Skip to main content
SpringerLink
Log in

Super-aligned films of sub-1 nm Bi2O3-polyoxometalate nanowires as interlayers in lithium-sulfur batteries

超顺排的Bi2O3-多酸亚纳米线薄膜用于锂硫电池中间层

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

Abstract

Sub-1 nm nanowires (SNWs) can not only be processed like polymers due to their polymer-analogue properties but also show multifunctions owing to their well-manipulated compositions and structures. Rationally designed and engineered multicomponent heterostructure SNWs can further enhance their multifunction performance while it is very challenging to achieve such SNWs at sub-nanoscale. Herein, we synthesized Bi2O3-polyoxometalate heterostructure SNWs (PMB SNWs), and fabricated super-aligned PMB SNWs films (S-PMB SNWs films), which can serve as interlayers to efficiently suppress lithium polysulfide (LPS) shuttling, intrinsically promote the redox kinetics of the LPS conversion and substantially protect the Li anode. The lithium-sulfur (Li-S) battery with the S-PMB SNWs film as the interlayer showcases an ultralow capacity decay rate with 0.013% per cycle over 850 cycles. This study demonstrates the potential of heterostructure SNWs to improve the performance of Li-S batteries.

摘要

亚纳米线(SNWs)具有类高分子的性质, 可以像高分子一样进行加工, 而且其组成和结构易于调控, 具有丰富的功能. 合理设计多组分异质结构SNWs可以进一步提高其功能性, 然而目前合成这种SNWs仍然面临着巨大的挑战. 本文合成了Bi2O3-多酸异质结构SNWs(PMB SNWs), 并制备了超顺排的PMB SNWs薄膜(S-PMBSNWs薄膜), 该薄膜可以作为中间层, 有效抑制多硫化锂(LPSs)的穿梭, 从本质上促进LPSs氧化还原转化动力学, 并对锂阳极起到保护作用. 以S-PMB SNWs膜作为中间层的锂硫(Li-S)电池在850次循环中表现出超低的容量衰减率, 每循环一圈只衰减0.013%. 本研究证明了这种异质结构的SNWs具有改善锂硫电池性能的潜力.

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, Chung SH, et al. Rechargeable lithium-sulfur batteries. Chem Rev, 2014, 114: 11751–11787

    Article  CAS  Google Scholar 

  2. He B, Li WC, Chen ZY, et al. Multilevel structured carbon film as cathode host for Li-S batteries with superhigh-areal-capacity. Nano Res, 2021, 14: 1273–1279

    Article  CAS  Google Scholar 

  3. Zhang Z, Wu DH, Zhou Z, et al. Sulfur/nickel ferrite composite as cathode with high-volumetric-capacity for lithium-sulfur battery. Sci China Mater, 2019, 62: 74–86

    Article  CAS  Google Scholar 

  4. Hu J, Wang Z, Fu Y, et al. In situ assembly of MnO2 nanosheets on sulfur-embedded multichannel carbon nanofiber composites as cathodes for lithium-sulfur batteries. Sci China Mater, 2020, 63: 728–738

    Article  CAS  Google Scholar 

  5. Lopez J, Mackanic DG, Cui Y, et al. Designing polymers for advanced battery chemistries. Nat Rev Mater, 2019, 4: 312–330

    Article  CAS  Google Scholar 

  6. Hu S, Liu H, Wang P, et al. Inorganic nanostructures with sizes down to 1 nm: A macromolecule analogue. J Am Chem Soc, 2013, 135: 11115–11124

    Article  CAS  Google Scholar 

  7. Wang P, Yang Y, Zhuang J, et al. Self-adjustable crystalline inorganic nanocoils. J Am Chem Soc, 2013, 135: 6834–6837

    Article  CAS  Google Scholar 

  8. Liu H, Li H, He P, et al. Sub-1 nm nickel molybdate nanowires as building blocks of flexible paper and electrochemical catalyst for water oxidation. Small, 2016, 12: 1006–1012

    Article  CAS  Google Scholar 

  9. Zhang S, Shi W, Siegler TD, et al. An all-inorganic colloidal nanocrystal flexible polarizer. Angew Chem Int Ed, 2019, 58: 8730–8735

    Article  CAS  Google Scholar 

  10. Zhang S, Shi Y, He T, et al. Ultrathin tungsten bronze nanowires with efficient photo-to-thermal conversion behavior. Chem Mater, 2018, 30: 8727–8731

    Article  CAS  Google Scholar 

  11. Liu H, Gong Q, Yue Y, et al. Sub-1 nm nanowire based superlattice showing high strength and low modulus. J Am Chem Soc, 2017, 139: 8579–8585

    Article  CAS  Google Scholar 

  12. Liu J, Shi W, Ni B, et al. Incorporation of clusters within inorganic materials through their addition during nucleation steps. Nat Chem, 2019, 11: 839–845

