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Title: Electrolyte Solvation Structure at Solid/Liquid Interface Probed by Nanogap Surface-Enhanced Raman Spectroscopy

Abstract

Understanding the fundamental factors that drive ion solvation structure and transport is key to design high performance, stable battery electrolytes. Reversible ion solvation and desolvation are critical to the interfacial charge transfer process across the solid-liquid interface as well as the resulting stability of the solid electrolyte interphase (SEI). Here in this paper, we report the first study of Li+ salt solvation structure in aprotic solution in the immediate vicinity (~ 20 nm) of the solid electrode-liquid interface using surface-enhanced Raman spectroscopy (SERS) from a gold nanoparticle (Au NP) monolayer. The plasmonic coupling between Au NPs produces strong electromagnetic field enhancement in the gap region, leading to 5 orders of magnitude increase in Raman intensity for electrolyte components and their mixtures namely, lithium hexafluorophosphate (LiPF6), fluoroethylene carbonate (FEC), ethylene carbonate (EC) and diethyl carbonate (DEC). Further, we estimate and compare the lithium-ion solvation number derived from SERS and Infra-Red (FTIR) spectroscopy experiments to monitor and ascertain the changes in the solvation shell diameter in the confined nanogap region where there is maximum enhancement of the electric field. Our findings provide a new multi-modal spectroscopic approach to gain fundamental insights into the molecular structure of the electrolyte at the solid-liquid interface.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Comenius Univ., Bratislava (Slovakia). Dept. of Nuclear Physics and Biophysics
  3. Florida A&M Univ.-Florida State Univ. College of Engineering (FAMU-FSU), 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:
1471928
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 10; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; interface; ion solvation; gold nanoparticle; SERS; FDTD; solvation number; Liion battery

Citation Formats

Yang, Guang, Ivanov, Ilia N., Ruther, Rose E., Sacci, Robert L., Subjakova, Veronika, Hallinan, Daniel T., and Nanda, Jagjit. Electrolyte Solvation Structure at Solid/Liquid Interface Probed by Nanogap Surface-Enhanced Raman Spectroscopy. United States: N. p., 2018. Web. doi:10.1021/acsnano.8b05038.
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Yang, Guang, Ivanov, Ilia N., Ruther, Rose E., Sacci, Robert L., Subjakova, Veronika, Hallinan, Daniel T., & Nanda, Jagjit. Electrolyte Solvation Structure at Solid/Liquid Interface Probed by Nanogap Surface-Enhanced Raman Spectroscopy. United States. https://doi.org/10.1021/acsnano.8b05038
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Yang, Guang, Ivanov, Ilia N., Ruther, Rose E., Sacci, Robert L., Subjakova, Veronika, Hallinan, Daniel T., and Nanda, Jagjit. Tue . "Electrolyte Solvation Structure at Solid/Liquid Interface Probed by Nanogap Surface-Enhanced Raman Spectroscopy". United States. https://doi.org/10.1021/acsnano.8b05038. https://www.osti.gov/servlets/purl/1471928.
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@article{osti_1471928,
title = {Electrolyte Solvation Structure at Solid/Liquid Interface Probed by Nanogap Surface-Enhanced Raman Spectroscopy},
author = {Yang, Guang and Ivanov, Ilia N. and Ruther, Rose E. and Sacci, Robert L. and Subjakova, Veronika and Hallinan, Daniel T. and Nanda, Jagjit},
abstractNote = {Understanding the fundamental factors that drive ion solvation structure and transport is key to design high performance, stable battery electrolytes. Reversible ion solvation and desolvation are critical to the interfacial charge transfer process across the solid-liquid interface as well as the resulting stability of the solid electrolyte interphase (SEI). Here in this paper, we report the first study of Li+ salt solvation structure in aprotic solution in the immediate vicinity (~ 20 nm) of the solid electrode-liquid interface using surface-enhanced Raman spectroscopy (SERS) from a gold nanoparticle (Au NP) monolayer. The plasmonic coupling between Au NPs produces strong electromagnetic field enhancement in the gap region, leading to 5 orders of magnitude increase in Raman intensity for electrolyte components and their mixtures namely, lithium hexafluorophosphate (LiPF6), fluoroethylene carbonate (FEC), ethylene carbonate (EC) and diethyl carbonate (DEC). Further, we estimate and compare the lithium-ion solvation number derived from SERS and Infra-Red (FTIR) spectroscopy experiments to monitor and ascertain the changes in the solvation shell diameter in the confined nanogap region where there is maximum enhancement of the electric field. Our findings provide a new multi-modal spectroscopic approach to gain fundamental insights into the molecular structure of the electrolyte at the solid-liquid interface.},
doi = {10.1021/acsnano.8b05038},
journal = {ACS Nano},
number = 10,
volume = 12,
place = {United States},
year = {2018},
month = {9}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acsnano.8b05038
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Figure 1 Figure 1: (a) Photograph of the semi-transparent pouch cell (top view). (b) Schematic illustration of the semi-transparent pouch cell (side view).
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Works referenced in this record:

Nanoscale Imaging of Fundamental Li Battery Chemistry: Solid-Electrolyte Interphase Formation and Preferential Growth of Lithium Metal Nanoclusters
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Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014

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    Works referencing / citing this record:

    Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy
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    Understanding the Role of Fluorination on the Interaction of Electrolytic Carbonates with Li + through an Electronic Structure Approach
    journal, January 2019

    • Kushwaha, Anoop Kumar; Sahoo, Mihir Ranjan; Nayak, Saroj Kumar
    • ChemistrySelect, Vol. 4, Issue 4
    • DOI: 10.1002/slct.201803372

    High‐Curvature Transition‐Metal Chalcogenide Nanostructures with a Pronounced Proximity Effect Enable Fast and Selective CO 2 Electroreduction
    journal, February 2020

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    • Angewandte Chemie, Vol. 132, Issue 22
    • DOI: 10.1002/ange.201912348

    High‐Curvature Transition‐Metal Chalcogenide Nanostructures with a Pronounced Proximity Effect Enable Fast and Selective CO 2 Electroreduction
    journal, February 2020

    • Gao, Fei‐Yue; Hu, Shao‐Jin; Zhang, Xiao‐Long
    • Angewandte Chemie International Edition, Vol. 59, Issue 22
    • DOI: 10.1002/anie.201912348
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