Infiltrating lithium into carbon cloth decorated with zinc oxide arrays for dendrite-free lithium metal anode

  • Xianshu Wang
  • Zhenghui Pan
  • Yang Wu
  • Xiaoyu Ding
  • Xujia Hong
  • Guoguang Xu
  • Meinan Liu
  • Yuegang ZhangEmail author
  • Weishan LiEmail author
Research Article


Lithium metal anode for batteries has attracted extensive attentions, but its application is restricted by the hazardous dendritic Li growth and dead Li formation. To address these issues, a novel Li anode is developed by infiltrating molten Li metal into conductive carbon cloth decorated with zinc oxide arrays. In carbonate-based electrolyte, the symmetric cell shows no short circuit over 1,500 h at 1 mA·cm−2, and stable voltage profiles at 3 mA·cm−2 for ∼ 300 h cycling. A low overpotential of ∼ 243 mV over 350 cycles at a high current density of 10 mA·cm−2 is achieved, compared to the seriously fluctuated voltage and fast short circuit in the cell using bare Li metal. Meanwhile, the asymmetric cell withstands 1,000 cycles at 10 C (1 C = 167 mAh·g−1) compared to the 210 cycles for the cell using bare Li anode. The excellent performance is attributed to the well-regulated Li plating/stripping driven from the formation of LiZn alloy on the wavy carbon fibers, resulting in the suppression of dendrite growth and pulverization of the Li electrode during cycling.


lithium metal anodes lithium plating/stripping dendrite-free thermal infiltration carbon cloth zinc oxide nanowire arrays 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.



This work is financially supported by the National Key Research and Development Program of China (Nos. 2016YFB0100100 and 2018YFB0104000), the Key Project of Science and Technology in Guangdong Province (No. 2017A010106006), and the National Natural Science Foundation of China (Nos. 21433013 and 51471073).

Supplementary material

Supplementary material, approximately 3.86 MB.

12274_2018_2245_MOESM2_ESM.pdf (4.3 mb)
Infiltrating lithium into carbon cloth decorated with zinc oxide arrays for dendrite-free lithium metal anode


