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Interfacial Electron Transfer and Ion Solvation in the Solid Electrolyte Interphase

Kim, Jeongmin and Savoie, Brett M. and Miller, Thomas F., III (2021) Interfacial Electron Transfer and Ion Solvation in the Solid Electrolyte Interphase. Journal of Physical Chemistry C, 125 (8). pp. 4614-4622. ISSN 1932-7447.

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As a chemically and structurally well-defined model for redox processes in the solid electrolyte interphase of battery electrodes, we investigate electron transfer (ET) to lithium ions at the interface between a platinum metal anode and a solid polymer electrolyte. Studied electrolytes include LiTFSI (lithium bis(trifluoromethane)sulfonimide) salts in polyethylene oxide and poly(diethylene oxide-alt-oxymethylene), as well as in the associated liquid electrolytes 1,2-dimethoxyethane and tetraglyme. Atomic-resolution simulations are performed with constant-potential polarizable electrodes to characterize interfacial ET kinetics, including lithium-ion solvation structures and solvent reorganization effects as a function of applied electrode potential. The linear-response assumptions of the Marcus theory for ET are found to be robust in these systems, yet ion-solvation behavior at the anode interface is strikingly dependent on chain connectivity, solvation environment, and the magnitude of the applied electrode potential, resulting in very different ET kinetics for lithium electroreduction.

Item Type:Article
Related URLs:
URLURL TypeDescription Paper
Savoie, Brett M.0000-0002-7039-4039
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2021 American Chemical Society. Received: December 16, 2020; Revised: February 3, 2021; Publication Date: February 19, 2021. T.F.M. acknowledges support from the Center for Synthetic Control Across Length-Scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under award no. DE-SC0019381. Computational resources were provided by the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the DOE Office of Science under contract DE-AC02-05CH11231. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0019381
Department of Energy (DOE)DE-AC02-05CH11231
Subject Keywords:Solvation, Electrodes, Ions, Electrolytes, Lithium
Issue or Number:8
Record Number:CaltechAUTHORS:20210119-101412986
Persistent URL:
Official Citation:Interfacial Electron Transfer and Ion Solvation in the Solid Electrolyte Interphase. Jeongmin Kim, Brett M. Savoie, and Thomas F. Miller. The Journal of Physical Chemistry C 2021 125 (8), 4614-4622; DOI: 10.1021/acs.jpcc.0c11194
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107535
Deposited By: Tony Diaz
Deposited On:19 Jan 2021 18:20
Last Modified:04 Mar 2021 22:28

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