Skip to main content
SpringerLink
Log in

An efficient and versatile biopolishing strategy to construct high performance zinc anode

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

Abstract

Conventional strategies for highly reversible Zn anodes usually involve complex and time-consuming production processes of current collectors, expensive and toxic electrolyte additives, or the introduction of inactive materials in protective layer. Here, we develop a fast, facile, and environmentally friendly biopolishing method to prepare dendrite-free Zn anodes, which merely involves the simple immersion of Zn foil in a biocompatible cysteine aqueous solution. The ravine structure formed by sulfhydryl etching for 30 min not only increases the electroactive area of Zn anode but also regulates the distribution of electric field and Zn ions, ensuring the homogeneous deposition and stripping of Zn ions. The biopolished Zn anode can be operated steadily for 2,000 h with a low voltage hysteresis at a current density of 1 mA·cm−2. In addition, Zn anodes with a cycle life of 500 h can be built by soaking for only 5 min, proving the high efficiency of the proposed method. This strategy is generalized to substances with sulfhydryl groups for polishing Zn electrodes with improved performance. The cysteine-polished Zn//activated carbon supercapacitor can stably run for 20,000 cycles without obvious capacity attenuation. The proposed strategy shows potential for producing advanced Zn anodes.

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. Kundu, D.; Adams, B. D.; Duffort, V.; Vajargah, S. H.; Nazar, L. F. A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode. Nat. Energy 2016, 1, 16119.

    Article  CAS  Google Scholar 

  2. Zhang, N.; Chen, X. Y.; Yu, M.; Niu, Z. Q.; Cheng, F. Y.; Chen, J. Materials chemistry for rechargeable zinc-ion batteries. Chem. Soc. Rev. 2020, 49, 4203–4219.

    Article  CAS  Google Scholar 

  3. Parker, J. F.; Chervin, C. N.; Pala, I. R.; Machler, M.; Burz, M. F.; Long, J. W.; Rolison, D. R. Rechargeable nickel-3D zinc batteries: An energy-dense, safer alternative to lithium-ion. Science 2017, 356, 415–418.

    Article  CAS  Google Scholar 

  4. Li, B. Q.; Zhang, S. Y.; Wang, B.; Xia, Z. J.; Tang, C.; Zhang, Q. A porphyrin covalent organic framework cathode for flexible Zn-air batteries. Energy Environ. Sci. 2018, 11, 1723–1729.

    Article  CAS  Google Scholar 

  5. Pan, H. L.; Shao, Y. Y.; Yan, P. F.; Cheng, Y. W.; Han, K. S.; Nie, Z. M.; Wang, C. M.; Yang, J. H.; Li, X. L.; Bhattacharya, P. et al. Reversible aqueous zinc/manganese oxide energy storage from conversion reactions. Nat. Energy 2016, 1, 16039.

    Article  CAS  Google Scholar 

  6. Xu, C. J.; Li, B. H.; Du, H. D.; Kang, F. Y. Energetic zinc ion chemistry: The rechargeable zinc ion battery. Angew. Chem., Int. Ed. 2012, 51, 933–935.

    Article  CAS  Google Scholar 

  7. Blanc, L. E.; Kundu, D.; Nazar, L. F. Scientific challenges for the implementation of Zn-Ion batteries. Joule 2020, 4, 771–799.

    Article  CAS  Google Scholar 

  8. Liu, H. Y.; Wang, J. G.; You, Z. Y.; Wei, C. G.; Kang, F. Y.; Wei, B. Q. Rechargeable aqueous zinc-ion batteries: Mechanism, design strategies and future perspectives. Mater. Today 2021, 42, 73–98.

    Article  CAS  Google Scholar 

  9. Sun, G. Q.; Yang, H. S.; Zhang, G. F.; Gao, J.; Jin, X. T.; Zhao, Y.; Jiang, L.; Qu, L. T. A capacity recoverable zinc-ion micro-supercapacitor. Energy Environ. Sci. 2018, 11, 3367–3374.

    Article  CAS  Google Scholar 

  10. Jia, H.; Wang, Z. Q.; Tawiah, B.; Wang, Y. D.; Chan, C. Y.; Fei, B.; Pan, F. Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries. Nano Energy 2020, 70, 104523.

