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Establishing reaction networks in the 16-electron sulfur reduction reaction

Nature volume 626, pages 98–104 (2024)Cite this article

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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 branches1,2,3. Establishing the complex reaction network is essential for rational tailoring of the SRR for improved Li-S batteries, but represents a daunting challenge4,5,6. 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.

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Fig. 1: Polysulfide conversion reactions involved in the Li-S battery.
Fig. 2: Charge analysis and reaction network for the SRR.
Fig. 3: In situ Raman results during discharge with the N,S–HGF catalytic electrode.
Fig. 4: Comparison of different catalysts in SRR.
Fig. 5: Simulated site-specific output potential of Li2S4 → Li2S conversion.

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Data availability

The data that support the findings of this study are available in the main text, figures and Supplementary Information files.  Source data are provided with this paper. All relevant data are available from the corresponding authors on request.

Code availability

The code used for simulated voltage-dependent concentrations and CV curves is available at https://github.com/lophocinalis/concentration_cv.

References

  1. Mikhaylik, Y. V. & Akridge, J. R. Polysulfide shuttle study in the Li/S battery system. J. Electrochem. Soc. 151, A1969–A1976 (2004).

    Article  CAS  Google Scholar 

  2. Yin, Y. X., Xin, S., Guo, Y. G. & Wan, L. J. Lithium-sulfur batteries: electrochemistry, materials, and prospects. Angew. Chem. Int. Edn Engl. 52, 13186–13200 (2013).

  3. Pang, Q., Liang, X., Kwok, C. Y. & Nazar, L. F. Advances in lithium-sulfur batteries based on multifunctional cathodes and electrolytes. Nat. Energy 1, 16132 (2016).

    Article  ADS  CAS  Google Scholar 

  4. Barchasz, C. et al. Lithium/sulfur cell discharge mechanism: an original approach for intermediate species identification. Anal. Chem. 84, 3973–3980 (2012).

    Article  CAS  PubMed  Google Scholar 

  5. Cuisinier, M. et al. Sulfur speciation in Li-S batteries determined by operando X-ray absorption spectroscopy. J. Phys. Chem. Lett. 4, 3227–3232 (2013).

    Article  CAS  Google Scholar 

  6. Wild, M. et al. Lithium sulfur batteries, a mechanistic review. Energy Environ. Sci. 8, 3477–3494 (2015).

    Article  CAS  Google Scholar 

  7. Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J. M. Li-O2 and Li-S batteries with high energy storage. Nat. Mater. 11, 19–29 (2011).

    Article  ADS  PubMed  Google Scholar 

  8. Manthiram, A., Fu, Y., Chung, S. H., Zu, C. & Su, Y. S. Rechargeable lithium-sulfur batteries. Chem. Rev. 114, 11751–11787 (2014).

    Article  CAS  PubMed  Google Scholar 

  9. Ji, X., Lee, K. T. & Nazar, L. F. A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries. Nat. Mater. 8, 500–506 (2009).

    Article  ADS  CAS  PubMed  Google Scholar 

  10. Jayaprakash, N., Shen, J., Moganty, S. S., Corona, A. & Archer, L. A. Porous hollow carbon@sulfur composites for high-power lithium-sulfur batteries. Angew. Chem. Int. Edn Engl. 50, 5904–5908 (2011).

  11. Wang, N. et al. Thickness-independent scalable high-performance Li-S batteries with high areal sulfur loading via electron-enriched carbon framework. Nat. Commun. 12, 4519 (2021).

    Article  ADS  PubMed  PubMed Central  Google Scholar 

  12. Wang, L. et al. A quantum-chemical study on the discharge reaction mechanism of lithium-sulfur batteries. J. Energy Chem. 22, 72–77 (2013).

    Article  ADS  Google Scholar 

  13. Zou, Q. & Lu, Y. C. Solvent-dictated lithium sulfur redox reactions: an operando UV-vis spectroscopic study. J. Phys. Chem. Lett. 7, 1518–1525 (2016).

    Article  CAS  PubMed  Google Scholar 

  14. He, Q., Freiberg, A. T. S., Patel, M. U. M., Qian, S. & Gasteiger, H. A. Operando identification of liquid intermediates in lithium-sulfur batteries via transmission UV-vis spectroscopy. J. Electrochem. Soc. 167, 080508 (2020).

    Article  ADS  CAS  Google Scholar 

  15. Zheng, D. et al. Investigation of the Li-S battery mechanism by real-time monitoring of the changes of sulfur and polysulfide species during the discharge and charge. ACS Appl. Mater. Interfaces 9, 4326–4332 (2017).

