Probing Electric Double-Layer Composition via in Situ Vibrational Spectroscopy and Molecular Simulations.

Raberg, Jonathan H.; Vatamanu, Jenel; Harris, Stephen J.; van Oversteeg, Christina M.; Ramos, Axel; Borodin, Oleg; Cuk, Tanja

doi:10.1021/acs.jpclett.9b00879

Title: Probing Electric Double-Layer Composition via in Situ Vibrational Spectroscopy and Molecular Simulations.

Journal Article · Wed May 29 00:00:00 EDT 2019 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.9b00879· OSTI ID:1650061

Raberg, Jonathan H. ^[1];

^[2]; Harris, Stephen J. ^[3];

^[4]; Ramos, Axel ^[1];

^[2];

^[5]

Univ. of California, Berkeley, CA (United States)
Army Research Lab., Adelphi, MD (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of Utrecht (Netherlands)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

At an electrode, ions and solvent accumulate to screen charge, leading to a nanometer-scale electric double layer (EDL). The EDL guides electrode passivation in batteries, while in (super)capacitors, it determines charge storage capacity. Despite its importance, quantification of the nanometer-scale and potential-dependent EDL remains a challenging problem. Here, we directly probe changes in the EDL composition with potential using in situ vibrational spectroscopy and molecular dynamics simulations for a Li-ion battery electrolyte (LiClO₄ in dimethyl carbonate). The accumulation rate of Li⁺ ions at the negative surface and ClO₄^- ions at the positive surface from vibrational spectroscopy compares well to that predicted by simulations using a polarizable APPLE&P force field. The ion solvation shell structure and ion-pairing within the EDL differs significantly from the bulk, especially at the negative electrode, suggesting that the common rationalization of interfacial electrochemical processes in terms of bulk ion solvation should be applied with caution.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1650061

Journal Information:: Journal of Physical Chemistry Letters, Vol. 10, Issue 12; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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