    Article  CAS  Google Scholar 

  11. Yang, Q.; Guo, Y.; Yan, B. X.; Wang, C. D.; Liu, Z. X.; Huang, Z. D.; Wang, Y. K.; Li, Y. R.; Li, H. F.; Song, L. et al. Hydrogen-substituted graphdiyne ion tunnels directing concentration redistribution for commercial-grade dendrite-free zinc anodes. Adv. Mater. 2020, 32, 2001755.

    Article  CAS  Google Scholar 

  12. Zhao, Z. M.; Zhao, J. W.; Hu, Z. L.; Li, J. D.; Li, J. J.; Zhang, Y. J.; Wang, C.; Cui, G. L. Long-life and deeply rechargeable aqueous Zn anodes enabled by a multifunctional brightener-inspired interphase. Energy Environ. Sci. 2019, 12, 1938–1949.

    Article  CAS  Google Scholar 

  13. Shin, J.; Lee, J.; Park, Y.; Choi, J. W. Aqueous zinc ion batteries: Focus on zinc metal anodes. Chem. Sci. 2020, 11, 2028–2044.

    Article  Google Scholar 

  14. Tian, Y.; An, Y. L.; Wei, C. L.; Xi, B. J.; Xiong, S. L.; Feng, J. K.; Qian, Y. T. Flexible and free-standing Ti3C2Tx MXene@Zn paper for dendrite-free aqueous zinc metal batteries and nonaqueous lithium metal batteries. ACS Nano 2019, 13, 11676–11685.

    Article  CAS  Google Scholar 

  15. Qian, Y.; Meng, C.; He, J. X.; Dong, X. A lightweight 3D Zn@Cu nanosheets@activated carbon cloth as long-life anode with large capacity for flexible zinc ion batteries. J. Power Sources 2020, 480, 228871.

    Article  CAS  Google Scholar 

  16. Lu, K.; Zhang, H.; Song, B.; Pan, W.; Ma, H. Y.; Zhang, J. T. Sulfur and nitrogen enriched graphene foam scaffolds for aqueous rechargeable zinc-iodine battery. Electrochim. Acta 2019, 296, 755–761.

    Article  CAS  Google Scholar 

  17. Kang, Z.; Wu, C. L.; Dong, L. B.; Liu, W. B.; Mou, J.; Zhang, J. W.; Chang, Z. W.; Jiang, B. Z.; Wang, G. X.; Kang, F. Y. et al. 3D porous copper skeleton supported zinc anode toward high capacity and long cycle life zinc ion batteries. ACS Sustainable Chem. Eng. 2019, 7, 3364–3371.

    Article  CAS  Google Scholar 

  18. Zhang, Q.; Luan, J. Y.; Fu, L.; Wu, S. A.; Tang, Y. G.; Ji, X. B.; Wang, H. Y. The three-dimensional dendrite-free zinc anode on a copper mesh with a zinc-oriented polyacrylamide electrolyte additive. Angew. Chem., Int. Ed. 2019, 58, 15841–15847.

    Article  CAS  Google Scholar 

  19. Sun, K. E. K.; Hoang, T. K. A.; Doan, T. N. L.; Yu, Y.; Zhu, X.; Tian, Y.; Chen, P. Suppression of dendrite formation and corrosion on zinc anode of secondary aqueous batteries. ACS Appl. Mater. Interfaces 2017, 9, 9681–9687.

    Article  CAS  Google Scholar 

  20. Zhang, N.; Cheng, F. Y.; Liu, Y. C.; Zhao, Q.; Lei, K. X.; Chen, C. C.; Liu, X. S.; Chen, J. Cation-deficient spinel ZnMn2O4 cathode in Zn(CF3SO3)2 electrolyte for rechargeable aqueous Zn-ion battery. J. Am. Chem. Soc. 2016, 138, 12894–12901.

    Article  CAS  Google Scholar 

  21. Cong, J. L.; Shen, X.; Wen, Z. P.; Wang, X.; Peng, L. Q.; Zeng, J.; Zhao, J. B. Ultra-stable and highly reversible aqueous zinc metal anodes with high preferred orientation deposition achieved by a polyanionic hydrogel electrolyte. Energy Storage Mater. 2021, 35, 586–594.

