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Title: The influence of FEC on the solvation structure and reduction reaction of LiPF6/EC electrolytes and its implication for solid electrolyte interphase formation

Journal Article · · Nano Energy
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© 2019 The Authors Fluoroethylene carbonate (FEC) has been proposed as an effective electrolyte additive that enhances the stability and elasticity of the solid electrolyte interphase (SEI) of emerging Si and Li metal anodes. However, uncertainties still remain on the exact mechanism through which FEC alters the electrolyte decomposition and SEI formation process. Herein, the influence of FEC on LiPF6/ethylene carbonate (EC) electrolytes for Si anodes is investigated through classical molecular dynamics, Fourier-transform infrared spectroscopy, and quantum chemical calculations. Albeit a minority species, FEC is found to significantly modify the solvation structure and reduction behavior of the electrolyte while being innocuous to transport properties. Even with limited 10% of FEC, the Li+ solvation structure exhibits a notably higher contact-ion pair ratio (14%) than the parent EC electrolyte (6%). Moreover, FEC itself, as a new fluorine-containing species, appears in 1/5 of the Li+ solvation shells. The Li+-coordinated FEC is found to reduce prior to EC and uncoordinated FEC which will passivate the anode surface at an early onset (ca. 0.3 V higher than EC) by forming LiF. The critical role of FEC in tailoring the Li+ solvation structure and as-formed protective SEI composition provides mechanistic insight that will aid in the rational design of novel electrolytes.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; AC05-00OR22725
OSTI ID:
1562977
Alternate ID(s):
OSTI ID: 1558552; OSTI ID: 1656538
Journal Information:
Nano Energy, Journal Name: Nano Energy Vol. 64 Journal Issue: C; ISSN 2211-2855
Publisher:
ElsevierCopyright Statement
Country of Publication:
Netherlands
Language:
English
Citation Metrics:
Cited by: 208 works
Citation information provided by
Web of Science

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
Silicon anodes
Lithium metal anodes
Fluoroethylene carbonates
Solvation structure
Reduction potential
Solid electrolyte interphases