Revealing the hidden electrochemical pathway for cathode electrolyte interface formation in lithium–sulfur batteries with carbonate-based electrolytes

García-Soriano, Francisco J. (author), Genorio, Boštjan (author), Vižintin, Alen (author)

This study investigates the role of microporous carbons and carbonate-based electrolytes in addressing challenges related to polysulfides dissolution and electrolyte compatibility in lithium−sulfur (Li−S) batteries. By employing microporous carbons and varying the sulfur content, we investigate the formation of the cathode-electrolyte interphase (CEI) during the first discharge process. We propose an electrochemical nucleophilic mechanism for the formation of the CEI involving polysulfides and solvent molecules in the confined small pores of the cathode. This interphase, primarily composed of LiF, effectively seals the carbon pores, preventing further solvent intrusion and stabilizing the system. Furthermore, it allows the use of wider pores without compromising the system. Our findings reveal that an increased sulfur content within the micropores enhances cycling stability, contradicting trends observed in ether-based systems. These insights highlight the potential of designing Li−S systems with optimized pore structures and electrolyte compositions to achieve greater stability and capacity retention, marking a significant step forward in the development of practical Li−S batteries.

• Language: English
• Keywords: lithium−sulfur batteries, cathode-electrolyte interphase, microporous carbon, carbonate-based electrolytes, polysulfides, batteries, electrodes, electrolytes, porosity, sulfur
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Publication status: Published
• Publication version: Version of Record
• Year: 2026
• Number of pages: Str. 211-221
• Numbering: Vol. 9, iss. 1
• PID: 20.500.12556/RUL-179021
• UDC: 66
• ISSN on article: 2574-0962
• DOI: 10.1021/acsaem.5c02970
• COBISS.SI-ID: 266744067
• Publication date in RUL: 03.02.2026

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: kemijska tehnologija, materiali, litij-žveplove baterije, ogljik