Sulfur speciation in Li–S batteries determined by operando laboratory X-ray emission spectroscopy

Rajh, Ava (author), Vižintin, Alen (author), Hoszowska, Joanna (author), Dominko, Robert (author), Kavčič, Matjaž (author)

In this work, operando sulfur X-ray emission measurements on a Li−S battery cathode were performed using a laboratory setup as an alternative to more common synchrotron radiation based absorption studies. Photoexcitation by an X-ray tube was used. Valence-to-core Kβ X-ray emission spectra were recorded with a wavelength dispersive crystal spectrometer in von Hamos geometry, providing excellent energy resolution and good detection efficiency. The setup was used to record ex situ S Kβ emission spectra from S cathodes from the Li−S battery and also under operando conditions. Average S oxidation state within the battery cathode during battery cycling was determined from the shape of the Kβ emission spectra. A more detailed S species characterization was performed by fitting a linear combination of previously measured laboratory synthesized standards to the measured spectra. Relative amounts of different S species in the cathode were determined during the cycling of the Li−S battery. The main advantage of X-ray emission spectroscopy is that it can be performed on concentrated samples with S loading comparable to a real battery. The approach shows great promise for routine laboratory analysis of electrochemical processes in Li−S batteries and other sulfur-based systems under operando conditions.

• Language: English
• Keywords: X-ray emission spectroscopy, lithium−sulfur batteries, operando measurements, oxidation state, von Hamos spectrometer
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FMF - Faculty of Mathematics and Physics
• Publication status: Published
• Publication version: Version of Record
• Year: 2024
• Number of pages: Str. 11135-11143
• Numbering: Vol. 7, iss. 23
• PID: 20.500.12556/RUL-165866
• UDC: 544.5/.6
• ISSN on article: 2574-0962
• DOI: 10.1021/acsaem.4c02330
• COBISS.SI-ID: 218392579
• Publication date in RUL: 12.12.2024

Record is a part of a journal

• Title: ACS applied energy materials
• Shortened title: ACS app. energy mater.
• Publisher: American Chemical Society
• ISSN: 2574-0962
• COBISS.SI-ID: 39550725

Licences

• License: CC BY 4.0, Creative Commons Attribution 4.0 International
• Link: http://creativecommons.org/licenses/by/4.0/
• Description: This is the standard Creative Commons license that gives others maximum freedom to do what they want with the work as long as they credit the author.

Secondary language

• Language: Slovenian
• Keywords: litij-žveplove baterije, elektrokemija, spektroskopija