Intercalation Kinetics in Multiphase-Layered Materials

Smith, Raymond B.; Khoo, Edwin; Bazant, Martin Z.

doi:10.1021/acs.jpcc.7b00185

Cited by 94 publications

(125 citation statements)

References 130 publications

(401 reference statements)

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“…Material models can easily use distinct discretization and/or geometries such as the homogeneous or CHR particles. We have also already included the two-repeating-layers model developed and applied to single graphite particles [76,89]. Other variations such as 2D particles of arbitrary geometry discretized using the finite volume [159] or finite element method would also be straightforward, especially with the DAE Tools interface to the deal.ii finite element library [154,160].…”

Section: A Software Organization and Structurementioning

confidence: 99%

“…This is the approach of "multiphase porous electrode theory" presented below. In principle, such models are required to predict multiphase battery performance over a wide range of temperatures and currents [40,44,75,76], as well as degradation related to mechanical stresses [25,72] and side reactions that depend on the local surface concentration profile [77].Regardless of the thermodynamic model, volume averaged simulations using porous electrode theory are carried out in a number of ways. Newman's dualfoil code uses a finite difference method via the BAND subroutine, and it is freely available [78] and commonly used.…”

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confidence: 99%

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Multiphase Porous Electrode Theory

Smith

Bazant

2017

J. Electrochem. Soc.

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187

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Porous electrode theory, pioneered by John Newman and collaborators, provides a macroscopic description of battery cycling behavior, rooted in microscopic physical models. Typically, the active materials are described as solid solution particles with transport and surface reactions driven by concentration fields, and the thermodynamics are incorporated through fitting of the open circuit potential. However, this approach does not apply to phase separating materials, for which the voltage is an emergent property of inhomogeneous concentration profiles, even in equilibrium. Here, we present a general framework, "multiphase porous electrode theory", based on nonequilibrium thermodynamics and implemented in an open-source software package called "MPET". Cahn-Hilliard-type phase field models are used to describe the active materials with suitably generalized models of interfacial reaction kinetics. Classical concentrated solution theory is implemented for the electrolyte phase, and Newman's porous electrode theory is recovered in the limit of solid solution active materials with Butler-Volmer kinetics. More general, quantum-mechanical models of faradaic reactions are also included, such as Marcus-Hush-Chidsey kinetics for electron transfer at electrodes, extended for concentrated solutions. The full model and implementation are described, and a variety of example calculations are presented to illustrate the novel features of the software compared to existing battery models. Lithium-based batteries have growing importance in global society 1 as a result of increased prevalence of portable electronic devices, 2 and their enabling role in the transition toward renewable energy sources.3 For example, lithium batteries can help mitigate intermittency of renewable energy sources such as solar power, and lithium battery powered electric vehicles are facilitating movement away from liquid fossil fuels for transportation. Each of these growing areas demands high performance batteries, with requirements specific to the particular needs of the application driving specialized battery design for sub-markets. Thus, it is critical that battery models be based on the underlying physics, enabling them to greatly facilitate cell design to take best advantage of the existing battery technologies.Lithium-ion batteries are generally constructed using two porous electrodes and a porous separator between them. The porous electrodes consist of various interpenetrating phases including electrolyte, active material, binder, and conductive additive. A schematic is shown in Figure 1. In a charged state, most of the lithium in the cell is contained in the active material within the negative electrode. During discharge, the lithium undergoes transport to the surface of the active material, electrochemical reaction to move from the active material to the electrolyte, transport through the electrolyte to the positive electrode, and reaction and transport to move into the active material of the positive electrode.4,5 Physical models must capture eac...

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Section: A Software Organization and Structurementioning

confidence: 99%

mentioning

confidence: 99%

Multiphase Porous Electrode Theory

Smith

Bazant

2017

J. Electrochem. Soc.

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187

232

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“…Similar to the phase-field model for graphite [43] this requires the introduction of two parameters (c 1 and c 2 ) that describe the Li concentration in the first and second lattice, respectively. In both lattices, the Gibbs free energy [g(c i )] is described by a Cahn-Hilliard regular solution model [9]: while a large i term will promote phase-separation.…”

Section: Phase-field Model For Anatasementioning

confidence: 99%

Explaining key properties of lithiation in TiO2 -anatase Li-ion battery electrodes using phase-field modeling

