Skip to main content
SpringerLink
Log in

Ni@N-doped graphene nanosheets and CNTs hybrids modified separator as efficient polysulfide barrier for high-performance lithium sulfur batteries

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Lithium-sulfur batteries (LSBs) have been regarded as one of the most promising energy storage systems to break through the upper limit of lithium-ion batteries. However, the rampant diffusions of soluble lithium polysulfides (LiPSs) in the electrolyte induced the shuttle effect between anode and cathode, resulting in low sulfur utilization, low energy efficiency and short cycling life. Herein, we prove the rational design and construction of Ni nanoparticles filled in vertically grown N-doped bamboo-like carbon nanotubes (CNTs) on graphene nanosheets (Ni@NG-CNTs) as efficient polysulfide barrier for high-performance LSBs. The unique design integrates graphene nanosheets and CNTs into hierarchical architectures with one-dimensional (1D) CNTs, two-dimensional (2D) ultrathin nanosheets and abundant carbon nanocages. This design provides large surface area for lithium polysulfides (LiPSs) adsorption, accelerates electron transport and enhances electrochemical redox of LiPSs. Benefiting from the unique structural features, the LSBs with the Ni@NG-CNTs as polysulfide barrier keep high reversible specific capacities of 309.1 and 265.0 mAh·g−1 at 5 and 10 C rates after 500 cycles. This work provides a new strategy for constructing self-assembled hybrids of CNTs and graphene nanosheets with abundant carbon nanocages for high-performance LSBs.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Manthiram, A.; Fu, Y. Z.; Chung, S. H.; Zu, C. X.; Su, Y. S. Rechargeable lithium-sulfur batteries. Chem. Rev. 2014, 114, 11751–11787.

    Article  Google Scholar 

  2. Jiang, J.; Zhu, J. H.; Ai, W.; Wang, X. L.; Wang, Y. L.; Zou, C. J.; Huang, W.; Yu, T. Encapsulation of sulfur with thin-layered nickel-based hydroxides for long-cyclic lithium-sulfur cells. Nat. Commun. 2015, 6, 8622.

    Article  Google Scholar 

  3. Tikekar, M. D.; Choudhury, S.; Tu, Z. Y.; Archer, L. A. Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 2016, 1, 16114.

    Article  Google Scholar 

  4. Fang, R. P.; Zhao, S. Y.; Pei, S. F.; Cheng, Y. X.; Hou, P. X.; Liu, M.; Cheng, H. M.; Liu, C.; Li, F. An integrated electrode/separator with nitrogen and nickel functionalized carbon hybrids for advanced lithium/polysulfide batteries. Carbon 2016, 109, 719–726.

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  7. Luo, L.; Chung, S. H.; Manthiram, A. A three-dimensional self-assembled SnS2-nano-dots@graphene hybrid aerogel as an efficient polysulfide reservoir for high-performance lithium-sulfur batteries. J. Mater. Chem. A 2018, 6, 7659–7667.

    Article  Google Scholar 

  8. Zhu, S. Y.; Wang, Y. Q.; Jiang, J. C.; Yan, X.; Sun, D. Y.; Jin, Y. C.; Nan, C. W.; Munakata, H.; Kanamura, K. Good low-temperature properties of nitrogen-enriched porous carbon as sulfur hosts for high-performance Li-S batteries. ACS Appl. Mater. Interfaces 2016, 8, 17253–17259.

    Article  Google Scholar 

  9. Bai, S. Y.; Liu, X. Z.; Zhu, K.; Wu, S. C.; Zhou, H. S. Metal–organic framework-based separator for lithium–sulfur batteries. Nat. Energy 2016, 1, 16094.

    Article  Google Scholar 

  10. Cao, J.; Chen, C.; Zhao, Q.; Zhang, N.; Lu, Q. Q.; Wang, X. Y.; Niu, Z. Q.; Chen, J. A flexible nanostructured paper of a reduced graphene oxide-sulfur composite for high-performance lithium-sulfur batteries with unconventional configurations. Adv. Mater. 2016, 28, 9629–9636.

