Identifying the Mechanism of Continued Growth of the Solid–Electrolyte Interphase

Single, Fabian; Latz, Arnulf; Horstmann, Birger

doi:10.1002/cssc.201800077

Cited by 100 publications

(174 citation statements)

References 37 publications

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“…3,19,[43][44][45] Our recent findings suggest that solvent molecules are effectively immobilized within these pores. 46,47 However, this result does not apply to smaller and more mobile lithium ions. They are also charged and subject to large electric forces.…”

Section: Sei Modelmentioning

confidence: 91%

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Theory of Impedance Spectroscopy for Lithium Batteries

2019

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In this article, we derive and discuss a physics-based model for impedance spectroscopy of lithium batteries. Our model for electrochemical cells with planar electrodes takes into account the solid-electrolyte interphase (SEI) as porous surface film. We present two improvements over standard impedance models. Firstly, our model is based on a consistent description of lithium transport through electrolyte and SEI. We use welldefined transport parameters, e.g., transference numbers, and consider convection of the center-of-mass. Secondly, we solve our model equations analytically and state the full transport parameter dependence of the impedance signals. Our consistent model results in an analytic expression for the cell impedance including bulk and surface processes. The impedance signals due to concentration polarizations highlight the importance of electrolyte convection in concentrated electrolytes. We simplify our expression for the complex impedance and compare it to common equivalent circuit models. Such simplified models are good approximations in concise parameter ranges. Finally, we compare our model with experiments of lithium metal electrodes and find large transference numbers for lithium ions. This analysis reveals that lithium-ion transport through the SEI has solid electrolyte character.

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Section: Sei Modelmentioning

confidence: 91%

“…The spatial dependence of these parts is given by e −ik1x and e −ik2x respectively, see eqs. (44) and (46). For illustrative purposes, k 2 has been chosen equal to k 1 /10.…”

Section: Interface Reactionmentioning

confidence: 99%

Theory of Impedance Spectroscopy for Lithium Batteries

2019

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“…Several growth limiting steps are assumed in literature, e. g., electron tunneling, electron conduction, solvent diffusion or lithium‐interstitial diffusion, which have been studied using continuum models for aging during battery storage or formation . Possibly there is a competition of several transport mechanisms in parallel and a two layer structure with a dense inner and porous outer layer .…”

Section: Microscopic Scalementioning

confidence: 99%

“…Since film properties have been assumed to be homogeneous and no morphological or structural aspects have been considered, thickness tends to equilibrate and spatial differences are only visible under extreme conditions, e. g., high currents or thick electrodes. Transport processes and growth limiting steps have been studied frequently with model based approaches, and strongly depend on the actual film morphology and molecular structure as will be discussed in more detail below. To conclude, single scale models presently do not enable simulation of the molecular buildup for long time scales in order to evaluate heterogeneity and spatial distribution of structural properties.…”

Section: Introductionmentioning

confidence: 99%

“…This can be achieved by adequate multiscale techniques [25] as has been demonstrated for several related electrochemical problems. [26,27] In our previous work we established the required methodology by detailed investigation of numerical implementations [28] and by demonstration for heterogeneous EC reduction within a continuum single particle model. [29] A similar multiscale model has been introduced by Shinagawa et al [30] to study film growth and capacity fade of a battery.…”

Section: Introductionmentioning

confidence: 99%

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Model Based Multiscale Analysis of Film Formation in Lithium‐Ion Batteries

Röder

Laue

Krewer

2019

Batteries & Supercaps

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Evidence for multiscale interaction of processes during surface film growth is provided using a multiscale modeling approach. The model directly couples a continuum pseudo two dimensional (P2D) battery model and a heterogeneous surface film growth model based on the kinetic Monte Carlo (kMC) method. Key parameters have been identified at basic electrochemical experiments, i. e., open circuit potential (OCP), C‐rate tests, and potential during filmformation. Simulations are in very good agreement with these experiments. Simulation results are shown for various formation procedures, i. e., for different applied C‐rates. Interaction between macroscopic transport processes on electrode scale and elementary reaction steps on atomistic scale are observed. Results reveal a distinct impact of the applied procedures on the atomistic structure of surface films. It can be seen that locally heterogeneous films are formed with very slow charging rate due to stochasticity of the growth process, while spatially heterogeneous films are formed with very fast charging rate due to the spatial heterogeneous distribution of concentration and potential. Therefore, the author's emphasize that in order to identify charging protocols for optimal film morphology multiscale interactions should be considered.

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A Perspective on the Molecular Modeling of Electrolyte Decomposition Reactions for Solid Electrolyte Interphase Growth in Lithium‐Ion Batteries

Bin Jassar,

Michel,

Abada

et al. 2024

Adv Funct Materials

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The solid electrolyte interphase (SEI) is a thin heterogeneous layer formed at the anode/electrolyte interface in lithium‐ion batteries as a consequence of the reduction of the electrolyte. The initial formation of the SEI inhibits the direct contact between the electrode and the electrolyte and thus protects the battery. However, the composition, structure, and size of the SEI evolve over time and the growth of the SEI is considered the primary mechanism leading to the gradual deterioration of the battery performance. Despite the importance of the SEI and its growth, the atomistic understanding of the underlying elementary reaction steps remains partial. Molecular modeling of the electrolyte decomposition is key to gain detailed insights that are complementary to experiments for the reactions occurring in this heterogenous interphase. In this perspective, the electron transport mechanisms are first described from the anode to the electrolyte through the SEI and highlight the importance of the inorganic/organic interface within the heterogeneous SEI: it is where the electrolyte decomposition reactions are likely to occur. Finally, a view is provided on the current progress on molecular modeling techniques (e.g., Density Functional Theory, force fields, machine learning potentials) of the SEI and the challenges each method faces.

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Identifying the Mechanism of Continued Growth of the Solid–Electrolyte Interphase

Cited by 100 publications

References 37 publications

Theory of Impedance Spectroscopy for Lithium Batteries

Theory of Impedance Spectroscopy for Lithium Batteries

Model Based Multiscale Analysis of Film Formation in Lithium‐Ion Batteries

A Perspective on the Molecular Modeling of Electrolyte Decomposition Reactions for Solid Electrolyte Interphase Growth in Lithium‐Ion Batteries

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