Phase Separation Dynamics in Isotropic Ion-Intercalation Particles

Zeng, Yi; Bazant, Martin Z.

doi:10.1137/130937548

Cited by 56 publications

(103 citation statements)

References 83 publications

(201 reference statements)

Supporting

Mentioning

100

Contrasting

Order By: Relevance

“…Finite volume discretization was used in space with minor modifications for geometry following the reference 29 . Time integration was carried out using DAE Tools 45 , which wraps the SUNDIALS integration suite 46 with the ADOL-C automatic differentiation library 47 …”

Section: Numerical Simulationsmentioning

confidence: 99%

Li Intercalation into Graphite: Direct Optical Imaging and Cahn–Hilliard Reaction Dynamics

Guo

Smith

et al. 2016

J. Phys. Chem. Lett.

Self Cite

100

134

View full text Add to dashboard Cite

Section: Numerical Simulationsmentioning

confidence: 99%

Li Intercalation into Graphite: Direct Optical Imaging and Cahn–Hilliard Reaction Dynamics

Guo

Smith

et al. 2016

J. Phys. Chem. Lett.

Self Cite

100

134

View full text Add to dashboard Cite

“…39 Fick's law of diffusion is only applicable to single-phase diffusion process. In highcapacity anode materials, two-phase diffusion is modeled by solving the Cahn-Hilliard equation, which is provided below: 39,50 (1 −ĉ s )), where, D Li corresponds to the diffusivity of lithium, R is the universal gas constant and T signifies the temperature in Kelvin. Also, ω is a non-dimensional parameter, which physically signifies the enthalpy of mixing, and mathematically produces the double well in the free energy functional.…”

Section: Methodsmentioning

confidence: 99%

“…50,53,54 A new lattice spring based methodology has been developed to incorporate the effect of large volume expansion observed in high capacity anode materials (such as, Si and Sn). The previous lattice-spring methodology was used for modeling small amount of volume expansion is active particles.…”

Section: Methodsmentioning

confidence: 99%

Mechano-Electrochemical Stochastics in High-Capacity Electrodes for Energy Storage

Barai

Mukherjee

2016

J. Electrochem. Soc.

View full text Add to dashboard Cite

High-capacity anode materials (such as, silicon) are of critical importance for lithium-ion batteries aimed at achieving longer drive range for electric vehicles. Large lithium retention in these alloying materials is, however, accompanied by high volume expansion, which results in severe mechanical degradation and capacity decay. The inherently coupled mechano-electrochemical stochastics is elucidated in this work. A stochastic computational methodology has been developed to capture the large deformation and mechanical degradation in high-capacity anode materials. Lithiation and delithiation in such active particles follow a two-phase diffusive interface formation and propagation. Mechano-electrochemical interactions lead to different tensile forces acting on the active particle that may lead to microcrack formation. In this study, we have demonstrated that: (a) concentration gradient induced stress at the two-phase interface does not lead to severe mechanical degradation; and (b) large volume expansion induced tensile force at the particle surface actually gives rise to multiple spanning crack formation and further propagation during delithiation. Anode materials with higher partial molar volume of the lithiated phase can lead to enhanced mechanical degradation. Functionally graded materials, with reduced elastic modulus near the surface, hold potential for significant reduction in crack formation. Lithium-ion batteries (LIBs) are poised to play a major role in the advancement toward wide-spread vehicle electrification.1-3 Significant effort is being invested to make use of lithium ion chemistry in commercial aircrafts (see 4,5 ) as well as large-scale grid energy storage systems (see 6,7 ). Increasing the specific energy of both cathode (see 8,9 ) and anode (see 10,11 ) electrode active material will effectively result in enhanced energy density of the LIB. Commercial batteries use lithium cobalt oxide (LiCoO 2 ) or nickel-manganese-cobalt (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) as the cathode material, which shows around 170mAh/g as the effective specific energy.12 Graphite is used regularly as anode active material within commercial batteries, which shows a maximum of 372mAh/g specific capacity. 12Next generation lithium ion batteries are supposed to use high capacity cathode as well as anode materials.11 Layered-layered composite cathode structures, represented as xLi 2 MnO 3 · (1-x)LiMO 2 (M = Mn, Ni, Co), has received attention due to high rechargeable capacity of 250mAh/g when cycled between 4.6 V and 2.0 V (see [13][14][15] ). Gas generation due to oxygen release is one of the major modes of degradation in these composite cathode materials. These high-capacity layered composite cathodes do not experience severe volume expansion during lithiation process. 16 High capacity anode materials can show almost ten times higher theoretical specific energy than graphite (such as, silicon (Si), tin (Sn) and germanium (Ge)) (see [17][18][19][20] ). The theoretical capacity of silicon is 4200mAh/g and the same for tin is 994...

show abstract

“…After obtaining the spatial discretization of the PDE system, we employ the implicit ODE solver "ode15s" in MATLAB for the time integration. The detailed derivations of the numerical scheme can be found in the full article of this project [29].…”

Section: Numerical Schemementioning

confidence: 99%

“…We will focus on the simulation results from the lithiation dynamics (the discharging case). A more detailed study on both lithiation and delithiation dynamics can be found in the full article of this work [29].…”

Section: Solid Solutionmentioning

confidence: 99%

Cahn-Hilliard Reaction Model for Isotropic Li-ion Battery Particles

Zeng

Bazant

2013

MRS Proc.

Self Cite

View full text Add to dashboard Cite

Using the recently developed Cahn-Hilliard reaction (CHR) theory, we present a simple mathematical model of the transition from solid-solution radial diffusion to two-phase shrinking-core dynamics during ion intercalation in a spherical solid particle. This general approach extends previous Li-ion battery models, which either neglect phase separation or postulate a spherical shrinking-core phase boundary under all conditions, by predicting phase separation only under appropriate circumstances. The effect of the applied current is captured by generalized ButlerVolmer kinetics, formulated in terms of the diffusional chemical potential in the CHR theory. We also consider the effect of surface wetting or de-wetting by intercalated ions, which can lead to shrinking core phenomena with three distinct phase regions. The basic physics are illustrated by different cases, including a simple model of lithium iron phosphate (neglecting crystal anisotropy and coherency strain).

show abstract

Phase Separation Dynamics in Isotropic Ion-Intercalation Particles

Cited by 56 publications

References 83 publications

Li Intercalation into Graphite: Direct Optical Imaging and Cahn–Hilliard Reaction Dynamics

Li Intercalation into Graphite: Direct Optical Imaging and Cahn–Hilliard Reaction Dynamics

Mechano-Electrochemical Stochastics in High-Capacity Electrodes for Energy Storage

Cahn-Hilliard Reaction Model for Isotropic Li-ion Battery Particles

Contact Info

Product

Resources

About