to that at the inlet is. At the outlet, the particle number concentration increases from the near-wall region to the near-center region. The larger the Schmidt number is and the higher the Reynolds number is, the larger the difference in particle number concentration between the near-wall region and near-center region is. Particle polydispersity increases from the near-center region to the near-wall region. The particles with a smaller Schmidt number and the flow with a higher Reynolds number show a higher polydispersity. The degree of particle polydispersity is higher considering fluctuating coagulation than that without considering fluctuating coagulation.     

Diffusion-reaction compromise the polymorphs of precipitated calcium carbonate

Diffusion is seldom considered by chemists and materialists in the preparation of materials while it plays an important role in the field of chemical engineering. If we look at crystallization at the atomic level, crystal growth in a solution starts from the diffusion of ions to the growing surface followed by the incorporation of ions into its lattice. Diffusion can be a rate determining step for the growth of crystals. In this paper, we take the crystallization of calcium carbonate as an example to illustrate the microscopic processes of diffusion and reaction and their compromising influence on the morphology of the crystals produced. The diffusion effect is studied in a specially designed three-cell reactor. Experiments show that a decrease of diffusion leads to retardation of supersaturation and the formation of a continuous concentration gradient in the reaction cell, thus promoting the formation of cubic calcite particles. The reaction rate is regulated by temperature. Increase of reaction rate favors the formation of needle-like aragonite particles. When diffusion and reaction play joint roles in the reaction system, their compromise dominates the formation of products, leading to a mixture of cubic and needle-like particles with a controllable ratio. Since diffusion and reaction are universal factors in the preparation of materials, the finding of this paper could be helpful in the controlled synthesis of other materials.     

Detonation waves in polydisperse gas suspensions of monofuel in tubes with an abrupt expansion

The distinctive features of detonation wave propagation in polydisperse (double-fraction) gas suspensions of a monofuel in tubes with an abrupt expansion are numerically investigated. Numerical calculations are performed for different sizes and relative mass contents of the particles of both fractions. A comparative analysis of the effect of mono- and polydisperse monofuel particles on the detonation wave mitigation is made. The dependences of the critical tube-diameter ratio of a sectional pipeline on the relative mass content and polydispersity of monofuel particles with different sizes are presented.     

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.     

Rheometrical and molecular dynamics simulation studies of incipient clot formation in fibrin-thrombin gels: An activation limited aggregation approach

A rheometrical investigation of incipient clots formed in fibrin-thrombin gels is reported in which the Gel Point (GP) is characterised by frequency independence of the loss tangent in small amplitude oscillatory shear measurements over a wide range of thrombin concentration. Values of the fractal dimension (D_f) of the GP network calculated from measurements are consistent with those reported in simulations of diffusion limited cluster-cluster aggregation (DLCCA) and reaction limited cluster-cluster aggregation (RLCCA), but differ insofar as the values of D_f calculated from the present experiments increase progressively with a reduction in gel formation time. A molecular dynamics simulation (MDS) of systems of rod-like particles was designed to (i) test the hypothesis that the presence of an activation profile in a cluster aggregation model could account for the trend of D_f as a function of gel formation time observed experimentally in fibrin-thrombin gels and whole heparinised blood without recourse to the inclusion of fibrinogen-specific interactions; and (ii) to explore the effect of monomer activation kinetics on the microstructure of fractal clusters formed in systems of rigid rod-like particles. The results identify two possible mechanisms for the increase in D_f as the gel formation time decreases, both being a consequence of altering the evolution of the clustering dynamics by a process referred to herein as activation limited aggregation (ALA). This ALA-based MDS substantiates the experimental findings by confirming the trend evident in the formation of incipient clots in fibrin-thrombin gels and in whole heparinised blood. A mechanism for ALA involving the aggregation of pre-GP sub-clusters is proposed.     

A new method for particle manipulation by combination of dielectrophoresis and field-modulated electroosmotic vortex

A field-modulated electroosmotic flow (FMEOF) in a microchannel can be obtained by applying modulating electric fields in a direction perpendicular to the channel wall. Micro-vortexes are generated around the electrodes along with an EOF due to the surface charge on the modulated wall. When polarizable particles are suspended near the electrodes, they experience dielectrophoretic forces due to a non-uniform electric field. In this paper, micro-vortexes and dielectrophoretic forces are combined to achieve separation and trap different sized particles in a continuous flow. Numerical results indicate that by adjusting the driving electric field parallel to the channel wall and the modulating electric field, the ratio of dielectrophoretic and hydrodynamic forces can be altered. One type of particles can be trapped by micro-vortexes (negative dielectrophoresis (DEP)), and the other particles are transported to the downstream so that the particles are separated. The influence of the electrode length and the channel height on the trapping rate is investigated.     

The velocity of sand particles relative to water and the variation of fluctuation velocity due to the concentration of suspended sand particles

In this paper, we discuss three fundamental problems of the theory of suspended sand particles based on the theory of fluid dynamics. They are: (1) the relative velocity of sand particles to the surrounding fluid in the turbulent flow, (2) the variation of the velocity fluctuation of the fluid when the suspended sand particles exist, (3) the profile of the vertical distribution of the concentration of the suspended sand particles in two-dimensional uniform steady channel flow and the modification of usual diffusion theory. The results of our theoretical analysis are somewhat different from the corresponding expressions in the textbooks of hydraulics and river mechanics.     

Kinetics of the coalescence of an emulsion in an electrical field

The article [1] considered the approach of two conducting spherical particles in a viscous liquid in the presence of a homogeneous external electrical field. As a result, the collision cross section of the particles was determined, and the kinetics of the simplest bidisperse system was discussed. The present article, which is a direct continuation of [1], examines the kinetics of coalescence with a continuous function of the particle-size distribution. Numerical and approximate (by the method of moments) solutions of the kinetic equation are obtained. Comparison of the solutions permits the conclusion that the change in the number of particles and their volumetric concentration are well described by the approximate solution.     

Balancing particle properties for practical lithium-ion batteries

As a state-of-the-art secondary battery, lithium-ion batteries (LIBs) have dominated the consumer electronics market since Sony unveiled the commercial secondary battery with LiCoO₂ as the negative electrode material in the early 1990s. The key to the efficient operation of LIBs lies in the effective contact between the Li-ion-rich electrolyte and the active material particles in the electrode. The particle properties of the electrode materials affect the lithium ion diffusion path, diffusion resistance, contact area with the active material, the electrochemical performance and the energy density of batteries. To achieve satisfied comprehensive performance and of LIBs, it is not only necessary to focus on the modification of materials, but also to balance the properties of electrode material particles. Therefore, in this review, we analyze the influence of particle properties on the battery performance from three perspectives: particle size, particle size distribution, and particle shape. A deep understanding of the effect and mechanism of particles on electrodes and batteries will help develop and manufacture practical LIBs.