  1. [1]
    Zhu, Y. Q.; Cao, T.; Li, Z.; Chen, C.; Peng, Q.; Wang, D. S.; Li, Y. D. Two-dimensional SnO2/graphene heterostructures for highly reversible electrochemical lithium storage. Sci. China Mater. 2018, 61, 1527–1535.CrossRefGoogle Scholar
  2. [2]
    Kim, H.; Jeong, G.; Kim, Y. U.; Kim, J. H.; Park, C. M.; Sohn, H. J. Metallic anodes for next generation secondary batteries. Chem. Soc. Rev. 2013, 42, 9011–9034.CrossRefGoogle Scholar
  3. [3]
    Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Toward safe lithium metal anode in rechargeable batteries: A review. Chem. Rev. 2017, 117, 10403–10473.CrossRefGoogle Scholar
  4. [4]
    Xu, W.; Wang, J. L.; Ding, F.; Chen, X. L.; Nasybulin, E.; Zhang, Y. H.; Zhang, J. G. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 2014, 7, 513–537.CrossRefGoogle Scholar
  5. [5]
    Wang, D.; Zhang, W.; Zheng, W. T.; Cui, X. Q.; Rojo, T.; Zhang, Q. Towards high-safe lithium metal anodes: Suppressing lithium dendrites via tuning surface energy. Adv. Sci. 2017, 4, 1600168.CrossRefGoogle Scholar
  6. [6]
    Lin, D. C.; Liu, Y. Y.; Pei, A.; Cui, Y. Nanoscale perspective: Materials designs and understandings in lithium metal anodes. Nano Res. 2017, 10, 4003–4026.CrossRefGoogle Scholar
  7. [7]
    Guo, Y. P.; Li, H. Q.; Zhai, T. Y. Reviving lithium-metal anodes for nextgeneration high-energy batteries. Adv. Mater. 2017, 29, 1700007.CrossRefGoogle Scholar
  8. [8]
    Li, N.; Wei, W. F.; Xie, K. Y.; Tan, J. W.; Zhang, L.; Luo, X. D.; Yuan, K.; Song, Q.; Li, H. J.; Shen, C. et al. Suppressing dendritic lithium formation using porous media in lithium metal-based batteries. Nano Lett. 2018, 18, 2067–2073.CrossRefGoogle Scholar
  9. [9]
    Zhang, K.; Lee, G. H.; Park, M.; Li, W. J.; Kang, Y. M. Recent developments of the lithium metal anode for rechargeable non-aqueous batteries. Adv. Energy Mater. 2016, 6, 1600811.CrossRefGoogle Scholar
  10. [10]
    Yin, Y. X.; Xin, S.; Guo, Y. G.; Wan, L. J. Lithium-sulfur batteries: Electrochemistry, materials, and prospects. Angew. Chem., Int. Ed. 2013, 52, 13186–13200.CrossRefGoogle Scholar
  11. [11]
    Choi, J. W.; Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 2016, 1, 16013.CrossRefGoogle Scholar
  12. [12]
    Xin, S.; Chang, Z. W.; Zhang, X. B.; Guo, Y. G. Progress of rechargeable lithium metal batteries based on conversion reactions. Natl. Sci. Rev. 2017, 4, 54–70.Google Scholar
  13. [13]
    Song, Q.; Yan, H. B.; Liu, K. D.; Xie, K. Y.; Li, W.; Gai, W. H.; Chen, G. H.; Li, H. J.; Shen, C.; Fu, Q. G. et al. Vertically grown edge-rich graphene nanosheets for spatial control of Li nucleation. Adv. Energy Mater. 2018, 8, 1800564.CrossRefGoogle Scholar
  14. [14]
    Yan, K.; Lee, H. W.; Gao, T.; Zheng, G. Y.; Yao, H. B.; Wang, H. T.; Lu, Z. D.; Zhou, Y.; Liang, Z.; Liu, Z. F. et al. Ultrathin two-dimensional atomic crystals as stable interfacial layer for improvement of lithium metal anode. Nano Lett. 2014, 14, 6016–6022.CrossRefGoogle Scholar
  15. [15]
    Zheng, G. Y.; Lee, S. W.; Liang, Z.; Lee, H. W.; Yan, K.; Yao, H. B.; Wang, H. T.; Li, W. Y.; Chu, S.; Cui, Y. Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nat. Nanotechnol. 2014, 9, 618–623.CrossRefGoogle Scholar
  16. [16]
    Lin, D. C.; Liu, Y. Y.; Cui, Y. Reviving the lithium metal anode for highenergy batteries. Nat. Nanotechnol. 2017, 12, 194–206.CrossRefGoogle Scholar
  17. [17]
    Zhang, R.; Cheng, X. B.; Zhao, C. Z.; Peng, H. J.; Shi, J. L.; Huang, J. Q.; Wang, J. F.; Wei, F.; Zhang, Q. Conductive nanostructured scaffolds render low local current density to inhibit lithium dendrite growth. Adv. Mater. 2016, 28, 2155–2162.CrossRefGoogle Scholar
