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A fundamental look at electrocatalytic sulfur reduction reaction

Abstract

The fundamental kinetics of the electrocatalytic sulfur reduction reaction (SRR), a complex 16-electron conversion process in lithium–sulfur batteries, is so far insufficiently explored. Here, by directly profiling the activation energies in the multistep SRR, we reveal that the initial reduction of sulfur to the soluble polysulfides is relatively easy owing to the low activation energy, whereas the subsequent conversion of the polysulfides into the insoluble Li2S2/Li2S has a much higher activation energy, contributing to the accumulation of polysulfides and exacerbating the polysulfide shuttling effect. We use heteroatom-doped graphene as a model system to explore electrocatalytic SRR. We show that nitrogen and sulfur dual-doped graphene considerably reduces the activation energy to improve SRR kinetics. Density functional calculations confirm that the doping tunes the p-band centre of the active carbons for an optimal adsorption strength of intermediates and electroactivity. This study establishes electrocatalysis as a promising pathway to tackle the fundamental challenges facing lithium–sulfur batteries.

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Fig. 1: Activation energy in sulfur reduction and PS conversion reaction.
Fig. 2: Material characterizations of the N,S-HGF.
Fig. 3: Catalytic SRR activity and kinetic analyses of heteroatom-doped HGFs in RDE.
Fig. 4: DFT calculations on the activity origin of the heteroatom-doped HGFs on SRR.
Fig. 5: Activation energy profiles and overall performance of the heteroatom-doped HGF cathodes in Li–S coin cells.

Data availability

The data that support the findings of this study are available from the corresponding authors on reasonable request.

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Acknowledgements

This work is supported by the Center for Synthetic Control Across Length-scales for Advancing Rechargeables, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science Basic Energy Sciences programme under award DE-SC0019381. Y.H. acknowledges the support by Office of Naval Research through grant no. N00010141712608 (initial effort on catalyst preparation and rotating disc electrode electrochemical characterizations). I.M. and Z.A. acknowledge the support by the International Scientific Partnership Program (ISPP-147) at King Saud University. We acknowledge the Electron Imaging Center at UCLA for SEM technical support and the Nanoelectronics Research Facility at UCLA for device fabrication technical support. We thank Diamond Light Source for access and support in use of the electron Physical Science Imaging Centre (MG23956). The calculations were performed on the Hoffman2 cluster at UCLA Institute for Digital Research and Education (IDRE), The National Energy Research Scientific Computing Center (NERSC), and the Extreme Science and Engineering Discovery Environment (XSEDE)52, which is supported by National Science Foundation grant number ACI-1548562, through allocation TG-CHE170060.

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X.D., Y.H. and L.P. conceived and designed the experimental research. P.S. and Z.W. designed and performed the DFT calculations. L.P. performed the experiments and conducted the data analysis with contributions from C.W., J.L., Z.C., D.Z., D.B., H.L., X.X., I.S., Z.A., S.T., B.D., Y.H. and X.D. C.S.A. and A.I.K. contributed to the TEM characterizations. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Yu Huang or Philippe Sautet or Xiangfeng Duan.

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Supplementary Information

Supplementary Figs. 1–14, Discussion, and Tables 1 and 2.

Supplementary Data

Atomic coordinates of the optimized computational models.

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Peng, L., Wei, Z., Wan, C. et al. A fundamental look at electrocatalytic sulfur reduction reaction. Nat Catal 3, 762–770 (2020). https://doi.org/10.1038/s41929-020-0498-x

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