    Article  Google Scholar 

  22. Wang, F.; Borodin, O.; Gao, T.; Fan, X. L.; Sun, W.; Han, F. D.; Faraone, A.; Dura, J. A.; Xu, K.; Wang, C. S. Highly reversible zinc metal anode for aqueous batteries. Nat. Mater. 2018, 17, 543–549.

    Article  CAS  Google Scholar 

  23. Zhao, K. N.; Wang, C. X.; Yu, Y. H.; Yan, M. Y.; Wei, Q. L.; He, P.; Dong, Y. F.; Zhang, Z. Y.; Wang, X. D.; Mai, L. Q. Ultrathin surface coating enables stabilized zinc metal anode. Adv. Mater. Interfaces 2018, 5, 1800848.

    Article  CAS  Google Scholar 

  24. Xie, X. S.; Liang, S. Q.; Gao, J. W.; Guo, S.; Guo, J. B.; Wang, C.; Xu, G. Y.; Wu, X. W.; Chen, G.; Zhou, J. Manipulating the ion-transfer kinetics and interface stability for high-performance zinc metal anodes. Energy Environ. Sci. 2020, 13, 503–510.

    Article  CAS  Google Scholar 

  25. Hao, J. N.; Li, B.; Li, X. L.; Zeng, X. H.; Zhang, S. L.; Yang, F. H.; Liu, S. L.; Li, D.; Wu, C.; Guo, Z. P. An in-depth study of Zn metal surface chemistry for advanced aqueous Zn-ion batteries. Adv. Mater. 2020, 32, 2003021.

    Article  CAS  Google Scholar 

  26. Hao, J. N.; Li, X. L.; Zhang, S. L.; Yang, F. H.; Zeng, X. H.; Zhang, S.; Bo, G. Y.; Wang, C. S.; Guo, Z. P. Designing dendrite-free zinc anodes for advanced aqueous zinc batteries. Adv. Funct. Mater. 2020, 30, 2001263.

    Article  CAS  Google Scholar 

  27. Hieu, L. T.; So, S.; Kim, I. T.; Hur, J. Zn anode with flexible β-PVDF coating for aqueous Zn-ion batteries with long cycle life. Chem. Eng. J. 2021, 411, 128584.

    Article  CAS  Google Scholar 

  28. Deng, C. B.; Xie, X. S.; Han, J. W.; Tang, Y.; Gao, J. W.; Liu, C. X.; Shi, X. D.; Zhou, J.; Liang, S. Q. A sieve-functional and uniformporous kaolin layer toward stable zinc metal anode. Adv. Funct. Mater. 2020, 30, 2000599.

    Article  CAS  Google Scholar 

  29. Qian, B. T.; Shen, Z. Q. Fabrication of superhydrophobic surfaces by dislocation-selective chemical etching on aluminum, copper, and zinc substrates. Langmuir 2005, 21, 9007–9009.

    Article  CAS  Google Scholar 

  30. Wang, H. J.; Yang, Z.; Yu, J.; Wu, Y. Z.; Shao, W. J.; Jiang, T. T.; Xu, X. L. Preparation of lotus-like hierarchical microstructures on zinc substrate and study of its wettability. RSC Adv. 2014, 4, 33730–33738.

    Article  CAS  Google Scholar 

  31. Sangaj, N. S.; Malshe, V. C. Permeability of polymers in protective organic coatings. Prog. Org. Coat. 2004, 50, 28–39.

    Article  CAS  Google Scholar 

  32. Winiarski, J.; Tylus, W.; Winiarska, K.; Szczygieł, I.; Szczygieł, B. XPS and FT-IR characterization of selected synthetic corrosion products of zinc expected in neutral environment containing chloride ions. J. Spectrosc. 2018, 2018, 2079278.

    Google Scholar 

  33. Cao, Z. Y.; Zhu, X. D.; Xu, D. X.; Dong, P.; Chee, M. O. L.; Li, X. J.; Zhu, K. Y.; Ye, M. X.; Shen, J. F. Eliminating Zn dendrites by commercial cyanoacrylate adhesive for zinc ion battery. Energy Storage Mater. 2021, 36, 132–138.

