Interfacial Electron Transfer and Ion Solvation in the Solid Electrolyte Interphase

Abstract

As a chemically and structurally well-defined model for redox processes in the solid electrolyte interphase of battery electrodes, we investigate electron transfer 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 electron-transfer kinetics, including lithium-ion solvation structures and solvent reorganization effects as a function of applied electrode potential. The linearresponse assumptions of the Marcus theory for electron transfer 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 electron-transfer kinetics for lithium electroreduction.

Galvanic Corrosion and Electric Field in Lithium Anode Passivation Films: Effects on Self-Discharge

“…This thickness should still allow electron leakage through the film . Hence, we do not consider Marcus theory for long-range e – transfer ,− or nonadiabatic effects . Finally, there are fundamental disconnects between the battery and other electrochemical computational literature concerning voltage definitions and electric fields/electric double layers (EDLs) at the interfaces of both liquid and solid electrolytes. ,,,,− SI section S5 attempts to reconcile different viewpoints.…”

Review on Action Mechanism and Characterization of Natural/Artificial Solid Electrolyte Interphase of Lithium Battery: Latest Progress and Future Directions

“…At the same time, the highly conductive graphite in BM accelerates charge transfer and has excellent rate performance. This work provides a new strategy for the practical application of silicon materials. − …”

Constant-potential molecular dynamics simulation and its application in rechargeable batteries

“…Nevertheless, the electron transfer reaction of Li occurring between a Pt electrode and a polymer SEI has found that the solvation of ions is affected by the chain connectivity of the SEI polymer. 74…”

“…Nevertheless, the electron transfer reaction of Li occurring between a Pt electrode and a polymer SEI has found that the solvation of ions is affected by the chain connectivity of the SEI polymer. 74 In contrast, signicant efforts have been made to comprehend the side reactions occurring at battery interfaces. More specically, many electrolyte species such as solvents and anions spontaneously decompose on reactive electrodes such as Li or Na, which produces the passivating SEI lm.…”