    Article  CAS  Google Scholar 

  13. Xu X, Chen S, Chen Y, et al. Polyoxometalate cluster-incorporated metal-organic framework hierarchical nanotubes. Small, 2016, 12: 2982–2990

    Article  CAS  Google Scholar 

  14. Liu J, Liu N, Wang H, et al. Hybrid MoO3-polyoxometallate sub-1 nm nanobelt superstructures. J Am Chem Soc, 2020, 142: 17557–17563

    Article  CAS  Google Scholar 

  15. Song Y, Zhao W, Kong L, et al. Synchronous immobilization and conversion of polysulfides on a VO2-VN binary host targeting high sulfur load Li-S batteries. Energy Environ Sci, 2018, 11: 2620–2630

    Article  CAS  Google Scholar 

  16. Xu H, Jiang Q, Zhang B, et al. Integrating conductivity, immobility, and catalytic ability into high-N carbon/graphene sheets as an effective sulfur host. Adv Mater, 2020, 32: 1906357

    Article  CAS  Google Scholar 

  17. Xu ZL, Lin S, Onofrio N, et al. Exceptional catalytic effects of black phosphorus quantum dots in shuttling-free lithium sulfur batteries. Nat Commun, 2018, 9: 4164

    Article  Google Scholar 

  18. Yuan H, Peng HJ, Li BQ, et al. Conductive and catalytic triple-phase interfaces enabling uniform nucleation in high-rate lithium-sulfur batteries. Adv Energy Mater, 2019, 9: 1802768

    Article  Google Scholar 

  19. Du Z, Chen X, Hu W, et al. Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries. J Am Chem Soc, 2019, 141: 3977–3985

    Article  CAS  Google Scholar 

  20. Fan L, Zhuang HL, Zhang W, et al. Stable lithium electrodeposition at ultra-high current densities enabled by 3D PMF/Li composite anode. Adv Energy Mater, 2018, 8: 1703360

    Article  Google Scholar 

  21. Ni X, Qian T, Liu X, et al. High lithium ion conductivity LiF/GO solid electrolyte interphase inhibiting the shuttle of lithium polysulfides in long-life Li-S batteries. Adv Funct Mater, 2018, 28: 1706513

    Article  Google Scholar 

  22. Ma L, Zhang W, Wang L, et al. Strong capillarity, chemisorption, and electrocatalytic capability of crisscrossed nanostraws enabled flexible, high-rate, and long-cycling lithium-sulfur batteries. ACS Nano, 2018, 12: 4868–4876

    Article  CAS  Google Scholar 

  23. Lei T, Chen W, Hu Y, et al. A nonflammable and thermotolerant separator suppresses polysulfide dissolution for safe and long-cycle lithium-sulfur batteries. Adv Energy Mater, 2018, 8: 1802441

    Article  Google Scholar 

  24. Lei T, Chen W, Lv W, et al. Inhibiting polysulfide shuttling with a graphene composite separator for highly robust lithium-sulfur batteries. Joule, 2018, 2: 2091–2104

    Article  CAS  Google Scholar 

  25. Zhang XQ, He B, Li WC, et al. Hollow carbon nanofibers with dynamic adjustable pore sizes and closed ends as hosts for highrate lithium-sulfur battery cathodes. Nano Res, 2018, 11: 1238–1246

    Article  CAS  Google Scholar 

  26. Xie J, Li BQ, Peng HJ, et al. Implanting atomic cobalt within mesoporous carbon toward highly stable lithium-sulfur batteries. Adv Mater, 2019, 31: 1903813

    Article  CAS  Google Scholar 

  27. Huang Y, Zheng M, Lin Z, et al. Flexible cathodes and multifunctional interlayers based on carbonized bacterial cellulose for high-performance lithium-sulfur batteries. J Mater Chem A, 2015, 3: 10910–10918

    Article  CAS  Google Scholar 

  28. Abbas SA, Ding J, Wu SH, et al. Modified separator performing dual physical/chemical roles to inhibit polysulfide shuttle resulting in ultrastable Li-S batteries. ACS Nano, 2017, 11: 12436–12445

    Article  CAS  Google Scholar 

  29. Peng HJ, Zhang ZW, Huang JQ, et al. A cooperative interface for highly efficient lithium-sulfur batteries. Adv Mater, 2016, 28: 9551–9558

    Article  CAS  Google Scholar 

  30. Yim T, Han SH, Park NH, et al. Effective polysulfide rejection by dipole-aligned BaTiO3 coated separator in lithium-sulfur batteries. Adv Funct Mater, 2016, 26: 7817–7823

    Article  CAS  Google Scholar 

  31. Chung SH, Han P, Singhal R, et al. Electrochemically stable rechargeable lithium-sulfur batteries with a microporous carbon nanofiber filter for polysulfide. Adv Energy Mater, 2015, 5: 1500738

    Article  Google Scholar 

  32. Xie J, Peng HJ, Huang JQ, et al. A supramolecular capsule for reversible polysulfide storage/delivery in lithium-sulfur batteries. Angew Chem Int Ed, 2017, 56: 16223–16227