    Article  CAS  PubMed  Google Scholar 

  16. Peng, L. et al. A fundamental look at electrocatalytic sulfur reduction reaction. Nat. Catal. 3, 762–770 (2020).

    Article  CAS  Google Scholar 

  17. Zhou, G. M., Paek, E., Hwang, G. S. & Manthiram, A. Long-life Li/polysulphide batteries with high sulphur loading enabled by lightweight three-dimensional nitrogen/sulphur-codoped graphene sponge. Nat. Commun. 6, 7760 (2015).

    Article  ADS  CAS  PubMed  Google Scholar 

  18. Yuan, Z. et al. Powering lithium-sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts. Nano Lett. 16, 519–527 (2016).

    Article  ADS  CAS  PubMed  Google Scholar 

  19. Peng, H. J. et al. Enhanced electrochemical kinetics on conductive polar mediators for lithium-sulfur batteries. Angew. Chem. Int. Edn Engl. 55, 12990–12995 (2016).

  20. Wang, L. et al. Li2S4 anchoring governs the catalytic sulfur reduction on defective SmMn2O5 in lithium-sulfur battery. Adv. Energy Mater. 12, 2200340 (2022).

    Article  CAS  Google Scholar 

  21. Zhou, T. et al. Twinborn TiO2-TiN heterostructures enabling smooth trapping-diffusion-conversion of polysulfides towards ultralong life lithium-sulfur batteries. Energy Environ. Sci. 10, 1694–1703 (2017).

    Article  CAS  Google Scholar 

  22. Zhou, J. et al. Deciphering the modulation essence of p bands in Co-based compounds on Li-S chemistry. Joule 2, 2681–2693 (2018).

    Article  CAS  Google Scholar 

  23. Hua, W. et al. Selective catalysis remedies polysulfide shuttling in lithium‐sulfur batteries. Adv. Mater. 33, 2101006 (2021).

    Article  CAS  Google Scholar 

  24. Zhou, G. et al. Theoretical calculation guided design of single-atom catalysts toward fast kinetic and long-life Li-S batteries. Nano Lett. 20, 1252–1261 (2019).

    Article  ADS  Google Scholar 

  25. Wang, L. et al. Design rules of a sulfur redox electrocatalyst for lithium-sulfur batteries. Adv. Mater. 34, 2110279 (2022).

    Article  CAS  Google Scholar 

  26. Lu, Y.-C., He, Q. & Gasteiger, H. A. Probing the lithium-sulfur redox reactions: a rotating-ring disk electrode study. J. Phys. Chem. C Nanomater. Interfaces 118, 5733–5741 (2014).

    Article  CAS  Google Scholar 

  27. Conder, J. et al. Direct observation of lithium polysulfides in lithium-sulfur batteries using operando X-ray diffraction. Nat. Energy 2, 17069 (2017).

    Article  ADS  CAS  Google Scholar 

  28. Wujcik, K. H. et al. Fingerprinting lithium-sulfur battery reaction products by X-ray absorption spectroscopy. J. Electrochem. Soc. 161, A1100–A1106 (2014).

    Article  CAS  Google Scholar 

  29. Hou, T. Z. et al. Lithium bond chemistry in lithium-sulfur batteries. Angew. Chem. Int. Edn Engl. 129, 8290–8294 (2017).

  30. Hagen, M. et al. In-situ Raman investigation of polysulfide formation in Li-S cells. J. Electrochem. Soc. 160, A1205–A1214 (2013).

    Article  CAS  Google Scholar 

  31. Zhou, G. et al. Catalytic oxidation of Li2S on the surface of metal sulfides for Li-S batteries. Proc. Natl Acad. Sci. USA 114, 840–845 (2017).

    Article  ADS  CAS  PubMed  PubMed Central  Google Scholar 

  32. Wujcik, K. H. et al. Characterization of polysulfide radicals present in an ether-based electrolyte of a lithium-sulfur battery during initial discharge using in situ X-ray absorption spectroscopy experiments and first‐principles calculations. Adv. Energy Mater. 5, 1500285 (2015).

    Article  Google Scholar 

  33. Rajput, N. N. et al. Elucidating the solvation structure and dynamics of lithium polysulfides resulting from competitive salt and solvent interactions. Chem. Mater. 29, 3375–3379 (2017).

    Article  CAS  Google Scholar 

  34. Assary, R. S., Curtiss, L. A. & Moore, J. S. Toward a molecular understanding of energetics in Li-S batteries using nonaqueous electrolytes: a high-level quantum chemical study. J. Phys. Chem. C Nanomater. Interfaces 118, 11545–11558 (2014).

    Article  CAS  Google Scholar 

  35. Xu, Y., Sheng, K., Li, C. & Shi, G. Self-assembled graphene hydrogel via a one-step hydrothermal process. ACS Nano 4, 4324–4330 (2010).