    Article  Google Scholar 

  11. Gnana Kumar, G.; Chung, S. H.; Raj Kumar, T.; Manthiram, A. Threedimensional graphene-carbon nanotube-Ni hierarchical architecture as a polysulfide trap for lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2018, 10, 20627–20634.

    Article  Google Scholar 

  12. Chung, S. H.; Chang, C. H.; Manthiram, A. A core-shell electrode for dynamically and statically stable Li–S battery chemistry. Energy Environ. Sci. 2016, 9, 3188–3200.

    Article  Google Scholar 

  13. Chen, C. Y.; Peng, H. J.; Hou, T. Z.; Zhai, P. Y.; Li, B. Q.; Tang, C.; Zhu, W. C.; Huang, J. Q.; Zhang, Q. A quinonoid-imine-enriched nanostructured polymer mediator for lithium-sulfur batteries. Adv. Mater. 2017, 29, 1606802.

    Article  Google Scholar 

  14. Cui, Z. M.; Zu, C. X.; Zhou, W. D.; Manthiram, A.; Goodenough, J. B. Mesoporous titanium nitride-enabled highly stable lithium-sulfur batteries. Adv. Mater. 2016, 28, 6926–6931.

    Article  Google Scholar 

  15. Wang, L.; Yang, Z.; Nie, H. G.; Gu, C. C.; Hua, W. X.; Xu, X. J.; Chen, X. A.; Chen, Y.; Huang, S. M. A lightweight multifunctional interlayer of sulfur-nitrogen dual-doped graphene for ultrafast, long-life lithium-sulfur batteries. J. Mater. Chem. A 2016, 4, 15343–15352.

    Article  Google Scholar 

  16. Ghazi, Z. A.; He, X.; Khattak, A. M.; Khan, N. A.; Liang, B.; Iqbal, A.; Wang, J. X.; Sin, H.; Li, L. S.; Tang, Z. Y. MoS2/Celgard separator as efficient polysulfide barrier for long-life lithium-sulfur batteries. Adv. Mater. 2017, 29, 1606817.

    Article  Google Scholar 

  17. Li, F.; Kaiser, M. R.; Ma, J. M.; Guo, Z. P.; Liu, H. K.; Wang, J. Z. Freestanding sulfur-polypyrrole cathode in conjunction with polypyrrole-coated separator for flexible Li-S batteries. Energy Storage Mater. 2018, 13, 312–322.

    Article  Google Scholar 

  18. Li, J.; Huang, Y. D.; Zhang, S.; Jia, W.; Wang, X. C.; Guo, Y.; Jia, D. Z.; Wang, L. S. Decoration of silica nanoparticles on polypropylene separator for lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2017, 9, 7499–7504.

    Article  Google Scholar 

  19. Song, J. J.; Su, D. W.; Xie, X. Q.; Guo, X.; Bao, W. Z.; Shao, G. J.; Wang, G. X. Immobilizing polysulfides with MXene-functionalized separators for stable lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2016, 8, 29427–29433.

    Article  Google Scholar 

  20. Balach, J.; Singh, H. K.; Gomoll, S.; Jaumann, T.; Klose, M.; Oswald, S.; Richter, M.; Eckert, J.; Giebeler, L. Synergistically enhanced polysulfide chemisorption using a flexible hybrid separator with N and S dual-doped mesoporous carbon coating for advanced lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2016, 8, 14586–14595.

    Article  Google Scholar 

  21. Su, D. W.; Cortie, M.; Fan, H. B.; Wang, G. X. Prussian blue nanocubes with an open framework structure coated with PEDOT as high-capacity cathodes for lithium-sulfur batteries. Adv. Mater. 2017, 29, 1700587.

