Skip to main content
SpringerLink
Log in

CoSe2 nanoparticles-decorated carbon nanofibers as a hierarchical self-supported sulfur host for high-energy lithium-sulfur batteries

CoSe2纳米颗粒修饰的碳纳米纤维硫宿主助力高性能锂硫电池

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Lithium-sulfur (Li-S) batteries have gained widespread attention owing to their high theoretical energy density and low cost. However, the commercial application of these batteries is hindered by the severe shuttle effect and slow redox reaction kinetics of polysulfides. In this study, a hierarchically porous membrane consisting of CoSe2 nanoparticle-decorated carbon nanofibers containing carbon nanotubes (CoSe2@CNF/CNT) is constructed as a self-supported sulfur host for Li-S batteries. The hierarchical conductive network of CNFs/CNTs with N-doped porous carbon facilitates electron/ion transport and provides sufficient space to mitigate the volume expansion of lithium polysulfides (LiPSs). Moreover, the modified CoSe2 nanoparticles serve as both chemical trappers and electrocatalysts, chemically anchoring LiPSs and accelerating the redox kinetics to inhibit the shuttle effect. As a result, an initial specific discharge capacity of 1098.8 mA h g−1 is achieved at 1 C. Importantly, the cathode exhibits superior cycling stability with a capacity decay rate as low as 0.06% over 500 cycles. This work offers a feasible approach to designing multi-functional sulfur hosts for high-energy-density Li-S batteries.

摘要

具有高理论容量和高能量密度的锂硫电池被认为是最具前景的储能器件, 但其实用化进程受到了多硫化物穿梭效应和氧化还原动力学缓慢等问题的影响. 本文将CoSe2纳米颗粒修饰的碳纳米纤维/碳纳米管(CoSe2@CNF/CNT)自支撑膜作为高性能锂硫电池硫宿主电极. 其中, 由氮掺杂多孔碳和CNF/CNT组成的导电碳网络能够促进电荷传输,并缓解硫在循环过程中的体积膨胀. CoSe2纳米颗粒兼具化学吸附位点和电催化剂的功能, 通过化学吸附锚定多硫化物并加速其氧化还原转换, 从而抑制穿梭效应和提高性能. 因此CoSe2@CNF/CNT-S电极具有优异的电化学性能, 1 C下能提供1098.8 mA h g−1的放电比容量, 循环500圈中每圈容量衰减率低至0.06%. 这项工作为高能量密度锂硫电池的开发提供了一种新方案.

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. Seh ZW, Sun Y, Zhang Q, et al. Designing high-energy lithium-sulfur batteries. Chem Soc Rev, 2016, 45: 5605–5634

    Article  CAS  Google Scholar 

  2. Chen ZX, Zhao M, Hou LP, et al. Toward practical high-energy-density lithium-sulfur pouch cells: A review. Adv Mater, 2022, 34: 2201555

    Article  CAS  Google Scholar 

  3. Rana M, Ahad SA, Li M, et al. Review on areal capacities and long-term cycling performances of lithium sulfur battery at high sulfur loading. Energy Storage Mater, 2019, 18: 289–310

    Article  Google Scholar 

  4. Chung SH, Manthiram A. Current status and future prospects of metal-sulfur batteries. Adv Mater, 2019, 31: 1901125

    Article  Google Scholar 

  5. Li Y, Guo S. Material design and structure optimization for rechargeable lithium-sulfur batteries. Matter, 2021, 4: 1142–1188

    Article  CAS  Google Scholar 

  6. Li J, Niu Z, Guo C, et al. Catalyzing the polysulfide conversion for promoting lithium sulfur battery performances: A review. J Energy Chem, 2021, 54: 434–451

    Article  CAS  Google Scholar 

  7. Li Y, Zhou Y, Muhammad Y, et al. Nanocellulose and its derivatives toward advanced lithium sulfur batteries. ACS Mater Lett, 2021, 3: 1130–1142

    Article  CAS  Google Scholar 

  8. Yang Y, Cao J, Li W, et al. Ultrahigh-capacity and dendrite-free lithium metal anodes enabled by lithiophilic bimetallic oxides. J Mater Chem A, 2022, 10: 23896–23904

