Effects of concentration-dependent elastic modulus on the diffusion of lithium ions and diffusion induced stress in layered battery electrodes

He, Yaolong; Hu, Hongjiu; Song, Yicheng; Guo, Zhan‐Sheng; Liu, C.; Zhang, Junqian

doi:10.1016/j.jpowsour.2013.09.118

Cited by 67 publications

(59 citation statements)

References 20 publications

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“…A few authors have investigated the contribution of concentrationdependent elastic constants [4][5][6][7][8][9][10] and concentration-dependent effective diffusivity [7,8,11,12] in the Li flux and resulting LIB electrode stress-state. Regarding the former, Yang et al [8] and He et al [10] used a linear Li-content-dependent Young's modulus in Si and Si-graphite, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Concentration-Dependent Chemical Expansion in Lithium-Ion Battery Cathode Particles

Malavé

Berger

Martín

2014

Journal of Applied Mechanics

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In this work, the effect of the concentration-dependent chemical-expansion coefficient, /?, on the chemo-elastic field in lithium-ion cathode particles is examined. To accomplish this, an isotropic linear-elastic model is developed for a single idealistic particle sub jected to potentiostatic-discharge and charge conditions. It is shown that p can be a key parameter in demarcating the chemo-stress-strain state of the cathode material under going nonlinear volumetric strains. As an example, such strains develop in the hexagonal-to-monoclinic-phase region of LixCoO 2 (0.37 < x< 0.55) and, subsequently, the corresponding p is a linear function of concentration. Previous studies have assumed a constant value for p. Findings suggest that the composition-generated chemo-elastic field that is based on a linear-p dramatically affects both the interdiffusion and the me chanical behavior of the LixCo02 cathode particle. Because the chemo-elastic phenom ena emanate in a reciprocal fashion, the resulting linear P-based hydrostatic-stress gradients significantly aid the diffusion of lithium. Thus, diffusion is accelerated in either electrochemical process that the cathode material undergoes.

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Section: Introductionmentioning

confidence: 99%

“…Regarding the former, Yang et al [8] and He et al [10] used a linear Li-content-dependent Young's modulus in Si and Si-graphite, respectively. In their work [8,10], the Larche-Cahn chemical-potential approach [2] for a binary-alloy solid solution was employed. He et al [10] expressed their modifi cation of Eq.…”

Section: Introductionmentioning

confidence: 99%

Concentration-Dependent Chemical Expansion in Lithium-Ion Battery Cathode Particles

Malavé

Berger

Martín

2014

Journal of Applied Mechanics

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“…While several works have considered the effects of the hydrostatic term, [1][2][3][4][5][6][7][8][9][10][11][12] very few have actually included the last two terms (σ kk σ ii and σ k j σ k j ) of the chemical potential in their analysis. [13][14][15][16] Most of the works neglect these terms since…”

Section: E DCmentioning

confidence: 99%

“…These conditions may be written as; σ rr | r =R = 0 Free surface [15] u| r =0 = 0 [16] Boundary condition in Eq. 15 implies…”

Section: Boundary Conditionsmentioning

confidence: 99%

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Elasticity and Size Effects on the Electrochemical Response of a Graphite, Li-Ion Battery Electrode Particle

Swaminathan

Balakrishnan

George

2015

J. Electrochem. Soc.

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The interactions between electrochemical response, elasticity and particle size of a cylindrical, Li-ion battery, graphite electrode particle is studied. First, a potentiostatic study is conducted to demonstrate the role of higher-order stress terms of the chemical potential on the distributions of flux, stresses and concentrations. Then, two cyclic voltammetry experiments are simulated to study the effects of elasticity on the voltammograms. In the first, the electrode is discharged and then charged, while the second, involves the opposite. Effects of elasticity on the anodic (discharging) portion of the voltammograms are more pronounced in the first experiment when compared to the second. The effects of the elasticity also vary with particle size in different ways for the two experiments. In the first, the effects of stresses on the anodic current increases with particle size and then reaches a plateau at around 30 μm. In the second, a maximum effect of elasticity is seen for a particle size of 5 μm. Our study shows that, stresses induced due to diffusion of Li atoms not only affect the mechanical integrity of the electrode particle, but also change the way the particle responds to an applied external potential, thereby affecting its electrochemical response. Interactions of chemistry and mechanics in Li ion battery (LIB) electrodes has gained a lot of interest recently.1-16 Chemical expansions of varying degrees have been observed and quantified in some of the existing electrode materials (graphite) and in prospective electrode materials like Sn, Al and Si.17 The intercalation and de-intercalation of Li ions into and out of the electrode causes local chemical strains in the latter. During the functioning of the LIB, gradients in Li concentration that arise lead to non-uniform strains throughout the electrode particle. When these chemically induced strains are not accommodated by appropriate deformation of the solid, stresses are induced which can result in local failure and degradation in the performance of the electrode and hence the battery. Local changes in Li concentration also alter the mechanical properties of the electrodes. For a recent, detailed review on the effects of stress-diffusion interactions in Li-ion battery materials and the various experimental techniques involved in their quantification please see Ref. 18. The effects of Li diffusion induced stresses (DIS) are well understood and modeled through the framework of thermoelasticity. The changes in concentration are treated in a manner analogous to changes in temperature, and hence chemical strains are introduced into the constitutive equations of elasticity in the form of eigen strains. The elastic equilibrium equations are then solved in order to predict the stresses, displacement and strains. Stresses also affect the thermodynamics of the electrodes. For example, stresses alter the electrochemical potential of Si by 50mV or more.19 Another associated effect is stress induced diffusion (SID), where the elastic stresses developed in the elec...

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Thermodynamic Understanding of Formation and Evolution of Solid Electrolyte Interface in Li‐Ion Batteries

He,

Wang,

Wang

et al. 2024

Batteries & Supercaps

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Formation is an essential process in the manufacturing of lithium‐ion batteries and determines the performance of batteries, including life time, rate capability and so forth. The core of formation is to form a stable solid electrolyte interphase (SEI), which profoundly influences interfacial reactions and ion transport within Li‐ion batteries, on the surface of electrode. It is crucial to fully and deeply understand the intricate structure and evolution of SEI, which remains largely uncharted. This paper aims to systematically analyze SEI thermodynamics, encompassing energy distribution, entropy dynamics during SEI formation, and enthalpy changes. SEI evolves towards an equilibrium state, maximizing entropy. The intricate relationship between SEI thermodynamics and battery performance is established by dissecting the impacts of temperature and current density on SEI thermodynamic parameters and battery characteristics. Elevated temperatures and higher current densities foster the development of a more porous and high‐entropy outer SEI layer, rendering organic SEI constituents prone to decompose into high‐energy gases and low‐energy inorganic compounds. Notably, a fast formation strategy within a high state‐of‐charge range offers a potential solution to high quality SEI. This review strives to bridge the divide between fundamental thermodynamics and practical battery performance, ultimately contributing to the advancement of battery manufacturing.

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Effects of concentration-dependent elastic modulus on the diffusion of lithium ions and diffusion induced stress in layered battery electrodes

Cited by 67 publications

References 20 publications

Concentration-Dependent Chemical Expansion in Lithium-Ion Battery Cathode Particles

Concentration-Dependent Chemical Expansion in Lithium-Ion Battery Cathode Particles

Elasticity and Size Effects on the Electrochemical Response of a Graphite, Li-Ion Battery Electrode Particle

Thermodynamic Understanding of Formation and Evolution of Solid Electrolyte Interface in Li‐Ion Batteries

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