    Article  Google Scholar 

  22. Zhang, J.; Yang, C. P.; Yin, Y. X.; Wan, L. J.; Guo, Y. G. Sulfur encapsulated in graphitic carbon nanocages for high-rate and long-cycle lithium-sulfur batteries. Adv. Mater. 2016, 28, 9539–9544.

    Article  Google Scholar 

  23. Jin, F. Y.; Xiao, S.; Lu, L. J.; Wang, Y. Efficient activation of high-loading sulfur by small CNTs confined inside a large CNT for high-capacity and high-rate lithium-sulfur batteries. Nano Lett. 2016, 16, 440–447.

    Article  Google Scholar 

  24. Wang, Y.; Kong, D. Z.; Shi, W. H.; Liu, B.; Sim, G. J.; Ge, Q.; Yang, H. Y. Ice templated free-standing hierarchically WS2/CNT-rGO aerogel for high-performance rechargeable lithium and sodium ion batteries. Adv. Energy Mater. 2016, 6, 1601057.

    Article  Google Scholar 

  25. Su, Y. S.; Manthiram, A. A new approach to improve cycle performance of rechargeable lithium-sulfur batteries by inserting a free-standing MWCNT interlayer. Chem. Commun. 2012, 48, 8817–8819.

    Article  Google Scholar 

  26. Pang, Y.; Wei, J. S.; Wang, Y. G.; Xia, Y. Y. Synergetic protective effect of the ultralight MWCNTs/NCQDs modified separator for highly stable lithium-sulfur batteries. Adv. Energy Mater. 2018, 8, 1702288.

    Article  Google Scholar 

  27. Su, D. W.; Cortie, M.; Wang, G. X. Fabrication of N-doped graphenecarbon nanotube hybrids from prussian blue for lithium-sulfur batteries. Adv. Energy Mater. 2017, 7, 1602014.

    Article  Google Scholar 

  28. Liang, J.; Yin, L. C.; Tang, X. N.; Yang, H. C.; Yan, W. S.; Song, L.; Cheng, H. M.; Li, F. Kinetically enhanced electrochemical redox of polysulfides on polymeric carbon nitrides for improved lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2016, 8, 25193–25201.

    Article  Google Scholar 

  29. Hu, G. J.; Xu, C.; Sun, Z. H.; Wang, S. G.; Cheng, H. M.; Li, F.; Ren, W. C. 3D graphene-foam-reduced-graphene-oxide hybrid nested hierarchical networks for high-performance Li-S batteries. Adv. Mater. 2016, 28, 1603–1609.

    Article  Google Scholar 

  30. Zhao, M. Q.; Liu, X. F.; Zhang, Q.; Tian, G. L.; Huang, J. Q.; Zhu, W. C.; Wei, F. Graphene/single-walled carbon nanotube hybrids: One-step catalytic growth and applications for high-rate Li-S batteries. ACS Nano 2012, 6, 10759–10769.

    Article  Google Scholar 

  31. Balamurugan, J.; Thanh, T. D.; Kim, N. H.; Lee, J. H. Facile synthesis of 3D hierarchical N-doped graphene nanosheet/cobalt encapsulated carbon nanotubes for high energy density asymmetric supercapacitors. J. Mater. Chem. A 2016, 4, 9555–9565.

    Article  Google Scholar 

  32. Su, L. W.; Zhou, Z.; Shen, P. W. Ni/C hierarchical nanostructures with Ni nanoparticles highly dispersed in N-containing carbon nanosheets: Origin of Li storage capacity. J. Phys. Chem. C 2012, 116, 23974–23980.

    Article  Google Scholar 

  33. Yoo, J.; Cho, S. J.; Jung, G. Y.; Kim, S. H.; Choi, K. H.; Kim, J. H.; Lee, C. K.; Kwak, S. K.; Lee, S. Y. COF-net on CNT-net as a molecularly designed, hierarchical porous chemical trap for polysulfides in lithium-sulfur batteries. Nano Lett. 2016, 16, 3292–3300.

