Issue 26, 2021

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

Abstract

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
09 Mar 2021
Accepted
28 May 2021
First published
01 Jun 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 9037-9041

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

X. Shen, P. Li, X. Liu, S. Chen, X. Ai, H. Yang and Y. Cao, Chem. Sci., 2021, 12, 9037 DOI: 10.1039/D1SC01363G

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements