Fluorinated ester additive to regulate nucleation behavior and interfacial chemistry of room temperature sodium-sulfur batteries

J Colloid Interface Sci. 2025 Jan 15;678(Pt B):1125-1134. doi: 10.1016/j.jcis.2024.09.069. Epub 2024 Sep 12.

Abstract

Room temperature sodium-sulfur (RT Na-S) batteries are considered as advanced energy storage technology due to their low cost and high theoretical energy density. However, challenges such as the growth of sodium dendrite and dissolution of sodium polysulfides significantly hinder the electrochemical performance. Herein, we developed a propylene carbonate (PC)-based electrolyte with Methyl 2-Fluoroisobutyrate (MFB) as an additive. The ester group in the MFB additive is capable of participating in and reconfiguring the coordination of their Na+ solvated structures, thereby lowering the desolvation barrier and regulating the Na anode's interfacial reaction and nucleation behavior. The polar C-F bond at the other end helps to reduce the lowest unoccupied molecular orbital (LUMO) energy of the MFB additive, enabling the preferential decomposition of MFB to form the F-rich inorganic phase strong polar solid electrolyte interphase (SEI), contributing to the inhibition of Na dendrite growth, the accumulation of dead Na. In addition, NaF-riched cathode electrolyte interphase (CEI) was also observed on sulfur-based cathode, which can effectively inhibited the shuttle effect. Consequently, the developed RT Na-S battery exhibit excellent electrochemical performance.

Keywords: Carbonate electrolyte; Cathode electrolyte interphase; Electrolyte additives; Room temperature sodium-sulfur batteries; Solid electrolyte interphase.