    Article  CAS  PubMed  Google Scholar 

  36. Chen, J.-J. et al. Conductive lewis base matrix to recover the missing link of Li2S8 during the sulfur redox cycle in Li-S battery. Chem. Mater. 27, 2048–2055 (2015).

    Article  CAS  Google Scholar 

  37. Zhu, X. et al. A highly stretchable cross-linked polyacrylamide hydrogel as an effective binder for silicon and sulfur electrodes toward durable lithium-ion storage. Adv. Funct. Mater. 28, 1705015 (2018).

    Article  Google Scholar 

  38. Wu, H. L., Huff, L. A. & Gewirth, A. A. In situ Raman spectroscopy of sulfur speciation in lithium-sulfur batteries. ACS Appl. Mater. Interfaces 7, 1709–1719 (2015).

    Article  CAS  PubMed  Google Scholar 

  39. Lei, T. et al. Inhibiting polysulfide shuttling with a graphene composite separator for highly robust lithium-sulfur batteries. Joule 2, 2091–2104 (2018).

    Article  CAS  Google Scholar 

  40. Chen, W. et al. A new hydrophilic binder enabling strongly anchoring polysulfides for high-performance sulfur electrodes in lithium-sulfur battery. Adv. Energy Mater. 8, 1702889 (2018).

    Article  Google Scholar 

  41. Hannauer, J. et al. The quest for polysulfides in lithium-sulfur battery electrolytes: an operando confocal Raman spectroscopy study. ChemPhysChem 16, 2709–2709 (2015).

    Article  CAS  Google Scholar 

  42. Zhang, Z.-M., Chen, S. & Liang, Y.-Z. Baseline correction using adaptive iteratively reweighted penalized least squares. Analyst 135, 1138–1146 (2010).

    Article  ADS  CAS  PubMed  Google Scholar 

  43. Zhu, W. et al. Investigation of the reaction mechanism of lithium sulfur batteries in different electrolyte systems by in situ Raman spectroscopy and in situ X-ray diffraction. Sustain. Energy Fuels 1, 737–747 (2017).

    Article  CAS  Google Scholar 

  44. Hohenberg, P. & Kohn, W. Inhomogeneous electron gas. Phys. Rev. 136, B864 (1964).

    Article  ADS  MathSciNet  Google Scholar 

  45. Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 140, A1133 (1965).

    Article  ADS  MathSciNet  Google Scholar 

  46. Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558 (1993).

    Article  ADS  CAS  Google Scholar 

  47. Sun, J., Ruzsinszky, A. & Perdew, J. P. Strongly constrained and appropriately normed semilocal density functional. Phys. Rev. Lett. 115, 036402 (2015).

    Article  ADS  PubMed  Google Scholar 

  48. Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. & Hennig, R. G. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).

    Article  ADS  PubMed  Google Scholar 

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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 no. DE-SC0019381.

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  1. These authors contributed equally: Rongli Liu, Ziyang Wei

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA

    Rongli Liu, Ziyang Wei, Lele Peng, Leyuan Zhang, Peiqi Wang, Chengzhang Wan, Dan Zhu, Zhaozong Wang, Sarah H. Tolbert, Philippe Sautet & Xiangfeng Duan

  2. Department of Materials Science and Engineering, University of California, Los Angeles, CA, USA

    Leyuan Zhang, Haotian Liu, Sarah H. Tolbert, Bruce Dunn & Yu Huang

  3. Materials Department and Materials Research Laboratory, University of California, Santa Barbara, CA, USA

    Arava Zohar

  4. California NanoSystems Institute, University of California, Santa Barbara, CA, USA

    Rachel Schoeppner

  5. California NanoSystems Institute, University of California, Los Angeles, CA, USA

    Sarah H. Tolbert, Bruce Dunn, Yu Huang, Philippe Sautet & Xiangfeng Duan

  6. Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, CA, USA

    Philippe Sautet

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Contributions

X.D. conceived the research. X.D. and R.L. designed the experimental research. P.S. and Z. Wei designed and performed density functional theory (DFT) calculations. R.L. performed experiments and conducted data analysis, with contributions from Z. Wei, L.P., L.Z., P.W., C.W., D.Z., H.L., Z. Wang, S.T., B.D., Y.H., P.S. and X.D. A.Z. and R.S. contributed to Raman data collection. R.L. and Z. Wei wrote the original draft. X.D. and P.S. revised the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Philippe Sautet or Xiangfeng Duan.

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Liu, R., Wei, Z., Peng, L. et al. Establishing reaction networks in the 16-electron sulfur reduction reaction. Nature 626, 98–104 (2024). https://doi.org/10.1038/s41586-023-06918-4

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