Communication—First-Principles Simulations of LiPF6 Decomposition in Ethylene Carbonate-Based Electrolytes

Jean Luc Fattebert; Lorena Alzate-Vargas

doi:10.1149/1945-7111/ad69ca

Communication—First-Principles Simulations of LiPF₆ Decomposition in Ethylene Carbonate-Based Electrolytes

Jean Luc Fattebert
, Lorena Alzate-Vargas

Multiscale Materials

Research output: Contribution to journal › Article › peer-review

Abstract

We revisit a theoretical result by Okamoto (2013 Journal of The Electrochemical Society, 160, A404) who calculated the energy barrier for the decomposition of lithium hexafluorophosphate (LiPF₆) into LiF + PF₅ when solvated in Ethylene carbonate (EC)-based electrolyte. Using different numerical techniques to discretize the Density Functional Theory (DFT) equations, and different continuum solvation models with the same dielectric constant, our results largely confirm the original calculation. However, simulations with a higher dielectric permittivity value, closer to that of EC, show a lower energy barrier. More importantly, First-Principles simulations with an explicit solvent show a substantially lower energy barrier.

Original language	English
Article number	080505
Journal	Journal of the Electrochemical Society
Volume	171
Issue number	8
DOIs	https://doi.org/10.1149/1945-7111/ad69ca
State	Published - Aug 1 2024

Funding

This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).

Keywords

Ethylene carbonate
Lithium-ion batteries
Theory and Modelling
lithium hexafluorophosphate
molecular dynamics
reaction constant

Access to Document

10.1149/1945-7111/ad69ca

Cite this

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title = "Communication—First-Principles Simulations of LiPF6 Decomposition in Ethylene Carbonate-Based Electrolytes",

abstract = "We revisit a theoretical result by Okamoto (2013 Journal of The Electrochemical Society, 160, A404) who calculated the energy barrier for the decomposition of lithium hexafluorophosphate (LiPF6) into LiF + PF5 when solvated in Ethylene carbonate (EC)-based electrolyte. Using different numerical techniques to discretize the Density Functional Theory (DFT) equations, and different continuum solvation models with the same dielectric constant, our results largely confirm the original calculation. However, simulations with a higher dielectric permittivity value, closer to that of EC, show a lower energy barrier. More importantly, First-Principles simulations with an explicit solvent show a substantially lower energy barrier.",

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AB - We revisit a theoretical result by Okamoto (2013 Journal of The Electrochemical Society, 160, A404) who calculated the energy barrier for the decomposition of lithium hexafluorophosphate (LiPF6) into LiF + PF5 when solvated in Ethylene carbonate (EC)-based electrolyte. Using different numerical techniques to discretize the Density Functional Theory (DFT) equations, and different continuum solvation models with the same dielectric constant, our results largely confirm the original calculation. However, simulations with a higher dielectric permittivity value, closer to that of EC, show a lower energy barrier. More importantly, First-Principles simulations with an explicit solvent show a substantially lower energy barrier.

KW - Ethylene carbonate

KW - Lithium-ion batteries

KW - Theory and Modelling

KW - lithium hexafluorophosphate

KW - molecular dynamics

KW - reaction constant

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