Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Developing high-power Li||S batteries via transition metal/carbon nanocomposite electrocatalyst engineering

Nature Nanotechnology (2024)Cite this article

Subjects

Abstract

The activity of electrocatalysts for the sulfur reduction reaction (SRR) can be represented using volcano plots, which describe specific thermodynamic trends. However, a kinetic trend that describes the SRR at high current rates is not yet available, limiting our understanding of kinetics variations and hindering the development of high-power Li||S batteries. Here, using Le Chatelier’s principle as a guideline, we establish an SRR kinetic trend that correlates polysulfide concentrations with kinetic currents. Synchrotron X-ray adsorption spectroscopy measurements and molecular orbital computations reveal the role of orbital occupancy in transition metal-based catalysts in determining polysulfide concentrations and thus SRR kinetic predictions. Using the kinetic trend, we design a nanocomposite electrocatalyst that comprises a carbon material and CoZn clusters. When the electrocatalyst is used in a sulfur-based positive electrode (5 mg cm−2 of S loading), the corresponding Li||S coin cell (with an electrolyte:S mass ratio of 4.8) can be cycled for 1,000 cycles at 8 C (that is, 13.4 A gS−1, based on the mass of sulfur) and 25 °C. This cell demonstrates a discharge capacity retention of about 75% (final discharge capacity of 500 mAh gS−1) corresponding to an initial specific power of 26,120 W kgS−1 and specific energy of 1,306 Wh kgS−1.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Application of Le Chatelier’s principle in Li||S batteries.
Fig. 2: Development of an SRR kinetic trend.
Fig. 3: Relationship between SRR kinetics and polysulfide concentration.
Fig. 4: Correlation between polysulfide concentration and molecular orbitals of catalysts.
Fig. 5: Electrocatalysts design to improve SRR kinetics in Li||S batteries.
Fig. 6: Electrochemical testing of high-power Li||S batteries.

Similar content being viewed by others

Data availability

Data supporting findings from this work are available within this Article and the Supplementary Information. All other relevant data supporting findings are available from the corresponding author on request. Source data are provided with this paper.

References

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

    Article  CAS  Google Scholar 

  2. Zhao, C. et al. A high-energy and long-cycling lithium–sulfur pouch cell via a macroporous catalytic cathode with double-end binding sites. Nat. Nanotechnol. 16, 166–173 (2020).

    Article  PubMed  ADS  Google Scholar 

  3. Zhao, C. X. et al. Semi-immobilized molecular electrocatalysts for high-performance lithium-sulfur batteries. J. Am. Chem. Soc. 143, 19865–19872 (2021).

    Article  CAS  PubMed  Google Scholar 

  4. Zhou, G., Chen, H. & Cui, Y. Formulating energy density for designing practical lithium–sulfur batteries. Nat. Energy 7, 312–319 (2022).

    Article  CAS  ADS  Google Scholar 

  5. Li, G., Chen, Z. & Lu, J. Lithium–sulfur batteries for commercial applications. Chem 4, 3–7 (2018).

    Article  CAS  Google Scholar 

  6. 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 

  7. Fang, R. et al. More reliable lithium–sulfur batteries: status, solutions and prospects. Adv. Mater. 29, 1606823 (2017).

    Article  Google Scholar 

  8. 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  CAS  ADS  Google Scholar 

  9. Tikekar, M. D., Choudhury, S., Tu, Z. Y. & Archer, L. A. Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 1, 16114–116120 (2016).

    Article  CAS  ADS  Google Scholar 

  10. Yang, X., Luo, J. & Sun, X. Towards high-performance solid-state Li–S batteries: from fundamental understanding to engineering design. Chem. Soc. Rev. 49, 2140–2195 (2020).

    Article  CAS  PubMed  Google Scholar 

  11. Yang, Y. et al. Electrocatalysis in lithium sulfur batteries under lean electrolyte conditions. Angew. Chem. Int. Ed. 57, 15549–15552 (2018).

    Article  CAS  ADS  Google Scholar 

  12. Song, Y. et al. Rationalizing electrocatalysis of Li–S chemistry by mediator design: progress and prospects. Adv. Energy Mater. 10, 1901075 (2019).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  14. Dibden, J. W., Smith, J. W., Zhou, N., Garcia-Araez, N. & Owen, J. R. Predicting the composition and formation of solid products in lithium-sulfur batteries by using an experimental phase diagram. Chem. Commun. 52, 12885–12888 (2016).

    Article  CAS  Google Scholar 

  15. Shen, Z. et al. Cation-doped ZnS catalysts for polysulfide conversion in lithium–sulfur batteries. Nat. Catal. 5, 555–563 (2022).

    Article  CAS  Google Scholar 

  16. Zhong, Y. R. et al. Surface chemistry in cobalt phosphide-stabilized lithium–sulfur batteries. J. Am. Chem. Soc. 140, 1455–1459 (2018).

    Article  CAS  PubMed  Google Scholar 

  17. Xue, W. et al. Intercalation-conversion hybrid cathodes enabling Li–S full-cell architectures with jointly superior gravimetric and volumetric energy densities. Nat. Energy 4, 374–382 (2019).

    Article  CAS  ADS  Google Scholar 

  18. Du, Z. et al. Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium–sulfur batteries. J. Am. Chem. Soc. 141, 3977–3985 (2019).

    Article  CAS  PubMed  Google Scholar 

  19. 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  CAS  PubMed  PubMed Central  ADS  Google Scholar 

  20. De Heer, J. The principle of Le Châtelier and Braun. J. Chem. Educ. 34, 375 (1957).

    Article  Google Scholar 

  21. Zhang, L. et al. In situ optical spectroscopy characterization for optimal design of lithium–sulfur batteries. Chem. Soc. Rev. 48, 5432–5453 (2019).

