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Title: Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by sum frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [4] ;  [4] ;  [5]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); National Inst. of Metrology, Quality and Technology, Rio de Janiero (Brazil)
  4. Honda Research Inst., Inc., Columbus, OH (United States)
  5. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Honda Research Inst., Inc., Columbus, OH (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 7; Journal Issue: 17; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Research Org:
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Honda Research Inst. (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; fluorinated electrolytes; lithium-ion batteries; solid-electrolyte interface; sum frequency vibrational spectroscopy
OSTI Identifier:
1379649
Alternate Identifier(s):
OSTI ID: 1378806

Horowitz, Yonatan, Han, Hui-Ling, Ralston, Walter T., de Araujo, Joyce Rodrigues, Kreidler, Eric, Brooks, Chris, and Somorjai, Gabor A.. Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy. United States: N. p., Web. doi:10.1002/aenm.201602060.
Horowitz, Yonatan, Han, Hui-Ling, Ralston, Walter T., de Araujo, Joyce Rodrigues, Kreidler, Eric, Brooks, Chris, & Somorjai, Gabor A.. Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy. United States. doi:10.1002/aenm.201602060.
Horowitz, Yonatan, Han, Hui-Ling, Ralston, Walter T., de Araujo, Joyce Rodrigues, Kreidler, Eric, Brooks, Chris, and Somorjai, Gabor A.. 2017. "Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy". United States. doi:10.1002/aenm.201602060. https://www.osti.gov/servlets/purl/1379649.
@article{osti_1379649,
title = {Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy},
author = {Horowitz, Yonatan and Han, Hui-Ling and Ralston, Walter T. and de Araujo, Joyce Rodrigues and Kreidler, Eric and Brooks, Chris and Somorjai, Gabor A.},
abstractNote = {Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by sum frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.},
doi = {10.1002/aenm.201602060},
journal = {Advanced Energy Materials},
number = 17,
volume = 7,
place = {United States},
year = {2017},
month = {5}
}

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