Three-dimensional particle-resolved models of Li-ion batteries to assist the evaluation of empirical parameters in one-dimensional models

Goldin, Graham M.; Colclasure, Andrew M.; Wiedemann, Andreas H.; Kee, Robert J.

doi:10.1016/j.electacta.2011.12.119

Cited by 114 publications

(131 citation statements)

References 14 publications

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“…On the right-hand side of Equation 21, the three terms contributing to the ion mass flux N i correspond to ion diffusion, electrostatic migration, and a correction due to the finite ion size, respectively. 95,99 Finally, the electric potential within the electrodes is governed by the continuity equation combined with Ohm's law to give, 185,186 ∇ · (σ s ∇ψ) = 0 [22] where σ s is the electrical conductivity of the electrode material. Note that Equations 20 to 22 are coupled and thus must be solved simultaneously subject to proper initial and boundary conditions.…”

mentioning

confidence: 99%

Recent Advances in Continuum Modeling of Interfacial and Transport Phenomena in Electric Double Layer Capacitors

Pilon

Wang

d’Entremont

2015

J. Electrochem. Soc.

119

105

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This paper reviews recent advances in physical modeling of interfacial and transport phenomena in electric double layer capacitors (EDLCs) under both equilibrium and dynamic cycling. The models are based on continuum theory and account for (i) the Stern layer at the electrode/electrolyte interface, (ii) finite ion sizes, (iii) steric repulsions, (iv) asymmetric electrolytes featuring ions with different valencies, effective diameters, or diffusion coefficients, (v) electric-field-dependent dielectric permittivity of the electrolyte, and/or (vi) porous three-dimensional morphology of the electrodes. Typical characterization methods such as electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic cycling were reproduced numerically to identify the dominant physical phenomena and to gain insight into experimental observations. In addition, recent thermal models derived from first principles for EDLCs under constant-current cycling accounting for irreversible Joule heating and reversible heat generation rates due to ion diffusion, steric effects, and changes in entropy are discussed. Scaling analyses of both equilibrium and dynamic models are also presented as a way to identify self-similar and asymptotic behaviors as well as to develop design rules for electrodes and electrolytes of next generation EDLCs. Electrical double layer capacitors (EDLCs) store energy by ion adsorption in the electrical double layer (EDL) forming at the electrode/electrolyte interfaces.1,2 This process is highly reversible and the cycle life of EDLCs exceeds 100,000 cycles.2,3 EDLCs can operate in a wide range of specific energy and power densities. This versatility is a key feature for electrical energy storage, energy harvesting, and energy regeneration applications. 2The performance of EDLCs is determined by the combination of the electrode material and morphology and of the electrolyte. In general, the key attributes of a good electrode include 1,3-7 (i) large surface area accessible to ions to maximize charge storage, (ii) optimum pore size, short pore length, and good pore connectivity to facilitate ion transport, (iii) large electrical conductivity to enable fast charging and discharging and low ohmic resistance, (iv) thin electrodes and current collectors to reduce the total resistance of the device, (v) small leakage current, (vi) small self-discharge, (vii) environmentally friendly materials, and (viii) low price. However, satisfying all these criteria simultaneously is challenging. For example, increasing surface area often results in larger electrode electrical resistivity.1 Micropores with diameter less than 2 nm contribute greatly to EDLCs capacitance.2 But pores smaller than the ion size are typically inactive and do not contribute to charge storage. 1,8 Porous electrodes must also be electrochemically accessible to ions. Then, interconnected mesopores with diameter ranging from 2 to 50 nm are necessary for fast charging thanks to their easier accessibility to ions. 1,6,[9][10][11] In practice, electrode...

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mentioning

confidence: 99%

Recent Advances in Continuum Modeling of Interfacial and Transport Phenomena in Electric Double Layer Capacitors

Pilon

Wang

d’Entremont

2015

J. Electrochem. Soc.

119

105

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“…[45][46][47][48][49][50][51] The dimensionless parameters α, β, γ and δ in the electrolyte and electrode phases, readily calculated from (7) and (19), are reported in Table II and plotted on the corresponding phase diagram for the electrolyte and electrode, Figure 3 and 4, respectively. LiC6 [43] LiC6 [44] LixC6 [45] Li1−xC6 [46] LiCoO2 [45] LiFePO4 [42] LiFePO4 [44] Li4Ti5O12 [47,48] Figure 4.…”

Section: Case Study For Commercial Batteries: Validity Of Macroscale mentioning

confidence: 99%

“…In particular, we compare the accuracy of continuum-scale models with either their fully resolved (3D) counterparts or with experiments as reported in a number of studies. [45][46][47][48][49][50][51] More importantly, we relate macroscale models' predictive performance to the applicability regimes defined in Figures (1) and (2), and employ the former as a screening tool to a priori evaluate continuum model predictivity under variable C-rate.…”

Section: Case Study For Commercial Batteries: Validity Of Macroscale mentioning

confidence: 99%

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On Veracity of Macroscopic Lithium-Ion Battery Models