    Article  CAS  PubMed  Google Scholar 

  22. Li, H. et al. Revealing principles for design of lean-electrolyte lithium metal anode via in-situ spectroscopy. J. Am. Chem. Soc. 142, 2012–2022 (2020).

    Article  CAS  PubMed  Google Scholar 

  23. Li, H. et al. Reversible electrochemical oxidation of sulfur in ionic liquid for high-voltage Al−S batteries. Nat. Commun. 12, 5714 (2021).

    Article  CAS  PubMed  PubMed Central  ADS  Google Scholar 

  24. Liu, L. & Corma, A. Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chem. Rev. 118, 4981–5079 (2018).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  25. 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 

  26. Li, H. et al. Unraveling the catalyst-solvent interactions in lean-electrolyte sulfur reduction electrocatalysis for Li–S batteries. Angew. Chem. Int. Ed. 61, e202213863 (2022).

  27. 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  CAS  ADS  Google Scholar 

  28. Hwang, J. et al. Perovskites in catalysis and electrocatalysis. Science 358, 751–756 (2017).

    Article  CAS  PubMed  ADS  Google Scholar 

  29. Singh, J. P., Park, J. Y., Chae, K. H., Ahn, D. & Lee, S. Soft X-ray absorption spectroscopic investigation of Li(Ni0.8Co0.1Mn0.1)O2 cathode materials. Nanomaterials 10, 759 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  30. Massalski, T. B. & Okamoto, H. Binary Alloy Phase Diagrams 2nd edn (ASM International, 1990).

  31. Kurata, H. & Colliex, C. Electron-energy-loss core-edge structures in manganese oxides. Phys. Rev. B 48, 2102–2108 (1993).

    Article  CAS  ADS  Google Scholar 

  32. Lin, F. et al. Synchrotron X-ray analytical techniques for studying materials electrochemistry in rechargeable batteries. Chem. Rev. 117, 13123–13186 (2017).

    Article  CAS  PubMed  Google Scholar 

  33. Fan, F. Y., Carter, W. C. & Chiang, Y. M. Mechanism and kinetics of Li2S precipitation in lithium–sulfur batteries. Adv. Mater. 27, 5203–5209 (2015).

    Article  CAS  PubMed  Google Scholar 

  34. Bhargav, A., He, J., Gupta, A. & Manthiram, A. Lithium–sulfur batteries: attaining the critical metrics. Joule 4, 285–291 (2020).

    Article  Google Scholar 

  35. Vivanco, J. P. & Rodriguez-Monroy, C. Graphene applications in the energy field: state-of-the-art and impact. In Proc. 16th LACCEI International Multi-Conference for Engineering, Education and Technology (2018).

Download references

Acknowledgements

This research was financially supported by the Australian Research Council (ARC) through the Discovery Project Program (grant numbers FL170100154 and DP220102596). Density functional theory computations were undertaken with the assistance of the National Computational Infrastructure (NCI), supported by the Australian Government. B.J. is supported by a Fellowship at the University of Wollongong. Part of this research was undertaken on the X-ray Absorption Spectroscopy (XAS), Powder Diffraction (PD) and Soft X-ray Spectroscopy (SXR) Beamlines at the Australian Synchrotron, part of ANSTO.

Author information

Author notes

  1. These authors contributed equally: Huan Li, Rongwei Meng.

Authors and Affiliations

  1. School of Chemical Engineering, The University of Adelaide, Adelaide, South Australia, Australia

    Huan Li, Chao Ye, Kenneth Davey & Shi-Zhang Qiao

  2. School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

    Rongwei Meng & Wuxing Hua

  3. Australian Synchrotron, ANSTO, Clayton, Victoria, Australia

    Anton Tadich, Qinfen Gu & Bernt Johannessen

  4. Institute for Superconducting and Electronic Materials, University of Wollongong, Wollongong, New South Wales, Australia

    Bernt Johannessen

  5. Beijing Key Laboratory of Green Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, China

    Xiao Chen

Authors
  1. Huan Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rongwei Meng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Chao Ye
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Anton Tadich
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wuxing Hua
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Qinfen Gu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Bernt Johannessen
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Xiao Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Kenneth Davey
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Shi-Zhang Qiao
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

S.-Z.Q. conceived and supervised this research. H.L. designed and carried out experiments and density functional theory computations. R.M. carried out the synthesis of the cluster catalysts and electrochemical tests. C.Y. assisted with the design of the sulfur positive electrode. A.T. assisted with soft X-ray spectroscopy and related data analyses. W.H. tested the Li−S battery performance. Q.G. assisted with the in situ synchrotron X-ray diffraction measurements. B.J. carried out X-ray adsorption spectroscopy and data analyses. X.C. captured scanning transmission electron microscope images. S.-Z.Q. and K.D. revised the paper. All authors discussed the results and commented on the paper.

Corresponding author

Correspondence to Shi-Zhang Qiao.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Nanotechnology thanks Bing Joe Hwang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–32, Tables 1 and 2, Notes 1–6 and References.

Source data

Source Data Fig. 1

Source data for Fig. 1 are in sheet 1. Source Data Fig. 2 Source data for Fig. 2 are in sheet 2. Source Data Fig. 3 Source data for Fig. 3 are in sheet 3. Source Data Fig. 4 Source data for Fig. 4 are in sheet 4. Source Data Fig. 5 Source data for Fig. 5 are in sheet 5. Source Data Fig. 6 Source data for Fig. 6 are in sheet 6.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, H., Meng, R., Ye, C. et al. Developing high-power Li||S batteries via transition metal/carbon nanocomposite electrocatalyst engineering. Nat. Nanotechnol. (2024). https://doi.org/10.1038/s41565-024-01614-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1038/s41565-024-01614-4

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing