Investigating the Chemical Reactivity of Lithium Silicate Model SEI Layers

Coyle, Jaclyn E.; Brumbach, Michael T.; Veith, Gabriel M.; Apblett, Christopher A.

doi:10.1021/acs.jpcc.0c01057

Investigating the Chemical Reactivity of Lithium Silicate Model SEI Layers

Journal Article · Thu Mar 19 00:00:00 EDT 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c01057· OSTI ID:1616815

^[1]; Brumbach, Michael T. ^[2]; ^[3]; Apblett, Christopher A. ^[2]

Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Silicon anodes suffer from an unstable solid electrolyte interphase (SEI) layer that contributes to undesirable capacity fade with cycling. A key part to addressing this unstable SEI formation is to examine how certain components of the SEI react with the electrolyte over time. One SEI component that has not been thoroughly studied in the context of the chemical reactivity against the electrolyte is lithiated silicate. Four model silicate thin films with increasing lithium content were deposited by radio frequency (RF) magnetron sputtering to study how the lithiation of the native oxide on a silicon anode affects the chemical stability of the anode surface. SiO₂, Li₂Si₂O₅, Li₂SiO₃, and Li₃SiO_x films were exposed to 1.2 M LiPF₆ in the 3:7 wt % ethylene carbonate/ethyl methyl carbonate (EC/EMC) electrolyte for periods of time that are representative of the amount of time it takes to undergo cell formations. Soaked samples were rinsed, dried, and characterized by a combination of attenuated total reflectance-infrared spectroscopy (ATR-IR), focused ion beam-secondary electron microscopy (FIB-SEM), and X-ray photoelectron spectroscopy (XPS) depth profiling. It was found that the rate of the decrease in film thickness of the silicates exposed to the electrolyte over time increases as a function of the lithium content in the thin film. This reaction involves HF etching and LiPF₆ salt degradation leading to silicate loss and fluorination throughout the bulk. Finally, understanding this chemical instability is critical to determining the overall mechanism of SEI degradation over time.

View Accepted Manuscript (DOE)

Research Organization:: 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:: 1616815

Alternate ID(s):: OSTI ID: 1969639

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 15 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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