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

Yang, Guang; Ivanov, Ilia N.; Ruther, Rose E.; Sacci, Robert L.; Subjakova, Veronika; Hallinan, Daniel T.; Nanda, Jagjit

doi:10.1021/acsnano.8b05038

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

Journal Article · 18 September 2018 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.8b05038 · OSTI ID:1471928

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^[1]; Subjakova, Veronika ^[2]; Hallinan, Daniel T. ^[3];

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Comenius Univ., Bratislava (Slovakia). Dept. of Nuclear Physics and Biophysics
Florida A&M Univ.-Florida State Univ. College of Engineering (FAMU-FSU), Tallahassee, FL (United States)

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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1471928

Journal Information:: ACS Nano, Vol. 12, Issue 10; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 57 works

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