  18. [18]
    Lu, L. L.; Ge, J.; Yang, J. N.; Chen, S. M.; Yao, H. B.; Zhou, F.; Yu, S. H. Free-standing copper nanowire network current collector for improving lithium anode performance. Nano Lett. 2016, 16, 4431–4437.CrossRefGoogle Scholar
  19. [19]
    Yan, K.; Lu, Z. D.; Lee, H. W.; Xiong, F.; Hsu, P. C.; Li, Y. Z.; Zhao, J.; Chu, S.; Cui, Y. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nat. Energy 2016, 1, 16010.CrossRefGoogle Scholar
  20. [20]
    Ye, H.; Xin, S.; Yin, Y. X.; Li, J. Y.; Guo, Y. G.; Wan, L. J. Stable Li plating/ stripping electrochemistry realized by a hybrid Li reservoir in spherical carbon granules with 3D conducting skeletons. J. Am. Chem. Soc. 2017, 139, 5916–5922.CrossRefGoogle Scholar
  21. [21]
    Jin, C. B.; Sheng, O. W.; Luo, J. M.; Yuan, H. D.; Fang, C.; Zhang, W. K.; Huang, H.; Gan, Y. P.; Xia, Y.; Liang, C. et al. 3D lithium metal embedded within lithiophilic porous matrix for stable lithium metal batteries. Nano Energy 2017, 37, 177–186.CrossRefGoogle Scholar
  22. [22]
    Yang, C. P.; Yin, Y. X.; Zhang, S. F.; Li, N. W.; Guo, Y. G. Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes. Nat. Commun. 2015, 6, 8058.CrossRefGoogle Scholar
  23. [23]
    Zuo, T. T.; Wu, X. W.; Yang, C. P.; Yin, Y. X.; Ye, H.; Li, N. W.; Guo, Y. G. Graphitized carbon fibers as multifunctional 3D current collectors for high areal capacity Li anodes. Adv. Mater. 2017, 29, 1700389.CrossRefGoogle Scholar
  24. [24]
    Raji, A. R. O.; Villegas Salvatierra, R.; Kim, N. D.; Fan, X. J.; Li, Y. L.; Silva, G. A. L.; Sha, J. W.; Tour, J. M. Lithium batteries with nearly maximum metal storage. ACS Nano 2017, 11, 6362–6369.CrossRefGoogle Scholar
  25. [25]
    Wang, X. S.; Pan, Z. H.; Wu, Y.; Xu, G. G.; Zheng, X. W.; Qiu, Y. C.; Liu, M. N.; Zhang, Y. G.; Li, W. S. Reducing lithium deposition overpotential with silver nanocrystals anchored on graphene aerogel. Nanoscale 2018, 10, 16562–16567.CrossRefGoogle Scholar
  26. [26]
    Liu, W.; Li, W. Y.; Zhuo, D.; Zheng, G. Y.; Lu, Z. D.; Liu, K.; Cui, Y. Core-shell nanoparticle coating as an interfacial layer for dendrite-free lithium metal anodes. ACS Cent. Sci. 2017, 3, 135–140.CrossRefGoogle Scholar
  27. [27]
    Zhang, R.; Chen, X. R.; Chen, X.; Cheng, X. B.; Zhang, X. Q.; Yan, C.; Zhang, Q. Lithiophilic sites in doped graphene guide uniform lithium nucleation for dendrite-free lithium metal anodes. Angew. Chem., Int. Ed. 2017, 56, 7764–7768.CrossRefGoogle Scholar
  28. [28]
    Zhang, Y.; Liu, B. Y.; Hitz, E.; Luo, W.; Yao, Y. G.; Li, Y. J.; Dai, J. Q.; Chen, C. J.; Wang, Y. B.; Yang, C. P. et al. A carbon-based 3D current collector with surface protection for Li metal anode. Nano Res. 2017, 10, 1356–1365.CrossRefGoogle Scholar
  29. [29]
    Liang, Z.; Lin, D. C.; Zhao, J.; Lu, Z. D.; Liu, Y. Y.; Liu, C.; Lu, Y. Y.; Wang, H. T.; Yan, K.; Tao, X. Y. et al. Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating. Proc. Natl. Acad. Sci. USA 2016, 113, 2862–2867.CrossRefGoogle Scholar
  30. [30]
    Liu, Y. Y.; Lin, D. C.; Liang, Z.; Zhao, J.; Yan, K.; Cui, Y. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode. Nat. Commun. 2016, 7, 10992.CrossRefGoogle Scholar
  31. [31]
    Zhang, R.; Chen, X.; Shen, X.; Zhang, X. Q.; Chen, X. R.; Cheng, X. B.; Yan, C.; Zhao, C. Z.; Zhang, Q. Coralloid carbon fiber-based composite lithium anode for robust lithium metal batteries. Joule 2018, 2, 764–777.CrossRefGoogle Scholar
