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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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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:

Electrode–Electrolyte Interface in Li-Ion Batteries: Current Understanding and New Insights
journal, October 2015

  • Gauthier, Magali; Carney, Thomas J.; Grimaud, Alexis
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 22
  • DOI: 10.1021/acs.jpclett.5b01727

Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy
journal, October 2017

Nanoscale Imaging of Fundamental Li Battery Chemistry: Solid-Electrolyte Interphase Formation and Preferential Growth of Lithium Metal Nanoclusters
journal, February 2015

  • Sacci, Robert L.; Black, Jennifer M.; Balke, Nina
  • Nano Letters, Vol. 15, Issue 3
  • DOI: 10.1021/nl5048626

Far-Field Optical Nanoscopy
journal, May 2007

Confocal Raman Microscopy: Why the Depth Resolution and Spatial Accuracy Can Be Much Worse Than You Think
journal, October 2000

Surface-enhanced Raman scattering
journal, January 1998

  • Campion, Alan; Kambhampati, Patanjali
  • Chemical Society Reviews, Vol. 27, Issue 4
  • DOI: 10.1039/a827241z

Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering
journal, February 1997

Surface-Enhanced Raman Scattering:  From Noble to Transition Metals and from Rough Surfaces to Ordered Nanostructures
journal, September 2002

  • Tian, Zhong-Qun; Ren, Bin; Wu, De-Yin
  • The Journal of Physical Chemistry B, Vol. 106, Issue 37
  • DOI: 10.1021/jp0257449

Surface enhanced Raman scattering from bare cobalt electrode surfaces
journal, January 2001

  • Y. Wu, D.; Xie, Y.; Ren, B.
  • PhysChemComm, Vol. 4, Issue 18
  • DOI: 10.1039/b105667k

Simple Strategy To Improve Surface-Enhanced Raman Scattering Based on Electrochemically Prepared Roughened Silver Substrates
journal, June 2010

  • Yang, Kuang-Hsuan; Liu, Yu-Chuan; Yu, Chung-Chin
  • Langmuir, Vol. 26, Issue 13
  • DOI: 10.1021/la100235x

Electrochemical Tip-Enhanced Raman Spectroscopy
journal, September 2015

  • Zeng, Zhi-Cong; Huang, Sheng-Chao; Wu, De-Yin
  • Journal of the American Chemical Society, Vol. 137, Issue 37
  • DOI: 10.1021/jacs.5b08143

Shell-isolated nanoparticle-enhanced Raman spectroscopy
journal, March 2010

  • Li, Jian Feng; Huang, Yi Fan; Ding, Yong
  • Nature, Vol. 464, Issue 7287, p. 392-395
  • DOI: 10.1038/nature08907

Nanostructured Surfaces and Assemblies as SERS Media
journal, October 2008

  • Ko, Hyunhyub; Singamaneni, Srikanth; Tsukruk, Vladimir V.
  • Small, Vol. 4, Issue 10
  • DOI: 10.1002/smll.200800337

Self-assembly of large-scale crack-free gold nanoparticle films using a ‘drain-to-deposit’ strategy
journal, April 2016

Gold Nanoparticle Monolayers from Sequential Interfacial Ligand Exchange and Migration in a Three-Phase System
journal, October 2016

  • Yang, Guang; Hallinan, Daniel T.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep35339

Self-Assembly of Large Gold Nanoparticles for Surface-Enhanced Raman Spectroscopy
journal, April 2017

  • Yang, Guang; Nanda, Jagjit; Wang, Boya
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 15
  • DOI: 10.1021/acsami.7b01121

Surface Enhanced Raman Spectroscopy of Individual Rhodamine 6G Molecules on Large Ag Nanocrystals
journal, November 1999

  • Michaels, Amy M.; Nirmal, M.; Brus, L. E.
  • Journal of the American Chemical Society, Vol. 121, Issue 43
  • DOI: 10.1021/ja992128q

Effects of Solute–Solvent Hydrogen Bonding on Nonaqueous Electrolyte Structure
journal, July 2015

  • Schroder, Kjell W.; Dylla, Anthony G.; Bishop, Logan D. C.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 15
  • DOI: 10.1021/acs.jpclett.5b01216

A Raman spectroscopic study of organic electrolyte solutions based on binary solvent systems of ethylene carbonate with low viscosity solvents which dissolve different lithium salts
journal, January 1998

  • Morita, Masayuki; Asai, Yoshiko; Yoshimoto, Nobuko
  • Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 23
  • DOI: 10.1039/a806278a

Solvate Structures and Computational/Spectroscopic Characterization of LiPF 6 Electrolytes
journal, April 2015

  • Han, Sang-Don; Yun, Sung-Hyun; Borodin, Oleg
  • The Journal of Physical Chemistry C, Vol. 119, Issue 16
  • DOI: 10.1021/acs.jpcc.5b00826

Gold Nanoparticle Monolayers with Tunable Optical and Electrical Properties
journal, April 2016

Solvation Structure around the Li + Ion in Mixed Cyclic/Linear Carbonate Solutions Unveiled by the Raman Noncoincidence Effect
journal, July 2015

  • Giorgini, Maria Grazia; Futamatagawa, Kazuma; Torii, Hajime
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 16
  • DOI: 10.1021/acs.jpclett.5b01524

Li+ solvation in ethylene carbonate–propylene carbonate concentrated solutions: A comprehensive model
journal, October 1997

