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Title: Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy

Abstract

Understanding the aprotic solution structures at the immediate vicinity of solid/liquid interface (SLI) is critically important for next generation lithium ion battery development. Yet, it is still challenging to investigate the carbonate chemical profiles close to the diffuse layer (about 10 nm) of the electrical double layer at SLI due to the lack of a ultrahigh surface sensitive tool. In this work, we demonstrate the structures of commonly used carbonate solvents (ethylene carbonate (EC) and diethyl carbonate (DEC)) and a carbonate additive (fluoroethylene carbonate (FEC)) in a commercial Li-ion battery electrolyte can be determined at ∼17 nm above the electrode surface. This is only enabled by a nanogap surface-enhanced Raman spectroscopy (SERS) technique based on a monolayer gold nanoparticle (Au NP) ensemble. The SERS enhancement factor (EF) of those carbonates was found to depend on the molecular polarizability, with the maximum EF at ∼10 5 found for EC and FEC. Despite their alike chemical structures, this monolayer Au NP SERS substrate is fully capable of discrimiating the different Raman finger prints of EC and FEC. Compared to EC, several vibration modes in FEC, such as C-C skeletal deformation, ring breathing band and C=O stretching band, shift to higher frequencies becausemore » of the displacement of a hydrogen atom by a much heavier fluorine atom in a methylene bridge. This counterintuitive observation against the commonly used “ball and spring” model in vibrational spectroscopy is mostly due to the increased bond strength in the FEC ring versus that of EC. A second order empirical polynomial best describes the correlation between the SERS band integration of EC or DEC molar concentration. Furthermore, our findings open up new opportunities for in-depth understanding of the electrolyte molecular vibrational behaviors at direct solid/liquid interface and developing advanced electrolytes for next generation lithium-ion batteries.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Florida A&M State Univ. College of Engineering, Tallahassee, FL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1491062
Alternate Identifier(s):
OSTI ID: 1526393
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 166; Journal Issue: 2; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Batteries - Lithium; electrode/electrolyte interface; electrolyte structure; surface-enhanced Raman spectroscopy

Citation Formats

Yang, Guang, Sacci, Robert L., Ivanov, Ilia N., Ruther, Rose, Hays, Kevin A., Zhang, Yiman, Cao, Pengfei, Veith, Gabriel M., Dudney, Nancy J., Saito, Tomonori, Hallinan, Daniel T., and Nanda, Jagjit. Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy. United States: N. p., 2019. Web. doi:10.1149/2.0391902jes.
Yang, Guang, Sacci, Robert L., Ivanov, Ilia N., Ruther, Rose, Hays, Kevin A., Zhang, Yiman, Cao, Pengfei, Veith, Gabriel M., Dudney, Nancy J., Saito, Tomonori, Hallinan, Daniel T., & Nanda, Jagjit. Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy. United States. doi:10.1149/2.0391902jes.
Yang, Guang, Sacci, Robert L., Ivanov, Ilia N., Ruther, Rose, Hays, Kevin A., Zhang, Yiman, Cao, Pengfei, Veith, Gabriel M., Dudney, Nancy J., Saito, Tomonori, Hallinan, Daniel T., and Nanda, Jagjit. Wed . "Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy". United States. doi:10.1149/2.0391902jes.
@article{osti_1491062,
title = {Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy},
author = {Yang, Guang and Sacci, Robert L. and Ivanov, Ilia N. and Ruther, Rose and Hays, Kevin A. and Zhang, Yiman and Cao, Pengfei and Veith, Gabriel M. and Dudney, Nancy J. and Saito, Tomonori and Hallinan, Daniel T. and Nanda, Jagjit},
abstractNote = {Understanding the aprotic solution structures at the immediate vicinity of solid/liquid interface (SLI) is critically important for next generation lithium ion battery development. Yet, it is still challenging to investigate the carbonate chemical profiles close to the diffuse layer (about 10 nm) of the electrical double layer at SLI due to the lack of a ultrahigh surface sensitive tool. In this work, we demonstrate the structures of commonly used carbonate solvents (ethylene carbonate (EC) and diethyl carbonate (DEC)) and a carbonate additive (fluoroethylene carbonate (FEC)) in a commercial Li-ion battery electrolyte can be determined at ∼17 nm above the electrode surface. This is only enabled by a nanogap surface-enhanced Raman spectroscopy (SERS) technique based on a monolayer gold nanoparticle (Au NP) ensemble. The SERS enhancement factor (EF) of those carbonates was found to depend on the molecular polarizability, with the maximum EF at ∼105 found for EC and FEC. Despite their alike chemical structures, this monolayer Au NP SERS substrate is fully capable of discrimiating the different Raman finger prints of EC and FEC. Compared to EC, several vibration modes in FEC, such as C-C skeletal deformation, ring breathing band and C=O stretching band, shift to higher frequencies because of the displacement of a hydrogen atom by a much heavier fluorine atom in a methylene bridge. This counterintuitive observation against the commonly used “ball and spring” model in vibrational spectroscopy is mostly due to the increased bond strength in the FEC ring versus that of EC. A second order empirical polynomial best describes the correlation between the SERS band integration of EC or DEC molar concentration. Furthermore, our findings open up new opportunities for in-depth understanding of the electrolyte molecular vibrational behaviors at direct solid/liquid interface and developing advanced electrolytes for next generation lithium-ion batteries.},
doi = {10.1149/2.0391902jes},
journal = {Journal of the Electrochemical Society},
number = 2,
volume = 166,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1149/2.0391902jes

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Cited by: 1 work
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Figures / Tables:

Figure 1 Figure 1: (a) (in red dash box, from top to bottom) TEM micrograph of the Au NP monolayer on copper grid, its fast Fourier Transform and a magnified TEM micrograph showing the nanogaps (marked by two parallel yellow dash lines) and SEM micrograph of Au NP monolayer on Ni-coated quartzmore » substrate. (b) FDTD simulated enhancement factor (EF) distribution of the Au NP monolater on the Ni-coated quartz substrate. The maximum EF (∼8.2 × 108), in the nanogap region about 17 nm above the Ni surface, is denoted.« less

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