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The underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries

Many organic solvents have very desirable solution properties, such as wide temperature range, high solubility of Li salts and nonflammability, and should be able but fail in reality to serve as electrolyte solvents for Li-ion or -metal batteries due to their reduction instability. The origin of thi...

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Autores principales: Shen, Xiaohui, Li, Peng, Liu, Xingwei, Chen, Shengli, Ai, Xinping, Yang, Hanxi, Cao, Yuliang
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8261714/
https://www.ncbi.nlm.nih.gov/pubmed/34276932
http://dx.doi.org/10.1039/d1sc01363g
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author Shen, Xiaohui
Li, Peng
Liu, Xingwei
Chen, Shengli
Ai, Xinping
Yang, Hanxi
Cao, Yuliang
author_facet Shen, Xiaohui
Li, Peng
Liu, Xingwei
Chen, Shengli
Ai, Xinping
Yang, Hanxi
Cao, Yuliang
author_sort Shen, Xiaohui
collection PubMed
description Many organic solvents have very desirable solution properties, such as wide temperature range, high solubility of Li salts and nonflammability, and should be able but fail in reality to serve as electrolyte solvents for Li-ion or -metal batteries due to their reduction instability. The origin of this interfacial instability remains unsolved and disputed so far. Here, we reveal for the first time the origin of the reduction stability of organic carbonate electrolytes by combining ab initio molecular dynamics (AIMD) simulations, density functional theory (DFT) calculations and electrochemical stability experiments. It is found that with the increase of the molar ratio (MR) of salt to solvent, the anion progressively enters into the solvation shell of Li(+) to form an anion-induced ion–solvent-coordinated (AI-ISC) structure, leading to a “V-shaped” change of the LUMO energy level of coordinated solvent molecules, whose interfacial stability first decreases and then increases with the increased MRs of salt to solvent. This mechanism perfectly explains the long-standing puzzle about the interfacial compatibility of organic electrolytes with Li or similar low potential anodes and provides a basic understanding and new insights into the rational design of the advanced electrolytes for next generation lithium secondary batteries.
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spelling pubmed-82617142021-07-16 The underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries Shen, Xiaohui Li, Peng Liu, Xingwei Chen, Shengli Ai, Xinping Yang, Hanxi Cao, Yuliang Chem Sci Chemistry Many organic solvents have very desirable solution properties, such as wide temperature range, high solubility of Li salts and nonflammability, and should be able but fail in reality to serve as electrolyte solvents for Li-ion or -metal batteries due to their reduction instability. The origin of this interfacial instability remains unsolved and disputed so far. Here, we reveal for the first time the origin of the reduction stability of organic carbonate electrolytes by combining ab initio molecular dynamics (AIMD) simulations, density functional theory (DFT) calculations and electrochemical stability experiments. It is found that with the increase of the molar ratio (MR) of salt to solvent, the anion progressively enters into the solvation shell of Li(+) to form an anion-induced ion–solvent-coordinated (AI-ISC) structure, leading to a “V-shaped” change of the LUMO energy level of coordinated solvent molecules, whose interfacial stability first decreases and then increases with the increased MRs of salt to solvent. This mechanism perfectly explains the long-standing puzzle about the interfacial compatibility of organic electrolytes with Li or similar low potential anodes and provides a basic understanding and new insights into the rational design of the advanced electrolytes for next generation lithium secondary batteries. The Royal Society of Chemistry 2021-06-01 /pmc/articles/PMC8261714/ /pubmed/34276932 http://dx.doi.org/10.1039/d1sc01363g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Shen, Xiaohui
Li, Peng
Liu, Xingwei
Chen, Shengli
Ai, Xinping
Yang, Hanxi
Cao, Yuliang
The underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries
title The underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries
title_full The underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries
title_fullStr The underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries
title_full_unstemmed The underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries
title_short The underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries
title_sort underlying mechanism for reduction stability of organic electrolytes in lithium secondary batteries
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8261714/
https://www.ncbi.nlm.nih.gov/pubmed/34276932
http://dx.doi.org/10.1039/d1sc01363g
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