Role of Polysulfide Anions in Solid-Electrolyte Interphase Formation at the Lithium Metal Surface in Li–S Batteries
- 22 September 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry Letters
- Vol. 12 (38), 9360-9367
- https://doi.org/10.1021/acs.jpclett.1c01930
Abstract
Delineating intricate interactions between highly reactive Li-metal electrodes and the diverse constituents of battery electrolytes has been a long-standing scientific challenge in materials design for advanced energy storage devices. Here, we isolated lithium polysulfide anions (LiS4–) from an electrolyte solution based on their mass-to-charge ratio and deposited them on Li-metal electrodes under clean vacuum conditions using ion soft landing (ISL), a highly controlled interface preparation technique. The molecular level precision in the construction of these model interfaces with ISL, coupled with in situ X-ray photoelectron spectroscopy and ab initio theoretical calculations, allowed us to obtain unprecedented insight into the parasitic reactions of well-defined polysulfides on Li-metal electrodes. Our study revealed that the oxide-rich surface layer, which is amenable to direct electron exchange, drives multielectron sulfur oxidation (S0 → S6+) processes. Our results have substantial implications for the rational design of future Li–S batteries with improved efficiency and durability.Funding Information
- Basic Energy Sciences
This publication has 39 references indexed in Scilit:
- Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteriesNature Communications, 2014
- Rechargeable Lithium–Sulfur BatteriesChemical Reviews, 2014
- Molecular structure and stability of dissolved lithium polysulfide speciesPhysical Chemistry Chemical Physics, 2014
- Lithium–Sulfur Batteries: Electrochemistry, Materials, and ProspectsAngewandte Chemie, 2013
- New Approaches for High Energy Density Lithium–Sulfur Battery CathodesAccounts of Chemical Research, 2012
- Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayerNature Communications, 2012
- On the Surface Chemical Aspects of Very High Energy Density, Rechargeable Li–Sulfur BatteriesJournal of the Electrochemical Society, 2009
- XPS of sulphide mineral surfaces: metal-deficient, polysulphides, defects and elemental sulphurSurface and Interface Analysis, 1999
- Quantitative determination of surface composition of sulfur bearing anion mixtures by Auger electron spectroscopyAnalytical Chemistry, 1980
- Soft landing of ions as a means of surface modificationInternational Journal of Mass Spectrometry and Ion Physics, 1977