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

Title: In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

Abstract

Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the for-mation of solid electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and oth-er electrolyte components are still unclear. We report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach in-volving AIMD modeling and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li2S, LiF, Li2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and elec-trolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS5) fouling process. These new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for themore » development of Li–S batteries.« less

Authors:
; ; ; ; ; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1371990
Report Number(s):
PNNL-SA-123618
Journal ID: ISSN 0897-4756; 49376; 48846; KC0208010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 11; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; Environmental Molecular Sciences Laboratory

Citation Formats

Nandasiri, Manjula I., Camacho-Forero, Luis E., Schwarz, Ashleigh M., Shutthanandan, Vaithiyalingam, Thevuthasan, Suntharampillai, Balbuena, Perla B., Mueller, Karl T., and Murugesan, Vijayakumar. In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b00374.
Nandasiri, Manjula I., Camacho-Forero, Luis E., Schwarz, Ashleigh M., Shutthanandan, Vaithiyalingam, Thevuthasan, Suntharampillai, Balbuena, Perla B., Mueller, Karl T., & Murugesan, Vijayakumar. In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries. United States. doi:10.1021/acs.chemmater.7b00374.
Nandasiri, Manjula I., Camacho-Forero, Luis E., Schwarz, Ashleigh M., Shutthanandan, Vaithiyalingam, Thevuthasan, Suntharampillai, Balbuena, Perla B., Mueller, Karl T., and Murugesan, Vijayakumar. Tue . "In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries". United States. doi:10.1021/acs.chemmater.7b00374.
@article{osti_1371990,
title = {In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries},
author = {Nandasiri, Manjula I. and Camacho-Forero, Luis E. and Schwarz, Ashleigh M. and Shutthanandan, Vaithiyalingam and Thevuthasan, Suntharampillai and Balbuena, Perla B. and Mueller, Karl T. and Murugesan, Vijayakumar},
abstractNote = {Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the for-mation of solid electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and oth-er electrolyte components are still unclear. We report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach in-volving AIMD modeling and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li2S, LiF, Li2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and elec-trolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS5) fouling process. These new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for the development of Li–S batteries.},
doi = {10.1021/acs.chemmater.7b00374},
journal = {Chemistry of Materials},
issn = {0897-4756},
number = 11,
volume = 29,
place = {United States},
year = {2017},
month = {5}
}

Works referencing / citing this record:

Mesoscale Physicochemical Interactions in Lithium–Sulfur Batteries: Progress and Perspective
journal, October 2017

  • Liu, Zhixiao; Mistry, Aashutosh; Mukherjee, Partha P.
  • Journal of Electrochemical Energy Conversion and Storage, Vol. 15, Issue 1
  • DOI: 10.1115/1.4037785