PNNL

Abstract

Solid-electrolyte interphase (SEI) is a key component that dictates the performance of most electrochemical devices, but the understanding of its chemistry and structure has been limited by the lack of in-situ tools. In this work, we report SEI live-formation in Li-ion battery under operando condition with liquid secondary ion mass spectrometry (SIMS), which, in combination with molecular dynamics (MD) simulation, presents the first dynamic picture with molecular-accuracy about this key component. Before any interphasial chemistry occurs during the initial charging, an electric double layer forms at the electrode-electrolyte interface via the self-assembly of solvent molecules directed by both Li+ and potential of the electrified surface. Such double layer structure predicts the eventual interphasial chemistries formed from the electrolytes, where the negatively-charged electrode surface repels salt anions from the inner-Helmholtz layer and results in an inner SEI that is thin, dense and inorganic in nature but LiF-depleted. It was this dense layer that exercises the major functions of an interphase, i.e., conducting Li+ but insulating electrons. An outer layer that is electrolyte-permeable and organic-rich appears after formation of the inner SEI. In highly-concentrated electrolyte, the presence of LiF in the inner-SEI is raised due to the high population of salt anions in the double layer. These real-time observations at nano-scale reveal in general sense how an interphase inherits chemistry from inner-Helmholtz layer structure, and establish guidelines in engineering desirable interphases for the future battery chemistries.