Arunachalam¹,

Onori²,

Battiato³

2015

J. Electrochem. Soc.

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Batteries are electrochemical energy storage devices that exhibit physico-chemical heterogeneity on a continuity of scales. As such, battery systems are amenable to mathematical descriptions on a multiplicity of scales that range from atomic to continuum. In this paper we present a new method to assess the veracity of macroscopic models of lithium-ion batteries. Macroscopic models treat the electrode as a continuum and are often employed to describe the mass and charge transfer of lithium since they are computational tractable and practical to model the system at the cell scale. Yet, they rely on a number of simplifications and assumptions that may be violated under given operating conditions. We use multiple-scale expansions to upscale the pore-scale Poisson-Nerst-Planck (PNP) equations and establish sufficient conditions under which macroscopic dual-continua mass and charge transport equations accurately represent pore-scale dynamics. We propose a new method to quantify the relative importance of three key pore-scale transport mechanisms (electromigration, diffusion and heterogenous reaction) by means of the electric Péclet (Pe) and Damköhler (Da) numbers in the electrolyte and the electrode phases. For the first time, applicability conditions of macroscopic models through a phase diagram in the (Da-Pe)-space are defined. Finally, we discuss how the new proposed tool can be used to assess the validity of macroscopic models across different battery chemistry and conditions of operation. In particular, a case study analysis is presented using commercial lithium-ion batteries that investigates the validity of Newman-type macroscopic models under temperature and current rate of charge/discharge variation. Predictive understanding of battery dynamical behavior still remains a major bottleneck in achieving diagnostic capabilities, safety, optimization and control of battery systems under different operating conditions. Such a difficulty arises from two main factors: i) nonlinearity of lithium-ion transport processes 1 and ii) battery systems multiscale structure that exhibits physicochemical heterogeneity on a continuity of scales (from the nanometer to the meter).2-5 Since the seminal work by Newman and Tiedemann, 6 where macroscopic ion transport equations were first formulated, a plethora of models have spurred in the past decades. They range from fully empirical approaches to generalizations of electrochemical models based on the porous electrode theory to account for concentrated solutions, 7,8 thermal effects 9 and capacity fade due to Solid-Electrolyte Interphase (SEI)-growth, [10][11][12] just to mention a few. In the past decade, ever increasing computational capabilities have fuelled the development of fully molecular/atomistic models and multiscale/multiphysics approaches. 13 For a thorough review on the topic, we refer the reader to Ref. 4. Microscale models 14,15 (e.g. molecular dynamics, kinetic Monte Carlo and pore-scale models) are theoretically robust, but are impractical as a predictive tool at t...

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“…For instance, Wang et al [6] found that the microstructure of the LIB electrode significantly affects achievable capacity by comparing the numerical results of the randomly and regularly packed electrode structures. Goldin et al [7] showed that the packing configuration of particles affects lithium ion transport, thereby affecting the performance of LIBs. Smith et al [8] developed a two dimensional (2D) ion transport model using scanning electron microscope (SEM) images of LIB electrodes.…”

Section: Introductionmentioning

confidence: 99%

Geometric Characteristics of Three Dimensional Reconstructed Anode Electrodes of Lithium Ion Batteries

et al. 2014

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Abstract:The realistic three dimensional (3D) microstructure of lithium ion battery (LIB) electrode plays a key role in studying the effects of inhomogeneous microstructures on the performance of LIBs. However, the complexity of realistic microstructures imposes a significant computational cost on numerical simulation of large size samples. In this work, we used tomographic data obtained for a commercial LIB graphite electrode to evaluate the geometric characteristics of the reconstructed electrode microstructure. Based on the analysis of geometric properties, such as porosity, specific surface area, tortuosity, and pore size distribution, a representative volume element (RVE) that retains the geometric characteristics of the electrode material was obtained for further numerical studies. In this work, X-ray micro-computed tomography (CT) with 0.56 μm resolution was employed to capture the inhomogeneous porous microstructures of LIB anode electrodes. The Sigmoid transform function was employed to convert the initial raw tomographic images to binary images. Moreover, geometric characteristics of an anode electrode after 2400 cycles at the charge/discharge rate of 1 C were compared with those of a new anode electrode to investigate morphological change of the electrode. In general, the cycled electrode shows larger porosity, smaller tortuosity, and similar specific surface area compared to the new electrode. OPEN ACCESSEnergies 2014, 7 2559

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Three-dimensional particle-resolved models of Li-ion batteries to assist the evaluation of empirical parameters in one-dimensional models

Cited by 114 publications

References 14 publications

Recent Advances in Continuum Modeling of Interfacial and Transport Phenomena in Electric Double Layer Capacitors

Recent Advances in Continuum Modeling of Interfacial and Transport Phenomena in Electric Double Layer Capacitors

On Veracity of Macroscopic Lithium-Ion Battery Models

Geometric Characteristics of Three Dimensional Reconstructed Anode Electrodes of Lithium Ion Batteries

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