Room-temperature sodium–sulfur batteries are promising next-generation energy storage alternatives for electric vehicles and large-scale applications. However, they still suffer from critical issues such as polysulfide shuttling, which inhibit them from commercialization. In this work, using first-principles methods, we investigated the cluster formation of soluble Na2S8 molecules, the reductive decomposition of ethylene carbonate (EC) and propylene carbonate (PC), and the role of fluoroethylene carbonate (FEC) additive in the solid electrolyte interphase formation on the Na anode. The clustering of Na2S8 in an EC solvent is found to be more favorable than in a PC solvent. In the presence of an electron-rich Na (001) surface, EC decomposition undergoes a two-electron transfer reaction with a barrier of 0.19 eV for a ring-opening process, whereas PC decomposition is difficult on the same surface. Although the reaction kinetics of an FEC ring opening in the EC and PC solvents are quite similar, the reaction mechanisms of the open FEC are found to be different in each solvent, although both lead to the production of NaF on the surface. The thick NaF layers reduce the extent of charge transfer to Na2S8 at the anode/electrolyte interface, thus decelerating the Na2S8 decomposition reaction. Our results provide an atomistic insight into the interfacial phenomena between the Na-metal anode surface and electrolyte media.
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28 March 2023
Research Article|
March 22 2023
Polysulfide cluster formation, surface reaction, and role of fluorinated additive on solid electrolyte interphase formation at sodium-metal anode for sodium–sulfur batteries
Special Collection:
Chemical Physics of Electrochemical Energy Materials
Sirisak Singsen
;
Sirisak Singsen
(Conceptualization, Formal analysis, Writing – original draft)
1
School of Physics, Institute of Science, Suranaree University of Technology
, Nakhon Ratchasima 30000, Thailand
2
Department of Chemical Engineering, Texas A&M University
, College Station, Texas 77843, USA
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Pussana Hirunsit
;
Pussana Hirunsit
(Formal analysis, Methodology, Writing – review & editing)
3
National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA)
, Pathum Thani, Thailand
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Suwit Suthirakun
;
Suwit Suthirakun
(Conceptualization, Investigation, Writing – review & editing)
4
School of Chemistry, Institute of Science, Suranaree University of Technology
, Nakhon Ratchasima 30000, Thailand
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Perla B. Balbuena
Perla B. Balbuena
a)
(Conceptualization, Supervision, Writing – review & editing)
2
Department of Chemical Engineering, Texas A&M University
, College Station, Texas 77843, USA
5
Department of Materials Science and Engineering, Texas A&M University
, College Station, Texas 77843, USA
a)Author to whom correspondence should be addressed: balbuena@tamu.edu
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a)Author to whom correspondence should be addressed: balbuena@tamu.edu
Note: This paper is part of the JCP Special Topic on Chemical Physics of Electrochemical Energy Materials.
J. Chem. Phys. 158, 124706 (2023)
Article history
Received:
November 23 2022
Accepted:
March 02 2023
Citation
Sirisak Singsen, Pussana Hirunsit, Suwit Suthirakun, Perla B. Balbuena; Polysulfide cluster formation, surface reaction, and role of fluorinated additive on solid electrolyte interphase formation at sodium-metal anode for sodium–sulfur batteries. J. Chem. Phys. 28 March 2023; 158 (12): 124706. https://doi.org/10.1063/5.0136005
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