    Article  CAS  Google Scholar 

  33. Qu H, Ju J, Chen B, et al. Inorganic separators enable significantly suppressed polysulfide shuttling in high-performance lithium-sulfur batteries. J Mater Chem A, 2018, 6: 23720–23729

    Article  CAS  Google Scholar 

  34. Wu C, Yuan L, Li Z, et al. High-performance lithium-selenium battery with Se/microporous carbon composite cathode and carbonate-based electrolyte. Sci China Mater, 2015, 58: 91–97

    Article  CAS  Google Scholar 

  35. Yang X, Chen Y, Wang M, et al. Phase inversion: A universal method to create high-performance porous electrodes for nanoparticle-based energy storage devices. Adv Funct Mater, 2016, 26: 8427–8434

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Ministry of Science and Technology of China (2017YFA0700101, 2016YFA0202801 and 2016YBF0100100), China Postdoctoral Science Foundation funded project (2020TQ0164), the Shuimu Tsinghua Scholar Program, the National Natural Science Foundation of China (22035004, 51872283 and 21805273), Liaoning BaiQianWan Talents Program, Liaoning Revitalization Talents Program (XLYC1807153), Dalian Institute of Chemical Physics (DICP ZZBS201708, DICP ZZBS201802 and DICP I202032), DICP&QIBEBT (DICP&QIBEBT UN201702), and Dalian National Laboratory For Clean Energy (DNL) Cooperation Fund, CAS (DNL180310, DNL180308, DNL201912 and DNL201915).

Author information

Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Simin Zhang  (张思敏) & Xun Wang  (王训)

  2. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Haodong Shi  (石浩东) & Zhong-Shuai Wu  (吴忠帅)

  3. Dalian National Laboratory for Clean Energy (DNL), Chinese Academy of Sciences (CAS), Dalian, 116023, China

    Haodong Shi  (石浩东) & Zhong-Shuai Wu  (吴忠帅)

  4. University of Chinese Academy of Sciences, Beijing, 100049, China

    Haodong Shi  (石浩东) & Zhong-Shuai Wu  (吴忠帅)

  5. Department of Chemical Engineering, University College London (UCL), WC1E 7JE, London, UK

    Junwang Tang  (唐军旺)

  6. Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300387, China

    Wenxiong Shi  (匙文雄)

Authors
  1. Simin Zhang  (张思敏)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Haodong Shi  (石浩东)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Junwang Tang  (唐军旺)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wenxiong Shi  (匙文雄)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhong-Shuai Wu  (吴忠帅)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Xun Wang  (王训)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Wang X initiated and guided the research. Zhang S designed and performed the experiments, and wrote the manuscript under the guidance of Wang X. Shi H and Wu ZS performed the electrochemical tests. Shi W and Tang J performed the simulations.

Corresponding authors

Correspondence to Wenxiong Shi  (匙文雄), Zhong-Shuai Wu  (吴忠帅) or Xun Wang  (王训).

Additional information

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Simin Zhang received her PhD degree in Prof. Xun Wang’s group from Tsinghua University in 2020. Currently, she is a post-doctor researcher in Prof. Xun Wang’s group at the Department of Chemistry, Tsinghua University. Her current research focuses on the synthesis and application of sub-1 nm nanowires/nanobelts.

Haodong Shi received his bachelor’s degree in applied chemistry from Northeastern University in 2016. He is pursuing the PhD degree from Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences (CAS), under the supervision of Prof. Zhong-Shuai Wu. His research interests focus on graphene and 2D materials for high-energy batteries.

Wenxiong Shi received his PhD degree from the Institute of Chemistry, CAS. And he is a professor at Tianjin University of Technology. His research interest focuses on simulation of polyoxometalate clusters and metal-organic frameworks.

Zhong-Shuai Wu received his PhD degree from the Institute for Metal Research, CAS, in 2011 and worked as a postdoctoral fellow at the Max Planck Institute for Polymer Research in Mainz, Germany, from 2011 to 2015. He is a DICP chair professor now. His research interests include graphene and 2D materials, surface- and nanoelectrochemistry, microscale electrochemical energy storage devices, supercapacitors, batteries and catalysts.

Xun Wang received his PhD degree from the Department of Chemistry, Tsinghua University in 2004. He then joined the faculty of the Department of Chemistry, Tsinghua University in 2004, and was promoted to associate professor and full professor in 2005 and 2007, respectively. His current research interests include the synthetic methodology, formation mechanism, and properties of monodisperse nanocrystals.

Supplementary data for

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, S., Shi, H., Tang, J. et al. Super-aligned films of sub-1 nm Bi2O3-polyoxometalate nanowires as interlayers in lithium-sulfur batteries. Sci. China Mater. 64, 2949–2957 (2021). https://doi.org/10.1007/s40843-021-1688-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-021-1688-7

Keywords

Search

Navigation