Establishing reaction networks in the 16-electron sulfur reduction reaction

Rongli Liu; Ziyang Wei; Lele Peng; Leyuan Zhang; Arava Zohar; Rachel Schoeppner; Peiqi Wang; Chengzhang Wan; Dan Zhu; Haotian Liu; Zhaozong Wang; Sarah H Tolbert; Bruce Dunn; Yu Huang; Philippe Sautet; Xiangfeng Duan

doi:10.1038/s41586-023-06918-4

Establishing reaction networks in the 16-electron sulfur reduction reaction

Nature. 2024 Feb;626(7997):98-104. doi: 10.1038/s41586-023-06918-4. Epub 2024 Jan 31.

Authors

Rongli Liu^#¹, Ziyang Wei^#¹, Lele Peng¹, Leyuan Zhang^{1

2}, Arava Zohar³, Rachel Schoeppner⁴, Peiqi Wang¹, Chengzhang Wan¹, Dan Zhu¹, Haotian Liu², Zhaozong Wang¹, Sarah H Tolbert^{1

2

5}, Bruce Dunn^{2

5}, Yu Huang^{2

5}, Philippe Sautet^{6

7

8}, Xiangfeng Duan^{9

10}

Affiliations

¹ Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA.
² Department of Materials Science and Engineering, University of California, Los Angeles, CA, USA.
³ Materials Department and Materials Research Laboratory, University of California, Santa Barbara, CA, USA.
⁴ California NanoSystems Institute, University of California, Santa Barbara, CA, USA.
⁵ California NanoSystems Institute, University of California, Los Angeles, CA, USA.
⁶ Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA. sautet@ucla.edu.
⁷ California NanoSystems Institute, University of California, Los Angeles, CA, USA. sautet@ucla.edu.
⁸ Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, CA, USA. sautet@ucla.edu.
⁹ Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA. xduan@chem.ucla.edu.
¹⁰ California NanoSystems Institute, University of California, Los Angeles, CA, USA. xduan@chem.ucla.edu.

^# Contributed equally.

PMID: 38297176
DOI: 10.1038/s41586-023-06918-4

Abstract

The sulfur reduction reaction (SRR) plays a central role in high-capacity lithium sulfur (Li-S) batteries. The SRR involves an intricate, 16-electron conversion process featuring multiple lithium polysulfide intermediates and reaction branches^1-3. Establishing the complex reaction network is essential for rational tailoring of the SRR for improved Li-S batteries, but represents a daunting challenge^4-6. Herein we systematically investigate the electrocatalytic SRR to decipher its network using the nitrogen, sulfur, dual-doped holey graphene framework as a model electrode to understand the role of electrocatalysts in acceleration of conversion kinetics. Combining cyclic voltammetry, in situ Raman spectroscopy and density functional theory calculations, we identify and directly profile the key intermediates (S₈, Li₂S₈, Li₂S₆, Li₂S₄ and Li₂S) at varying potentials and elucidate their conversion pathways. Li₂S₄ and Li₂S₆ were predominantly observed, in which Li₂S₄ represents the key electrochemical intermediate dictating the overall SRR kinetics. Li₂S₆, generated (consumed) through a comproportionation (disproportionation) reaction, does not directly participate in electrochemical reactions but significantly contributes to the polysulfide shuttling process. We found that the nitrogen, sulfur dual-doped holey graphene framework catalyst could help accelerate polysulfide conversion kinetics, leading to faster depletion of soluble lithium polysulfides at higher potential and hence mitigating the polysulfide shuttling effect and boosting output potential. These results highlight the electrocatalytic approach as a promising strategy for tackling the fundamental challenges regarding Li-S batteries.