Klerk

Vasileiadis

Smith

et al. 2017

Phys. Rev. Materials

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The improvement of Li-ion battery performance requires development of models that capture the essential physics and chemistry in Li-ion battery electrode materials. Phase-field modeling has recently been shown to have this ability, providing new opportunities to gain understanding of these complex systems. In this paper, a novel electrochemical phase-field model is presented that captures the thermodynamic and kinetic properties of lithium insertion in TiO 2 -anatase, a well-known and intensively studied Li-ion battery electrode material. Using a linear combination of two regular solution models, the two phase transitions during lithiation are described as lithiation of two separate lattices with different physical properties. Previous elaborate experimental work on lithiated anatase TiO 2 provides all parameters necessary for the phase-field simulations, giving the opportunity to gain fundamental insight in the lithiation of anatase and validate this phase-field model. The phase-field model captures the essential experimentally observed phenomena, rationalizing the impact of C rate, particle size, surface area, and the memory effect on the performance of anatase as a Li-ion battery electrode. Thereby a comprehensive physical picture of the lithiation of anatase TiO 2 is provided. The results of the simulations demonstrate that the performance of anatase is limited by the formation of the poor Li-ion diffusion in the Li 1 TiO 2 phase at the surface of the particles. Unlike other electrode materials, the kinetic limitations of individual anatase particles limit the performance of full electrodes. Hence, rather than improving the ionic and electronic network in electrodes, improving the performance of anatase TiO 2 electrodes requires preventing the formation of a blocking Li 1 TiO 2 phase at the surface of particles. Additionally, the qualitative agreement of the phase-field model, containing only parameters from literature, with a broad spectrum of experiments demonstrates the capabilities of phase-field models for understanding Li-ion electrode materials, and its promise for guiding the design of electrodes through a thorough understanding of material properties and their interactions.

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“…Aside from the terms involving c max a,i , the electrochemical kinetics described by (13a)- (14) are consistent with those derived by Ferguson and Bazant [19] using non-equilibrium thermodynamics. The theoretical open-circuit potential, which is consistent with the Butler-Volmer kinetics (13), is given by…”

Section: Electrochemical Kineticsmentioning

confidence: 55%

“…Mathematical modelling plays an important role in LIB research because it provides cost-effective insights that can be difficult to obtain through experimental measurement. Modelling has led to improved understanding of many aspects of batteries, including intercalation kinetics [13], active-material utilisation [14] and distribution [15], mechanics [16,17], phase separation [18][19][20][21][22][23], electrode fabrication [24], and model parameter estimation [25,26]. The development of porous electrode theory by Newman [27,28] laid the foundation on which nearly every battery model is now built upon.…”

Section: Introductionmentioning

confidence: 99%

Asymptotic reduction and homogenization of a thermo-electrochemical model for a lithium-ion battery

Hennessy

Moyles

2020

Applied Mathematical Modelling

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We study two thermo-electrochemical models for lithium-ion batteries. The first is based on volume averaging the electrode microstructure whereas the second is based on the pseudo-two-dimensional (P2D) approach which treats the electrode as a collection of spherical particles. A scaling analysis is used to reduce the volume-averaged model and show that the electrochemical reactions are the dominant source of heat. Matched asymptotic expansions are used to compute solutions of the volume-averaged model for the cases of constant applied current, oscillating applied current, and constant cell potential. The asymptotic and numerical solutions of the volume-averaged model are in remarkable agreement with numerical solutions of the thermal P2D model for (dis)charge rates up to 2C, and reasonable agreement is found at 4C. Homogenisation is then used to derive a thermal model for a battery consisting of several connected lithium-ion cells. Despite accounting for the Arrhenius dependence of the reaction coefficients, we show that thermal runaway does not occur in the model. Instead, the cell potential is simply pushedcloser to the open-circuit potential. We also show that in many cases, the homogenised battery model can be solved analytically, making it ideal for use in on-board thermal management systems.

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Intercalation Kinetics in Multiphase-Layered Materials

Cited by 94 publications

References 130 publications

Multiphase Porous Electrode Theory

Multiphase Porous Electrode Theory

Explaining key properties of lithiation in TiO2 -anatase Li-ion battery electrodes using phase-field modeling

Asymptotic reduction and homogenization of a thermo-electrochemical model for a lithium-ion battery

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