Catalytically altering the redox pathway of sulfur in propylene carbonate electrolyte using dual-nitrogen/oxygen-containing carbon

doi:10.1016/S1872-2067(24)60096-3

Abstract

Abstract:

Carbonate electrolytes are one of the most desirable electrolytes for high-energy lithium-sulfur batteries (LSBs) because of their successful implementation in commercial Li-ion batteries. The low-polysulfide-solubility feature of some carbonate solvents also makes them very promising for overcoming the shuttle effects of LSBs. However, regular sulfur electrodes experience undesired electrochemical mechanisms in carbonate electrolytes due to side reactions. In this study, we report a catalytic redox mechanism of sulfur in propylene carbonate (PC) electrolyte based on a comparison study. The catalytic mechanism is characterized by the interactions between polysulfides and dual N/O functional groups on the host carbon, which largely prevents side reactions between polysulfides and the carbonate electrolyte. Such a mechanism coupled with the low-polysulfide-solubility feature leads to stable cycling of LSBs in PC electrolyte. Favorable dual N/O functional groups are identified via a density functional theory study. This work provides an alternative route for enabling LSBs in carbonate electrolytes.

Key words: Energy storage, Lithium-sulfur battery, Catalytic redox reaction, Porous carbon, Carbonate electrolyte

Linghui Yu, Heng Zhang, Luyuan Paul Wang, Samuel Jun Hoong Ong, Shibo Xi, Bo Chen, Rui Guo, Ting Wang, Yonghua Du, Wei Chen, Ovadia Lev, Zhichuan J. Xu. Catalytically altering the redox pathway of sulfur in propylene carbonate electrolyte using dual-nitrogen/oxygen-containing carbon[J]. Chinese Journal of Catalysis, 2024, 63: 224-233.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60096-3

https://www.cjcatal.com/EN/Y2024/V63/I8/224

Figures/Tables 8

Fig. 1. Morphological analysis of N/O-C and N2 (77 K) adsorption analysis of N/O-C and O-C. SEM (a) and TEM (b) images of N/O-C. Adsorption isotherms (c) and corresponding pore size distributions (d).

Fig. 2. Preparation and properties of S52@N/O-C. (a) Schematic of preparation of S52@N/O-C from porous carbon (N/O-C). (b) XRD patterns of pristine sulfur and S52@N/O-C. (c,d) Electrochemical properties of S52@N/O-C. (c) The first five charge/discharge profiles in the PC electrolyte. (d) Rate capability in the PC electrolyte. (e) First two charge/discharge profiles in the diglyme electrolyte. (f) Rate capability and cyclability in the PC electrolyte.

Fig. 3. Properties of S20@N/O-C and S20@O-C. (a) XRD patterns. (b) TEM image of S20@N/O-C. Elemental mapping of S20@N/O-C for carbon (c), nitrogen (d), and sulfur (e). (f) TEM image of S20@O-C. Elemental mapping of S20@O-C for carbon (g) and sulfur (h).

Fig. 4. Electrochemical properties of S20@N/O-C and S20@O-C in PC electrolyte. First five charge/discharge profiles (a) and rate capability (b) of S20@N/O-C. (c) First five charge/discharge profiles of S20@O-C. (d) Rate capability and cyclability of S20@N/O-C.

Fig. 5. XANES study in the PC electrolyte. (a) Sulfur K-edge XANES spectra of S20@N/O-C electrodes at different lithiation states. (b) Sulfur K-edge XANES spectra of fresh S20@N/O-C electrodes and S20@N/O-C electrodes at discharged states at 1.0 V. (c) Points chosen for the XANES measurements of S20@N/O-C. (d) Sulfur K-edge XANES spectra of S20@O-C electrodes at different lithiation states. (e) Points chosen for the XANES measurements of S20@O-C. 1D, 1C, 2D, and 2C in the legends of (c,e) stand for the first discharge, first charge, second discharge, and second charge, respectively.

Fig. 6. XPS spectra of N/O-C. (a) C 1s; (b) N 1s.

Fig. 7. DFT calculations. Optimized adsorption structures (top view) of Li2S8 adsorbed on graphite (a), carbon with COOH (b), carbon with graphitic nitrogen (GN) and COOH (c), carbon with pyridinic nitrogen (PDN) and COOH (d), carbon with PDN and COH (e), and carbon with pyrrolic nitrogen (PRN) and C=O (f). (g) Adsorption energies of Li2S8 on different functional groups of carbon. More optimized adsorption structures can be found in Fig. S10 and Fig. S11.

Fig. 8. Schematic showing a catalytic redox mechanism of sulfur in the presence of N/O-containing carbon in carbonate electrolyte, comparing the mechanism when using a regular sulfur electrode.

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