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Title: Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering

Abstract

The key to understanding the cycling mechanism of lithium-ion battery electrodes is to develop methods to monitor the dynamic cell chemistry, but the complexity of the problem has continued to pose an obstacle. Here we describe the use of operando small-angle neutron scattering (SANS) to show directly how the use of concentrated LiTFSI electrolyte in Li/ordered mesoporous carbon (OMC) half-cells influences the mechanism of solid electrolyte interphase (SEI) formation, lithium intercalation, and carbon framework expansion. We find that a complex interplay between the viscosity, lithium solvation shell and electrode microstructure in the concentrated 4 M electrolyte changes the dynamics of SEI formation and pore filling at a given applied potential. Both the filling of micropores and co-intercalation are found to drive the expansion of the carbon framework. Lithium-rich reduction products form at much higher potentials in the micropores of the 4 M electrolyte system, while on mesopore surfaces the lithium-rich salts form quickly before giving way to carbonaceous products. As a result, this study reveals operando SANS as a unique method for providing microstructure dependent information on the dynamics of electrochemical processes.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1543225
Alternate Identifier(s):
OSTI ID: 1493369
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 12; Journal Issue: 6; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jafta, Charl J., Sun, Xiao -Guang, Veith, Gabriel M., Jensen, Grethe V., Mahurin, Shannon Mark, Paranthaman, Mariappan P., Dai, Sheng, and Bridges, Craig A. Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering. United States: N. p., 2019. Web. doi:10.1039/C8EE02703J.
Jafta, Charl J., Sun, Xiao -Guang, Veith, Gabriel M., Jensen, Grethe V., Mahurin, Shannon Mark, Paranthaman, Mariappan P., Dai, Sheng, & Bridges, Craig A. Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering. United States. doi:10.1039/C8EE02703J.
Jafta, Charl J., Sun, Xiao -Guang, Veith, Gabriel M., Jensen, Grethe V., Mahurin, Shannon Mark, Paranthaman, Mariappan P., Dai, Sheng, and Bridges, Craig A. Fri . "Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering". United States. doi:10.1039/C8EE02703J. https://www.osti.gov/servlets/purl/1543225.
@article{osti_1543225,
title = {Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering},
author = {Jafta, Charl J. and Sun, Xiao -Guang and Veith, Gabriel M. and Jensen, Grethe V. and Mahurin, Shannon Mark and Paranthaman, Mariappan P. and Dai, Sheng and Bridges, Craig A.},
abstractNote = {The key to understanding the cycling mechanism of lithium-ion battery electrodes is to develop methods to monitor the dynamic cell chemistry, but the complexity of the problem has continued to pose an obstacle. Here we describe the use of operando small-angle neutron scattering (SANS) to show directly how the use of concentrated LiTFSI electrolyte in Li/ordered mesoporous carbon (OMC) half-cells influences the mechanism of solid electrolyte interphase (SEI) formation, lithium intercalation, and carbon framework expansion. We find that a complex interplay between the viscosity, lithium solvation shell and electrode microstructure in the concentrated 4 M electrolyte changes the dynamics of SEI formation and pore filling at a given applied potential. Both the filling of micropores and co-intercalation are found to drive the expansion of the carbon framework. Lithium-rich reduction products form at much higher potentials in the micropores of the 4 M electrolyte system, while on mesopore surfaces the lithium-rich salts form quickly before giving way to carbonaceous products. As a result, this study reveals operando SANS as a unique method for providing microstructure dependent information on the dynamics of electrochemical processes.},
doi = {10.1039/C8EE02703J},
journal = {Energy & Environmental Science},
number = 6,
volume = 12,
place = {United States},
year = {2019},
month = {1}
}

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