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A strategic approach to recharging lithium-sulphur batteries for long cycle life

Nature Communications volume 4, Article number: 2985 (2013) | Download Citation

Abstract

The success of rechargeable lithium-ion batteries has brought indisputable convenience to human society for the past two decades. However, unlike commercialized intercalation cathodes, high-energy-density sulphur cathodes are still in the stage of research because of the unsatisfactory capacity retention and long-term cyclability. The capacity degradation over extended cycles originates from the soluble polysulphides gradually diffusing out of the cathode region. Here we report an applicable way to recharge lithium-sulphur cells by a simple charge operation control that offers tremendous improvement with various lithium-sulphur battery systems. Adjusting the charging condition leads to long cycle life (over 500 cycles) with excellent capacity retention (>99%) by inhibiting electrochemical reactions along with severe polysulphide dissolution. This charging strategy and understanding of the reactions in different discharge steps will advance progress in the development of lithium-sulphur batteries.

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References

  1. 1.

    , , & Li-O2 and Li-S batteries with high energy storage. Nat. Mater. 11, 19–29 (2012).

  2. 2.

    , & Challenges and prospects of lithium–sulfur batteries. Acc. Chem. Res. 46, 1125–1134 (2013).

  3. 3.

    & Advances in Li-S batteries. J. Mater. Chem. 20, 9821–9826 (2010).

  4. 4.

    Liquid electrolyte lithium/sulfur battery: fundamental chemistry, problems, and solutions. J. Power Sources 231, 153–162 (2013).

  5. 5.

    et al. Sulphur-TiO2 yolk-shell nanoarchitecture with internal void space for long-cycle lithium-sulphur batteries. Nat. Commun. 4, 1331 (2013).

  6. 6.

    , , , & A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries. Nat. Commun. 4, 1481 (2013).

  7. 7.

    et al. Spherical ordered mesoporous carbon nanoparticles with high porosity for lithium-sulfur batteries. Angew. Chem. Int. Ed. 51, 3591–3595 (2012).

  8. 8.

    , , , & Confining sulfur in double-shelled hollow carbon spheres for lithium-sulfur batteries. Angew. Chem. Int. Ed. 51, 9592–9595 (2012).

  9. 9.

    , , , & Porous hollow carbon@sulfur composites for high-power lithium-sulfur batteries. Angew. Chem. Int. Ed. 50, 5904–5908 (2011).

  10. 10.

    , , , & Hollow carbon nanofiber-encapsulated sulfur cathodes for high specific capacity rechargeable lithium batteries. Nano Lett. 11, 4462–4467 (2011).

  11. 11.

    et al. Amphiphilic surface modification of hollow carbon nanofibers for improved cycle life of lithium sulfur batteries. Nano Lett. 13, 1265–1270 (2013).

  12. 12.

    , & Ultrasound assisted design of sulfur/carbon cathodes with partially fluorinated ether electrolytes for highly efficient Li/S batteries. Adv. Mater. 25, 1608–1615 (2013).

  13. 13.

    et al. Smaller sulfur molecules promise better lithium-sulfur batteries. J. Am. Chem. Soc. 134, 18510–18513 (2012).

  14. 14.

    , , & Comparison of the chemical stability of the high energy density cathodes of lithium-ion batteries. Electrochem. Commun. 3, 624–627 (2001).

  15. 15.

    Role of LiNO3 in rechargeable lithium/sulfur battery. Electrochim. Acta 70, 344–348 (2012).

  16. 16.

    & A facile in situ sulfur deposition route to obtain carbon-wrapped sulfur composite cathodes for lithium–sulfur batteries. Electrochim. Acta 77, 272–278 (2012).

  17. 17.

    & Polysulfide shuttle study in the Li/S battery system. J. Electrochem. Soc. 151, A1969–A1976 (2004).

  18. 18.

    , , , & Fast, reversible lithium storage with a sulfur/long-chain-polysulfide redox couple. Chemistry 19, 8621–8626 (2013).

  19. 19.

    , & A membrane-free lithium/polysulfide semi-liquid battery for large-scale energy storage. Energy Environ. Sci. 6, 1552–1558 (2013).

  20. 20.

    & Lithium-sulphur batteries with a microporous carbon paper as a bifunctional interlayer. Nat. Commun. 3, 1166 (2012).

  21. 21.

    , , & New insight into the discharge process of sulfur cathode by electrochemical impedance spectroscopy. J. Power Sources 189, 127–132 (2009).

  22. 22.

    , , & In-situ X-ray diffraction studies of lithium-sulfur batteries. J. Power Sources 226, 313–319 (2013).

  23. 23.

    et al. In operando X-ray diffraction and transmission X-ray microscopy of lithium sulfur batteries. J. Am. Chem. Soc. 134, 6337–6343 (2012).

  24. 24.

    et al. Rechargeable lithium sulfur battery—I. Structural change of sulfur cathode during discharge and charge. J. Electrochem. Soc. 150, A796–A799 (2003).

  25. 25.

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

  26. 26.

    , , & Analysis of polysulfide dissolved in electrolyte in discharge-charge process of Li-S battery. J. Electrochem. Soc. 159, A421–A425 (2012).

  27. 27.

    , , & Properties of surface film on lithium anode with LiNO3 as lithium salt in electrolyte solution for lithium-sulfur batteries. Electrochim. Acta 83, 78–86 (2012).

  28. 28.

    et al. On the surface chemical aspects of very high energy density, rechargeable Li-sulfur batteries. J. Electrochem. Soc. 156, A694–A702 (2009).

  29. 29.

    , & Highly reversible lithium/dissolved polysulfide batteries with carbon nanotube electrodes. Angew. Chem. Int. Ed. 52, 6930–6935 (2013).

  30. 30.

    , , , & Lithium sulfur battery oxidation/reduction mechanisms of polysulfides in THF solutions. J. Electrochem. Soc. 135, 1045–1048 (1988).

  31. 31.

    , , & Lithium‐sulfur battery: evaluation of dioxolane‐based electrolytes. J. Electrochem. Soc. 136, 1621–1625 (1989).

  32. 32.

    , , , & Electrochemical properties of the soluble reduction products in rechargeable Li/S battery. J. Power Sources 195, 2945–2949 (2010).

  33. 33.

    , , & Formation of lithium polysulfides in aprotic media. J. Inorg. Nucl. Chem. 39, 1761–1766 (1977).

  34. 34.

    & A new approach to improve cycle performance of rechargeable lithium-sulfur batteries by inserting a free-standing MWCNT interlayer. Chem. Commun. 48, 8817–8819 (2012).

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Acknowledgements

This work was supported by Seven One Limited. We thank the National Science Foundation (Grant number 0618242) for funding the Kratos Axis Ultra XPS used in this study and Dr Hugo Celio for the design of the custom interface for XPS sample transfer.

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Affiliations

  1. Materials Science and Engineering Program, The University of Texas at Austin, Austin, Texas 78712, USA

    • Yu-Sheng Su
    • , Yongzhu Fu
    • , Thomas Cochell
    •  & Arumugam Manthiram

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Contributions

Y.-S.S. conceived the research and performed the experiments; Y.F. prepared and analysed the Li/dissolved polysulphide cells; T.C. conducted the air-sensitive XPS measurements; A.M. supervised the work and involved in the discussions; Y.-S.S wrote the paper and all participated in the preparation of the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Arumugam Manthiram.

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DOI

https://doi.org/10.1038/ncomms3985

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