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

Title: Fluoroethylene Carbonate Induces Ordered Electrolyte Interface on Silicon and Sapphire Surfaces as Revealed by Sum Frequency Generation Vibrational Spectroscopy and X-ray Reflectivity

Abstract

Here, the cyclability of silicon anodes in lithium ion batteries (LIBs) is affected by the reduction of the electrolyte on the anode surface to produce a coating layer termed the solid electrolyte interphase (SEI). One of the key steps for a major improvement of LIBs is unraveling the SEI’s structure-related diffusion properties as charge and discharge rates of LIBs are diffusion-limited. To this end, we have combined two surface sensitive techniques, sum frequency generation (SFG) vibrational spectroscopy, and X-ray reflectivity (XRR), to explore the first monolayer and to probe the first several layers of electrolyte, respectively, for solutions consisting of 1 M lithium perchlorate (LiClO 4) salt dissolved in ethylene carbonate (EC) or fluoroethylene carbonate (FEC) and their mixtures (EC/FEC 7:3 and 1:1 wt %) on silicon and sapphire surfaces. Our results suggest that the addition of FEC to EC solution causes the first monolayer to rearrange itself more perpendicular to the anode surface, while subsequent layers are less affected and tend to maintain their, on average, surface-parallel arrangements. This fundamental understanding of the near-surface orientation of the electrolyte molecules can aid operational strategies for designing high-performance LIBs.

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [3];  [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  4. Stanford Univ., Stanford, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1457398
Grant/Contract Number:  
AC02-05CH1123; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 18; Journal Issue: 3; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; electrolyte additives; Lithium ion batteries; sum frequency generation vibrational spectroscopy; X-ray reflectivity

Citation Formats

Horowitz, Yonatan, Steinruck, Hans -Georg, Han, Hui -Ling, Cao, Chuntian, Abate, Iwnetim Iwnetu, Tsao, Yuchi, Toney, Michael F., and Somorjai, Gabor A. Fluoroethylene Carbonate Induces Ordered Electrolyte Interface on Silicon and Sapphire Surfaces as Revealed by Sum Frequency Generation Vibrational Spectroscopy and X-ray Reflectivity. United States: N. p., 2018. Web. doi:10.1021/acs.nanolett.8b00298.
Horowitz, Yonatan, Steinruck, Hans -Georg, Han, Hui -Ling, Cao, Chuntian, Abate, Iwnetim Iwnetu, Tsao, Yuchi, Toney, Michael F., & Somorjai, Gabor A. Fluoroethylene Carbonate Induces Ordered Electrolyte Interface on Silicon and Sapphire Surfaces as Revealed by Sum Frequency Generation Vibrational Spectroscopy and X-ray Reflectivity. United States. doi:10.1021/acs.nanolett.8b00298.
Horowitz, Yonatan, Steinruck, Hans -Georg, Han, Hui -Ling, Cao, Chuntian, Abate, Iwnetim Iwnetu, Tsao, Yuchi, Toney, Michael F., and Somorjai, Gabor A. Fri . "Fluoroethylene Carbonate Induces Ordered Electrolyte Interface on Silicon and Sapphire Surfaces as Revealed by Sum Frequency Generation Vibrational Spectroscopy and X-ray Reflectivity". United States. doi:10.1021/acs.nanolett.8b00298. https://www.osti.gov/servlets/purl/1457398.
@article{osti_1457398,
title = {Fluoroethylene Carbonate Induces Ordered Electrolyte Interface on Silicon and Sapphire Surfaces as Revealed by Sum Frequency Generation Vibrational Spectroscopy and X-ray Reflectivity},
author = {Horowitz, Yonatan and Steinruck, Hans -Georg and Han, Hui -Ling and Cao, Chuntian and Abate, Iwnetim Iwnetu and Tsao, Yuchi and Toney, Michael F. and Somorjai, Gabor A.},
abstractNote = {Here, the cyclability of silicon anodes in lithium ion batteries (LIBs) is affected by the reduction of the electrolyte on the anode surface to produce a coating layer termed the solid electrolyte interphase (SEI). One of the key steps for a major improvement of LIBs is unraveling the SEI’s structure-related diffusion properties as charge and discharge rates of LIBs are diffusion-limited. To this end, we have combined two surface sensitive techniques, sum frequency generation (SFG) vibrational spectroscopy, and X-ray reflectivity (XRR), to explore the first monolayer and to probe the first several layers of electrolyte, respectively, for solutions consisting of 1 M lithium perchlorate (LiClO4) salt dissolved in ethylene carbonate (EC) or fluoroethylene carbonate (FEC) and their mixtures (EC/FEC 7:3 and 1:1 wt %) on silicon and sapphire surfaces. Our results suggest that the addition of FEC to EC solution causes the first monolayer to rearrange itself more perpendicular to the anode surface, while subsequent layers are less affected and tend to maintain their, on average, surface-parallel arrangements. This fundamental understanding of the near-surface orientation of the electrolyte molecules can aid operational strategies for designing high-performance LIBs.},
doi = {10.1021/acs.nanolett.8b00298},
journal = {Nano Letters},
number = 3,
volume = 18,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Fluor und Lithium: Ideale Partner für Elektrolyte in wiederaufladbaren Hochleistungsbatterien
journal, July 2019

  • Aspern, N.; Röschenthaler, G. ‐V.; Winter, M.
  • Angewandte Chemie, Vol. 131, Issue 45
  • DOI: 10.1002/ange.201901381

Fluor und Lithium: Ideale Partner für Elektrolyte in wiederaufladbaren Hochleistungsbatterien
journal, July 2019

  • Aspern, N.; Röschenthaler, G. ‐V.; Winter, M.
  • Angewandte Chemie, Vol. 131, Issue 45
  • DOI: 10.1002/ange.201901381