    Article  Google Scholar 

  34. Xu, J. Q.; Zhou, K.; Chen, F.; Chen, W.; Wei, X. F.; Liu, X. W.; Liu, J. H. Natural integrated carbon architecture for rechargeable lithium–sulfur batteries. ACS Sustain. Chem. Eng. 2016, 4, 666–670.

    Article  Google Scholar 

  35. Yang, J. Q.; Zhou, X. L.; Wu, D. H.; Zhao, X. D.; Zhou, Z. S-doped N-rich carbon nanosheets with expanded interlayer distance as anode materials for sodium-ion batteries. Adv. Mater. 2017, 29, 1604108.

    Article  Google Scholar 

  36. Yuan, X. Q.; Wu, L. S.; He, X. L.; Zeinu, K.; Huang, L.; Zhu, X. L.; Hou, H. J.; Liu, B. C.; Hu, J. P.; Yang, J. K. Separator modified with N,S co-doped mesoporous carbon using egg shell as template for high performance lithium-sulfur batteries. Chem. Eng. J. 2017, 320, 178–188.

    Article  Google Scholar 

  37. Zhang, W. L.; Xu, C.; Ma, C. Q.; Li, G. X.; Wang, Y. Z.; Zhang, K. Y.; Li, F.; Liu, C.; Cheng, H. M.; Du, Y. W. et al. Nitrogen-superdoped 3D graphene networks for high-performance supercapacitors. Adv. Mater. 2017, 29, 1701677.

    Article  Google Scholar 

  38. Anantharaj, S.; Karthick, K.; Venkatesh, M.; Simha, T. V. S. V.; Salunke, A. S.; Ma, L.; Liang, H.; Kundu, S. Enhancing electrocatalytic total water splitting at few layer Pt-NiFe layered double hydroxide interfaces. Nano Energy 2017, 39, 30–43.

    Article  Google Scholar 

  39. Chen, G. P.; Song, X.; Wang, S. Q.; Wang, Y.; Gao, T.; Ding, L. X.; Wang, H. H. A multifunctional separator modified with cobalt and nitrogen co-doped porous carbon nanofibers for Li-S batteries. J. Membr. Sci. 2018, 548, 247–253.

    Article  Google Scholar 

  40. Song, X.; Wang, S. Q.; Chen, G. P.; Gao, T.; Bao, Y.; Ding, L. X.; Wang, H. H. Fe-N-doped carbon nanofiber and graphene modified separator for lithium-sulfur batteries. Chem. Eng. J. 2018, 333, 564–571.

    Article  Google Scholar 

  41. Zeng, P.; Huang, L. W.; Zhang, X. L.; Zhang, R. X.; Wu, L.; Chen, Y. G. Long-life and high-areal-capacity lithium-sulfur batteries realized by a honeycomb-like N, P dual-doped carbon modified separator. Chem. Eng. J. 2018, 349, 327–337.

    Article  Google Scholar 

  42. Chen, X. X.; Ding, X. Y.; Wang, C. S.; Feng, Z. Y.; Xu, L. Q.; Gao, X.; Zhai, Y. J.; Wang, D. B. A multi-shelled CoP nanosphere modified separator for highly efficient Li-S batteries. Nanoscale 2018, 10, 13694–13701.

    Article  Google Scholar 

  43. Ding, H. B.; Zhang, Q. F.; Liu, Z. M.; Wang, J.; Ma, R. F.; Fan, L.; Wang, T.; Zhao, J. G.; Ge, J. M.; Lu, X. L. et al. TiO2 quantum dots decorated multi-walled carbon nanotubes as the multifunctional separator for highly stable lithium sulfur batteries. Electrochim. Acta. 2018, 284, 314–320.

    Article  Google Scholar 

  44. Yang, Y. F.; Zhang, J. P. Highly stable lithium-sulfur batteries based on laponite nanosheet-coated celgard separators. Adv. Energy Mater. 2018, 8, 1801778.

