Physical Chemistry

Gently Does It!: In Situ Preparation of Alkali Metal - Solid Electrolyte Interfaces for Photoelectron Spectroscopy

Authors

Abstract

The key charge transfer processes in energy storage devices occur at the electrode-electrolyte interface, which is typically buried making it challenging to access the interfacial chemistry. In the case of Li-ion batteries, metallic Li electrodes hold promise for increasing energy and power densities, and when used in conjunction with solid electrolytes (SEs) adverse safety implications associated with dendrite formation in organic liquid electrolytes can potentially be overcome. To better understand the stability of SEs when in contact with alkali metals and the reactions that occur, here we consider the deposition of thin (~10 nm) alkali metal films onto SE surfaces, that are thin enough that X-ray photoelectron spectroscopy can probe the buried electrode-electrolyte interface. We highlight the importance of in situ alkali metal deposition, by assessing the contaminant species that are present after glovebox handling and the use of ‘inert’ transfer devices. Consequently, we compare and contrast three available methods for in situ alkali-metal deposition; Li sputter deposition, Li evaporation, and Li plating induced by e− flood-gun irradiation. Studies on both a sulphide SE (Li6PS5Cl), and a single-layer graphene probe surface reveal that the more energetic Li deposition methods, such as sputtering, can induce surface damage and interfacial mixing that is not seen with thermal evaporation. This indicates that appropriate selection of the Li deposition method for in situ studies is required to observe representative behaviour, and the results of previous studies involving energetic deposition may warrant further evaluation.

Content

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Supplementary material

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Gently Does It!: In Situ Preparation of Alkali Metal - Solid Electrolyte Interfaces for Photoelectron Spectroscopy – Supporting Information
Supporting information showing supporting SOXPES and HAXPES data for Li deposited on Argyrodite solid electrolyte, the comparison of in situ Li metal sputtering and argon ion bombardment, and surface contamination resulting from use of inert transfer devices.