    Article  CAS  Google Scholar 

  9. Deng R, Ke B, Xie Y, et al. All-solid-state thin-film lithium-sulfur batteries. Nano-Micro Lett, 2023, 15: 73

    Article  CAS  Google Scholar 

  10. Hu G, Xu C, Sun Z, et al. 3D graphene-foam-reduced-graphene-oxide hybrid nested hierarchical networks for high-performance Li-S batteries. Adv Mater, 2016, 28: 1603–1609

    Article  CAS  Google Scholar 

  11. Xie Y, Cao J, Wang X, et al. MOF-derived bifunctional Co0.85Se nanoparticles embedded in N-doped carbon nanosheet arrays as efficient sulfur hosts for lithium-sulfur batteries. Nano Lett, 2021, 21: 8579–8586

    Article  CAS  Google Scholar 

  12. Pu X, Yang G, Yu C. Liquid-type cathode enabled by 3D sponge-like carbon nanotubes for high energy density and long cycling life of Li-S batteries. Adv Mater, 2014, 26: 7456–7461

    Article  CAS  Google Scholar 

  13. Liu H, Liu X, Li W, et al. Porous carbon composites for next generation rechargeable lithium batteries. Adv Energy Mater, 2017, 7: 1700283

    Article  Google Scholar 

  14. Zheng M, Chi Y, Hu Q, et al. Carbon nanotube-based materials for lithium-sulfur batteries. J Mater Chem A, 2019, 7: 17204–17241

    Article  CAS  Google Scholar 

  15. Lin L, Pei F, Peng J, et al. Fiber network composed of interconnected yolk-shell carbon nanospheres for high-performance lithium-sulfur batteries. Nano Energy, 2018, 54: 50–58

    Article  CAS  Google Scholar 

  16. Wang M, Zhou X, Cai X, et al. Hierarchically porous, ultrathin N-doped carbon nanosheets embedded with highly dispersed cobalt nanoparticles as efficient sulfur host for stable lithium-sulfur batteries. J Energy Chem, 2020, 50: 106–114

    Article  Google Scholar 

  17. Cheng Q, Yin Z, Pan S, et al. Enhancing adsorption and reaction kinetics of polysulfides using CoP-coated N-doped mesoporous carbon for high-energy-density lithium-sulfur batteries. ACS Appl Mater Interfaces, 2020, 12: 43844–43853

    Article  CAS  Google Scholar 

  18. Liu J, Xiao S, Liu X, et al. Encapsulating Co9S8 nanocrystals into CNT-reinforced N-doped carbon nanofibers as a chainmail-like electrocatalyst for advanced Li-S batteries with high sulfur loading. Chem Eng J, 2021, 423: 130246

    Article  CAS  Google Scholar 

  19. Li T, Liu K, Wang S, et al. Mesoporous hierarchical NiCoSe2–NiO composite self-supported on carbon nanoarrays as synergistic electrocatalyst for flexible lithium-sulfur batteries. J Colloid Interface Sci, 2022, 629: 114–124

    Article  Google Scholar 

  20. Fang Y, Yu XY, Lou XWD. Formation of hierarchical Cu-doped CoSe2 microboxes via sequential ion exchange for high-performance sodium-ion batteries. Adv Mater, 2018, 30: 1706668

    Article  Google Scholar 

  21. Yang D, Zhang C, Biendicho JJ, et al. ZnSe/N-doped carbon nanoreactor with multiple adsorption sites for stable lithium-sulfur batteries. ACS Nano, 2020, 14: 15492–15504

    Article  CAS  Google Scholar 

  22. Ye Z, Jiang Y, Li L, et al. A high-efficiency CoSe electrocatalyst with hierarchical porous polyhedron nanoarchitecture for accelerating polysulfides conversion in Li-S batteries. Adv Mater, 2020, 32: 2002168

    Article  CAS  Google Scholar 

  23. Xiang M, Wu H, Liu H, et al. A flexible 3D multifunctional MgO-decorated carbon foam@CNTs hybrid as self-supported cathode for high-performance lithium-sulfur batteries. Adv Funct Mater, 2017, 27: 1702573

    Article  Google Scholar 

  24. Yun X, Lu T, Zhou R, et al. Heterostructured NiSe2/CoSe2 hollow microspheres as battery-type cathode for hybrid supercapacitors: Electrochemical kinetics and energy storage mechanism. Chem Eng J, 2021, 426: 131328

    Article  CAS  Google Scholar 

  25. Cao J, Xie Y, Yang Y, et al. Achieving uniform Li plating/stripping at ultrahigh currents and capacities by optimizing 3D nucleation sites and Li2Se-enriched SEI. Adv Sci, 2022, 9: 2104689