    Article  Google Scholar 

  34. Kang, L. T.; Cui, M. W.; Jiang, F. Y.; Gao, Y. F.; Luo, H. J.; Liu, J. J.; Liang, W.; Zhi, C. Y. Nanoporous CaCO3 coatings enabled uniform Zn stripping/plating for long-life zinc rechargeable aqueous batteries. Adv. Energy Mater. 2018, 8, 1801090.

    Article  CAS  Google Scholar 

  35. Zeng, Y. X.; Zhang, X. Y.; Qin, R. F.; Liu, X. Q.; Fang, P. P.; Zheng, D. Z.; Tong, Y. X.; Lu, X. H. Dendrite-free zinc deposition induced by multifunctional CNT frameworks for stable flexible Zn-ion batteries. Adv. Mater. 2019, 31, 1903675.

    Article  CAS  Google Scholar 

  36. Wang, J. D.; Cai, Z.; Xiao, R.; Ou, Y. T.; Zhan, R. M.; Yuan, Z.; Sun, Y. M. A chemically polished zinc metal electrode with a ridge-like structure for cycle-stable aqueous batteries. ACS Appl. Mater. Interfaces 2020, 12, 23028–23034.

    Article  CAS  Google Scholar 

  37. Wang, Z.; Huang, J. H.; Guo, Z. W.; Dong, X. L.; Liu, Y.; Wang, Y. G.; Xia, Y. Y. A metal-organic framework host for highly reversible dendrite-free zinc metal anodes. Joule 2019, 3, 1289–1300.

    Article  CAS  Google Scholar 

  38. Kim, J. Y.; Liu, G. C.; Shim, G. Y.; Kim, H.; Lee, J. K. Functionalized Zn@ZnO hexagonal pyramid array for dendrite-free and ultrastable zinc metal anodes. Adv. Funct. Mater. 2020, 30, 2004210.

    Article  CAS  Google Scholar 

  39. Zhou, M.; Guo, S.; Li, J. L.; Luo, X. B.; Liu, Z. X.; Zhang, T. S.; Cao, X. X.; Long, M. Q.; Lu, B. A.; Pan, A. Q. et al. Surface-preferred crystal plane for a stable and reversible zinc anode. Adv. Mater. 2021, 33, 2100187.

    Article  CAS  Google Scholar 

  40. Bayaguud, A.; Luo, X.; Fu, Y. P.; Zhu, C. B. Cationic surfactant-type electrolyte additive enables three-dimensional dendrite-free zinc anode for stable zinc-ion batteries. ACS Energy Lett. 2020, 5, 3012–2020.

    Article  CAS  Google Scholar 

  41. Li, D.; Cao, L. S.; Deng, T.; Liu, S. F.; Wang, C. S. Design of a solid electrolyte interphase for aqueous Zn batteries. Angew. Chem., Int. Ed. 2021, 60, 13035–13041.

    Article  CAS  Google Scholar 

  42. Lopez, J.; Pei, A.; Oh, J. Y.; Wang, G. J. N.; Cui, Y.; Bao, Z. N. Effects of polymer coatings on electrodeposited lithium metal. J. Am. Chem. Soc. 2018, 140, 11735–11744.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21825106 and 92061201), the Program for Innovative Research Team (in Science and Technology) in Universities of Henan Province (No. 19IRTSTHN022) and Zhengzhou University.

Author information

Authors and Affiliations

  1. Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China

    Guoqiang Sun, Mengqi Zhou, Xi-Yan Dong & Shuang-Quan Zang

  2. College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo, 454000, China

    Xi-Yan Dong

  3. Department of Chemistry & Department of Mechanical Engineering, Tsinghua University, Beijing, 100084, China

    Liangti Qu

Authors
  1. Guoqiang Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mengqi Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xi-Yan Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Shuang-Quan Zang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Liangti Qu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Shuang-Quan Zang or Liangti Qu.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sun, G., Zhou, M., Dong, XY. et al. An efficient and versatile biopolishing strategy to construct high performance zinc anode. Nano Res. 15, 5081–5088 (2022). https://doi.org/10.1007/s12274-022-4116-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-022-4116-x

Keywords

Search

Navigation