The solid electrolyte interphase (SEI) is a multistructured thin layer that forms at the anode (e.g., lithium-metal)/electrolyte (e.g., ethylene carbonate EC) interface due to electrolyte reduction. At the initial battery cycles, the SEI protects the electrolyte from further reduction. However, the SEI continues to grow with time, leading to capacity loss and eventually the death of the battery. In this work, we modeled the battery-aging process at storage conditions (calendar aging). We studied EC decomposition reactions using density functional theory (DFT) simulations in the gas-phase in isolation and over the inorganic layer found inside the SEI composed of Li2CO3. We used the values obtained from DFT alongside diffusion coefficients from the literature to explore the temporal evolution of the concentration of the species by kinetic Monte Carlo (kMC) simulations. We found that reactions occurring over Li2CO3 (001) led to a relatively slow SEI growth which is compatible with the general use of carbonate-based solvents in LIBs for protection/passivation purposes. Our simulations over Li2CO3 (001) predict the formation of a multilayered structured SEI. Moreover, our kMC simulations predict the shift from a nonlinear initial behavior to a linear behavior for the capacity loss induced by the formation and growth of the SEI over time which was reported in previous experimental and theoretical studies for lithiated graphite-based batteries. We extended our analysis to the decomposition reactions over the Li2O (111) surface, which could form from the decomposition of Li2CO3. We found that the selectivity of the decomposition reactions strongly depends on the inorganic surface. The main conclusion of this study is to highlight the crucial role played by surface reactions inside the SEI on the nature and selectivity of the decomposition kinetics of EC for the SEI growth.
Authors
Mohammed Bin Jassar, Carine Michel, Sara Abada, Theodorus de Bruin, Sylvain Tant, Carlos Nieto-Draghi, Stephan Steinmann
Related Organizations
- Bibliographic Reference
- Mohammed Bin Jassar, Carine Michel, Sara Abada, Theodorus de Bruin, Sylvain Tant, et al.. A Joint DFT-kMC Study to Model Ethylene Carbonate Decomposition Reactions : SEI Formation, Growth, and Capacity Loss During Calendar aging of Li-Metal Batteries. ACS Applied Energy Materials, 2023, 6 (13), pp.6934-6945. ⟨10.1021/acsaem.3c00372⟩. ⟨hal-04172957⟩
- DOI
- https://doi.org/10.1021/acsaem.3c00372
- HAL Collection
- ['École Normale Supérieure de Lyon', "Sciences De l'Environnement", 'IFP Energies Nouvelles', 'CNRS - Centre national de la recherche scientifique', 'Université Claude Bernard - Lyon I', 'GIP Bretagne Environnement', 'Institut de Chimie du CNRS', 'UDL', 'Université de Lyon']
- HAL Identifier
- 4172957
- Institution
- ['Stellantis (Centre technique de Carrières-sous-Poissy)', 'École normale supérieure de Lyon', 'Université Claude Bernard Lyon 1', 'Institut de Chimie - CNRS Chimie', 'IFP Energies nouvelles']
- Laboratory
- Laboratoire de Chimie - UMR5182
- Published in
- France
Table of Contents
- A Joint DFT-kMC Study to Model Ethylene Carbonate Decomposition Reactions SEI Formation Growth and Capacity Loss During Calendar aging of Li-Metal Batteries 1
- A joint DFT-kMC study to model ethylene 2
- Li-metal batteries 2
- Abstract 3
- EC Decomposition Reactions in the Gas-Phase Isolation 15
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