    Article  CAS  Google Scholar 

  26. Wu J, Pan Z, Zhang Y, et al. The recent progress of nitrogen-doped carbon nanomaterials for electrochemical batteries. J Mater Chem A, 2018, 6: 12932–12944

    Article  CAS  Google Scholar 

  27. Wu ZS, Ren W, Xu L, et al. Doped graphene sheets as anode materials with superhigh rate and large capacity for lithium ion batteries. ACS Nano, 2011, 5: 5463–5471

    Article  CAS  Google Scholar 

  28. Su H, Lu L, Yang M, et al. Decorating CoSe2 on N-doped carbon nanotubes as catalysts and efficient polysulfides traps for Li-S batteries. Chem Eng J, 2022, 429: 132167

    Article  CAS  Google Scholar 

  29. Wang M, Fan L, Sun X, et al. Nitrogen-doped CoSe2 as a bifunctional catalyst for high areal capacity and lean electrolyte of Li-S battery. ACS Energy Lett, 2020, 5: 3041–3050

    Article  CAS  Google Scholar 

  30. Zhu J, Pitcheri R, Kang T, et al. Electrospun carbon nanofibers decorated with MnO nanoparticles as a sulfur-absorbent for lithium-sulfur batteries. Ceramics Int, 2018, 44: 16837–16843

    Article  CAS  Google Scholar 

  31. Wong H, Ou X, Zhuang M, et al. Selenium edge as a selective anchoring site for lithium-sulfur batteries with MoSe2/graphene-based cathodes. ACS Appl Mater Interfaces, 2019, 11: 19986–19993

    Article  CAS  Google Scholar 

  32. Mao Y, Li G, Guo Y, et al. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries. Nat Commun, 2017, 8: 14628

    Article  Google Scholar 

  33. Su D, Cortie M, Wang G. Fabrication of N-doped graphene-carbon nanotube hybrids from Prussian blue for lithium-sulfur batteries. Adv Energy Mater, 2017, 7: 1602014

    Article  Google Scholar 

  34. Cao Z, Wang Y, Guo J, et al. CoSe-catalyzed growth of graphene sheath to construct CNF@graphene-CoSe cable/sheath heterostructure for high-performance lithium-sulfur batteries. Carbon, 2023, 204: 102–111

    Article  CAS  Google Scholar 

  35. Zhang F, Wang H, Ji S, et al. Catalytically active CoSe2 supported on nitrogen-doped three dimensional porous carbon as a cathode for highly stable lithium-sulfur battery. ChemPhysChem, 2022, 23: e202100811

    Article  CAS  Google Scholar 

  36. Cao Y, Lei F, Li Y, et al. Interface engineering in NiSe2/Ni2Co/CoSe2 heterostructures encapsulated in hollow carbon shells for high-rate Li-Se batteries. Nanoscale, 2022, 14: 13227–13235

    Article  CAS  Google Scholar 

  37. Huang T, Sun Y, Wu J, et al. A dual-functional fibrous skeleton implanted with single-atomic Co-N dispersions for longevous Li-S full batteries. ACS Nano, 2021, 15: 14105–14115

    Article  CAS  Google Scholar 

  38. Zhang H, Xin S, Li J, et al. Synergistic regulation of polysulfides immobilization and conversion by MOF-derived CoP-HNC nanocages for high-performance lithium-sulfur batteries. Nano Energy, 2021, 85: 106011

    Article  CAS  Google Scholar 

  39. Xu J, Xu L, Zhang Z, et al. Heterostructure ZnSe–CoSe2 embedded with yolk-shell conductive dodecahedral as two-in-one hosts for cathode and anode protection of lithium-sulfur full batteries. Energy Storage Mater, 2022, 47: 223–234

    Article  Google Scholar 

  40. Feng T, Zhao T, Zhu S, et al. Anion-doped cobalt selenide with porous architecture for high-rate and flexible lithium-sulfur batteries. Small Methods, 2021, 5: 2100649

    Article  CAS  Google Scholar 

  41. Cai D, Liu B, Zhu D, et al. Ultrafine Co3Se4 nanoparticles in nitrogen-doped 3D carbon matrix for high-stable and long-cycle-life lithium sulfur batteries. Adv Energy Mater, 2020, 10: 1904273

