skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: In situ quantification of interphasial chemistry in Li-ion battery

Abstract

The solid-electrolyte-interphase (SEI) is probably the least understood component in Li-ion batteries. Considerable effort has been put in the understanding of its formation and electrochemistry under realistic battery conditions, but mechanistic insights have been inferred mostly indirectly. Here we show the formation of the SEI between a graphite anode and a carbonate electrolyte using combined atomic scale microscopy and in-situ and operando techniques. In particular, we weigh the graphitic anode during its initial lithiation process with electrochemical quartz crystal microbalance, which unequivocally identifies lithium fluoride (LiF) and lithium alkylcarbonates as the main chemical components at different potentials. In-situ gas analysis confirmed the preferential reduction of cyclic over acyclic carbonate molecules, making its reduction product the major component in SEI. We find that SEI formation starts at graphite edge-sites with dimerization of solvated Li +-intercalation between graphite-layers. As a result, we also show that this lithium salt, at least in its nascent form, is re-oxidizable, despite the general belief that an SEI is electrochemically inert and its formation irreversible.

Authors:
 [1];  [2];  [3];  [2];  [2];  [2];  [2];  [3]; ORCiD logo [3];  [4];  [5];  [2]
  1. Peking Univ., Shenzhen (China); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Peking Univ., Shenzhen (China)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States); Stanford Univ., Stanford, CA (United States)
  5. US Army Research Lab., Adelphi, MD (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1493749
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Nanotechnology
Additional Journal Information:
Journal Volume: 14; Journal Issue: 1; Journal ID: ISSN 1748-3387
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Liu, Tongchao, Lin, Lingpiao, Bi, Xuanxuan, Tian, Leilei, Yang, Kai, Liu, Jiajie, Li, Maofan, Chen, Zonghai, Lu, Jun, Amine, Khalil, Xu, Kang, and Pan, Feng. In situ quantification of interphasial chemistry in Li-ion battery. United States: N. p., 2018. Web. doi:10.1038/s41565-018-0284-y.
Liu, Tongchao, Lin, Lingpiao, Bi, Xuanxuan, Tian, Leilei, Yang, Kai, Liu, Jiajie, Li, Maofan, Chen, Zonghai, Lu, Jun, Amine, Khalil, Xu, Kang, & Pan, Feng. In situ quantification of interphasial chemistry in Li-ion battery. United States. doi:10.1038/s41565-018-0284-y.
Liu, Tongchao, Lin, Lingpiao, Bi, Xuanxuan, Tian, Leilei, Yang, Kai, Liu, Jiajie, Li, Maofan, Chen, Zonghai, Lu, Jun, Amine, Khalil, Xu, Kang, and Pan, Feng. Mon . "In situ quantification of interphasial chemistry in Li-ion battery". United States. doi:10.1038/s41565-018-0284-y.
@article{osti_1493749,
title = {In situ quantification of interphasial chemistry in Li-ion battery},
author = {Liu, Tongchao and Lin, Lingpiao and Bi, Xuanxuan and Tian, Leilei and Yang, Kai and Liu, Jiajie and Li, Maofan and Chen, Zonghai and Lu, Jun and Amine, Khalil and Xu, Kang and Pan, Feng},
abstractNote = {The solid-electrolyte-interphase (SEI) is probably the least understood component in Li-ion batteries. Considerable effort has been put in the understanding of its formation and electrochemistry under realistic battery conditions, but mechanistic insights have been inferred mostly indirectly. Here we show the formation of the SEI between a graphite anode and a carbonate electrolyte using combined atomic scale microscopy and in-situ and operando techniques. In particular, we weigh the graphitic anode during its initial lithiation process with electrochemical quartz crystal microbalance, which unequivocally identifies lithium fluoride (LiF) and lithium alkylcarbonates as the main chemical components at different potentials. In-situ gas analysis confirmed the preferential reduction of cyclic over acyclic carbonate molecules, making its reduction product the major component in SEI. We find that SEI formation starts at graphite edge-sites with dimerization of solvated Li+-intercalation between graphite-layers. As a result, we also show that this lithium salt, at least in its nascent form, is re-oxidizable, despite the general belief that an SEI is electrochemically inert and its formation irreversible.},
doi = {10.1038/s41565-018-0284-y},
journal = {Nature Nanotechnology},
issn = {1748-3387},
number = 1,
volume = 14,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on November 12, 2019
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Challenges for Rechargeable Li Batteries
journal, February 2010

  • Goodenough, John B.; Kim, Youngsik
  • Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
  • DOI: 10.1021/cm901452z

In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode
journal, December 2010


Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004


Lithium Ion Battery Graphite Solid Electrolyte Interphase Revealed by Microscopy and Spectroscopy
journal, January 2013

  • Nie, Mengyun; Chalasani, Dinesh; Abraham, Daniel P.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 3, p. 1257-1267
  • DOI: 10.1021/jp3118055