    Article  Google Scholar 

  45. Jiang, K.; Gao, S.; Wang, R. X.; Jiang, M.; Han, J.; Gu, T. T.; Liu, M. Y.; Cheng, S. J.; Wang, K. L. Lithium sulfonate/carboxylate-anchored polyvinyl alcohol separators for lithium sulfur batteries. ACS Appl. Mater. Interfaces 2018, 10, 18310–18315.

    Article  Google Scholar 

  46. Song, X.; Chen, G. P.; Wang, S. Q.; Huang, Y. P.; Jiang, Z. Y.; Ding, L. X.; Wang, H. H. Self-assembled close-packed MnO2 nanoparticles anchored on a polyethylene separator for lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2018, 10, 26274–26282.

    Article  Google Scholar 

  47. Wu, F.; Zhao, S. Y.; Chen, L.; Lu, Y.; Su, Y. F.; Jia, Y. N.; Bao, L. Y.; Wang, J.; Chen, S.; Chen, R. J. Metal-organic frameworks composites threaded on the CNT knitted separator for suppressing the shuttle effect of lithium sulfur batteries. Energy Storage Mater. 2018, 14, 383–391.

    Article  Google Scholar 

  48. Zhai, P. Y.; Peng, H. J.; Cheng, X. B.; Zhu, L.; Huang, J. Q.; Zhu, W. C.; Zhang, Q. Scaled-up fabrication of porous-graphene-modified separators for high-capacity lithium–sulfur batteries. Energy Storage Mater. 2017, 7, 56–63.

    Article  Google Scholar 

  49. Li, H. P.; Sun, L. C.; Zhang, Y. G.; Tan, T. Z.; Wang, G. K.; Bakenov, Z. Enhanced cycle performance of Li/S battery with the reduced graphene oxide/activated carbon functional interlayer. J. Energy Chem. 2017, 26, 1276–1281.

    Article  Google Scholar 

  50. Huang, J. Q.; Zhuang, T. Z.; Zhang, Q.; Peng, H. J.; Chen, C. M.; Wei, F. Permselective graphene oxide membrane for highly stable and anti-selfdischarge lithium-sulfur batteries. ACS Nano 2015, 9, 3002–3011.

    Article  Google Scholar 

  51. Pang, Q.; Tang, J. T.; Huang, H.; Liang, X.; Hart, C.; Tam, K. C.; Nazar, L. F. A nitrogen and sulfur dual-doped carbon derived from polyrhodanine@cellulose for advanced lithium-sulfur batteries. Adv. Mater. 2015, 27, 6021–6028.

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by funding from the Postdoctoral Science Foundation of China (No. 2017M611171), the National Natural Science Foundation of China (NSFC) (Nos. 21571170, 21501168, and 51702236), Tianjin Municipal Science and Technology Commission (No. 17JCZDJC38000).

Author information

Authors and Affiliations

  1. Tianjin Key Laboratory of Advanced Functional Porous Materials and Center for Electron Microscopy, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300071, China

    Xintao Zuo, Mengmeng Zhen & Cheng Wang

  2. Tianjin Key Laboratory of Clean Energy and Pollution Control, School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin, 300401, China

    Mengmeng Zhen

Authors
  1. Xintao Zuo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mengmeng Zhen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Cheng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Mengmeng Zhen or Cheng Wang.

Electronic supplementary material

12274_2019_2298_MOESM1_ESM.pdf

Ni@N-doped graphene nanosheets and CNTs hybrids modified separator as efficient polysulfide barrier for high-performance lithium sulfur batteries

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zuo, X., Zhen, M. & Wang, C. Ni@N-doped graphene nanosheets and CNTs hybrids modified separator as efficient polysulfide barrier for high-performance lithium sulfur batteries. Nano Res. 12, 829–836 (2019). https://doi.org/10.1007/s12274-019-2298-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-019-2298-7

Keywords

Search

Navigation