    Article  CAS  Google Scholar 

  42. Jin B, Yang L, Zhang J, et al. Bioinspired binders actively controlling ion migration and accommodating volume change in high sulfur loading lithium-sulfur batteries. Adv Energy Mater, 2019, 9: 1902938

    Article  CAS  Google Scholar 

  43. Lieu WY, Fang D, Li Y, et al. Spherical templating of CoSe2 nanoparticle-decorated MXenes for lithium-sulfur batteries. Nano Lett, 2022, 22: 8679–8687

    Article  CAS  Google Scholar 

  44. Qiu Y, Yin XJ, Wang MX, et al. Constructed conductive CoSe2 nanoarrays as efficient electrocatalyst for high-performance Li-S battery. Rare Met, 2021, 40: 3147–3155

    Article  CAS  Google Scholar 

  45. He L, Yang D, Zhao H, et al. Bipolar CoSe2 nanocrystals embedded in porous carbon nanocages as an efficient electrocatalyst for Li-S batteries. Chem Eng J, 2022, 440: 135820

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (U22A20118), Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China (2021ZR146 and 2021ZZ122), and the Award Program for Fujian Minjiang Scholar Professorship. We would also like to thank Shuting Ren from Shiyanjia Lab (www.shiyanjia.com) for carrying out the XPS analyses.

Author information

Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. College of Physics and Information Engineering, Institute of Micro-Nano Devices and Solar Cells, Fuzhou University, Fuzhou, 350108, China

    Juan Ao  (奥娟), Yonghui Xie  (谢永辉), Yunda Lai  (赖运达), Ming Yang  (杨名), Jing Xu  (许静), Fan Wu  (吴燔), Shuying Cheng  (程树英) & Xinghui Wang  (王星辉)

  2. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, 350108, China

    Juan Ao  (奥娟), Shuying Cheng  (程树英) & Xinghui Wang  (王星辉)

  3. Jiangsu Collaborative Innovation Center of Photovoltaic Science and Engineering, Changzhou, 213000, China

    Shuying Cheng  (程树英) & Xinghui Wang  (王星辉)

Authors
  1. Juan Ao  (奥娟)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yonghui Xie  (谢永辉)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yunda Lai  (赖运达)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ming Yang  (杨名)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jing Xu  (许静)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Fan Wu  (吴燔)
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Shuying Cheng  (程树英)
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Xinghui Wang  (王星辉)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Wang X supervised the whole project. Ao J, Xie Y, and Wang X conceived the concept and initiated the project. Ao J and Xie Y designed and conducted the experiments and drafted the manuscript. All authors participated in the discussion of the results and revision of the manuscript.

Corresponding author

Correspondence to Xinghui Wang  (王星辉).

Additional information

Supplementary information

Supporting data are available in the online version of the paper.

Conflict of interest

The authors declare that they have no conflict of interest.

Juan Ao received her BSc degree from Yanshan University in 2019. Now she is an MSc student at the College of Physics and Information Engineering, Fuzhou University. Her current research focuses on the design of novel sulfur cathode for high performance lithium-sulfur batteries.

Yonghui Xie is a PhD candidate at the School of Physics and Information Engineering, Fuzhou University, focusing on the design and performance control of electrode materials for high energy density lithium-sulfur batteries.

Xinghui Wang completed his PhD degree in condensed matter physics from Lanzhou University in 2013, and then worked as a research staff at Nanyang Technological University and Singapore-MIT Alliance for Research and Technology in sequence. He is currently a Minjiang Scholar Professor at the College of Physics and Information Engineering, Fuzhou University. His research interests involve the fabrication of nanomaterials and thin film electrodes for energy storage application, mainly including thin film microbatteries, planar supercapacitors, flexible energy storage devices, lithium metal anodes, and sulfur cathodes.

Supporting Information

40843_2022_2462_MOESM1_ESM.pdf

CoSe2 Nanoparticles-decorated Carbon Nanofibers as A Hierarchical Self-supported Sulfur Host for high-energy lithium-sulfur batteries

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ao, J., Xie, Y., Lai, Y. et al. CoSe2 nanoparticles-decorated carbon nanofibers as a hierarchical self-supported sulfur host for high-energy lithium-sulfur batteries. Sci. China Mater. 66, 3075–3083 (2023). https://doi.org/10.1007/s40843-022-2462-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-022-2462-x

Keywords

Search

Navigation