  • Cazzanelli, E.; Croce, Fausto; Appetecchi, Giovanni Battista
  • The Journal of Chemical Physics, Vol. 107, Issue 15
  • DOI: 10.1063/1.474334

Activated vibrational modes and Fermi resonance in tip-enhanced Raman spectroscopy
journal, February 2013

Infrared and Raman spectra and vibrational assignment of ethylene carbonate
journal, September 1971

  • Fortunato, Bruno; Mirone, Paolo; Fini, Glancaelo
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 27, Issue 9
  • DOI: 10.1016/0584-8539(71)80245-3

The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes
journal, August 2015

Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials
journal, April 2016

Raman Spectra and Transport Properties of Lithium Perchlorate in Ethylene Carbonate Based Binary Solvent Systems for Lithium Batteries
journal, June 1998

  • Klassen, B.; Aroca, R.; Nazri, M.
  • The Journal of Physical Chemistry B, Vol. 102, Issue 24
  • DOI: 10.1021/jp973099d

Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014

Role of Mixed Solvation and Ion Pairing in the Solution Structure of Lithium Ion Battery Electrolytes
journal, June 2015

  • Seo, Daniel M.; Reininger, Stefanie; Kutcher, Mary
  • The Journal of Physical Chemistry C, Vol. 119, Issue 25
  • DOI: 10.1021/acs.jpcc.5b03694

Vibrational spectra and structure of small ring compounds11For Part XVI see J.R. Durig and J.N. Willis, Jr., J. Mol. Spectry., in press.
journal, February 1970

Role of Solution Structure in Solid Electrolyte Interphase Formation on Graphite with LiPF 6 in Propylene Carbonate
journal, November 2013

  • Nie, Mengyun; Abraham, Daniel P.; Seo, Daniel M.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 48
  • DOI: 10.1021/jp409765w

Spectroscopic and Density Functional Theory Characterization of Common Lithium Salt Solvates in Carbonate Electrolytes for Lithium Batteries
journal, January 2017

  • Chapman, Navid; Borodin, Oleg; Yoon, Taeho
  • The Journal of Physical Chemistry C, Vol. 121, Issue 4
  • DOI: 10.1021/acs.jpcc.6b12234

Competitive lithium solvation of linear and cyclic carbonates from quantum chemistry
journal, January 2016

  • Borodin, Oleg; Olguin, Marco; Ganesh, P.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 1
  • DOI: 10.1039/C5CP05121E

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery
journal, March 2017

  • Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14658

Preferential Solvation of Li+ Directs Formation of Interphase on Graphitic Anode
journal, January 2011

  • von Cresce, Arthur; Xu, Kang
  • Electrochemical and Solid-State Letters, Vol. 14, Issue 10
  • DOI: 10.1149/1.3615828

Understanding Li + –Solvent Interaction in Nonaqueous Carbonate Electrolytes with 17 O NMR
journal, May 2013

  • Bogle, Xavier; Vazquez, Rafael; Greenbaum, Steven
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 10
  • DOI: 10.1021/jz400661k

Lithium Hexamethyldisilazide:  A View of Lithium Ion Solvation through a Glass-Bottom Boat
journal, November 1999

  • Lucht, Brett L.; Collum, David B.
  • Accounts of Chemical Research, Vol. 32, Issue 12
  • DOI: 10.1021/ar960300e

Accurate Static and Dynamic Properties of Liquid Electrolytes for Li-Ion Batteries from ab initio Molecular Dynamics
journal, March 2011

  • Ganesh, P.; Jiang, De-en; Kent, P. R. C.
  • The Journal of Physical Chemistry B, Vol. 115, Issue 12
  • DOI: 10.1021/jp2003529

Evaluating the Free Energies of Solvation and Electronic Structures of Lithium-Ion Battery Electrolytes
journal, June 2016

  • Shakourian-Fard, Mehdi; Kamath, Ganesh; Sankaranarayanan, Subramanian K. R. S.
  • ChemPhysChem, Vol. 17, Issue 18
  • DOI: 10.1002/cphc.201600338

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

Surface-Enhanced Raman Trajectories on a Nano-Dumbbell: Transition from Field to Charge Transfer Plasmons as the Spheres Fuse
journal, October 2012

  • Banik, Mayukh; El-Khoury, Patrick Z.; Nag, Amit
  • ACS Nano, Vol. 6, Issue 11
  • DOI: 10.1021/nn304277n

Liquid Structure with Nano-Heterogeneity Promotes Cationic Transport in Concentrated Electrolytes
journal, October 2017

Molecular Dynamics Simulation Studies of the Structure of a Mixed Carbonate/LiPF 6 Electrolyte near Graphite Surface as a Function of Electrode Potential
journal, December 2011

  • Vatamanu, Jenel; Borodin, Oleg; Smith, Grant D.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 1
  • DOI: 10.1021/jp2101539
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    Works referencing / citing this record:

    Probing Electrolyte Solvents at Solid/Liquid Interface Using Gap-Mode Surface-Enhanced Raman Spectroscopy
    journal, January 2019

    • Yang, Guang; Sacci, Robert L.; Ivanov, Ilia N.
    • Journal of The Electrochemical Society, Vol. 166, Issue 2
    • DOI: 10.1149/2.0391902jes

    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

    • Gao, Fei‐Yue; Hu, Shao‐Jin; Zhang, Xiao‐Long
    • 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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