  32. [32]
    Lin, D. C.; Liu, Y. Y.; Liang, Z.; Lee, H. W.; Sun, J.; Wang, H. T.; Yan, K.; Xie, J.; Cui, Y. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes. Nat. Nanotechnol. 2016, 11, 626–632.CrossRefGoogle Scholar
  33. [33]
    Zhang, Y.; Luo, W.; Wang, C. W.; Li, Y. J.; Chen, C. J.; Song, J. W.; Dai, J. Q.; Hitz, E. M.; Xu, S. M.; Yang, C. P. et al. High-capacity, low-tortuosity, and channel-guided lithium metal anode. Proc. Natl. Acad. Sci. USA 2017, 114, 3584–3589.CrossRefGoogle Scholar
  34. [34]
    Chi, S. S.; Liu, Y. C.; Song, W. L.; Fan, L. Z.; Zhang, Q. Prestoring lithium into stable 3D nickel foam host as dendrite-free lithium metal anode. Adv. Funct. Mater. 2017, 27, 1700348.CrossRefGoogle Scholar
  35. [35]
    Wang, C. W.; Gong, Y. H.; Liu, B. Y.; Fu, K.; Yao, Y. G.; Hitz, E.; Li, Y. J.; Dai, J. Q.; Xu, S. M.; Luo, W. et al. Conformal, nanoscale ZnO surface modification of garnet-based solid-state electrolyte for lithium metal anodes. Nano Lett. 2017, 17, 565–571.CrossRefGoogle Scholar
  36. [36]
    Fu, K.; Gong, Y. H.; Liu, B. Y.; Zhu, Y. Z.; Xu, S. M.; Yao, Y. G.; Luo, W.; Wang, C. W.; Lacey S. D.; Dai, J. Q. et al. Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface. Sci. Adv. 2017, 3, e1601659.CrossRefGoogle Scholar
  37. [37]
    Deng, W.; Zhou, X. F.; Fang, Q. L.; Liu, Z. P. Microscale lithium metal stored inside cellular graphene scaffold toward advanced metallic lithium anodes. Adv. Energy Mater. 2018, 8, 1703152.CrossRefGoogle Scholar
  38. [38]
    He, S. S.; Qiu, L. B.; Fang, X.; Guan, G. Z.; Chen, P. N.; Zhang, Z. T.; Peng, H. S. Radically grown obelisk-like ZnO arrays for perovskite solar cell fibers and fabrics through a mild solution process. J. Mater. Chem. A 2015, 3, 9406–9410.CrossRefGoogle Scholar
  39. [39]
    Greene, L. E.; Law, M.; Tan, D. H.; Montano, M.; Goldberger, J.; Somorjai, G.; Yang, P. D. General route to vertical ZnO nanowire arrays using textured ZnO seeds. Nano Lett. 2005, 5, 1231–1236.CrossRefGoogle Scholar
  40. [40]
    Yi, S. H.; Choi, S. K.; Jang, J. M.; Kim, J. A.; Jung, W. G. Low-temperature growth of ZnO nanorods by chemical bath deposition. J. Colloid Interface Sci. 2007, 313, 705–710.CrossRefGoogle Scholar
  41. [41]
    Li, Q.; Zhu, S. P.; Lu, Y. Y. 3D porous Cu current collector/Li-metal composite anode for stable lithium-metal batteries. Adv. Funct. Mater. 2017, 27, 1606422.CrossRefGoogle Scholar
  42. [42]
    Bieker, G.; Winter, M.; Bieker, P. Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode. Phys. Chem. Chem. Phys. 2015, 17, 8670–8679.CrossRefGoogle Scholar
  43. [43]
    Li, N. W.; Yin, Y. X.; Li, J. Y.; Zhang, C. H.; Guo, Y. G. Passivation of lithium metal anode via hybrid ionic liquid electrolyte toward stable Li plating/stripping. Adv. Sci. 2017, 4, 1600400.CrossRefGoogle Scholar
  44. [44]
    Heine, J.; Krüger, S.; Hartnig, C.; Wietelmann, U.; Winter, M.; Bieker, P. Coated lithium powder (CLiP) electrodes for lithium-metal batteries. Adv. Energy Mater. 2014, 4, 1300815.CrossRefGoogle Scholar
  45. [45]
    Hafez, A. M.; Jiao, Y. C.; Shi, J. J.; Ma, Y.; Cao, D. X.; Liu, Y. Y.; Zhu, H. L. Stable metal anode enabled by porous lithium foam with superior ion accessibility. Adv. Mater. 2018, 30, 1802156.CrossRefGoogle Scholar
  46. [46]
    Liu, S. F.; Xia, X. H.; Yao, Z. J.; Wu, J. B.; Zhang, L. Y.; Deng, S. J.; Zhou, C. G.; Shen, S. H.; Wang, X. L.; Tu, J. P. Straw-brick-like carbon fiber cloth/lithium composite electrode as an advanced lithium metal anode. Small Methods 2018, 2, 1800035.CrossRefGoogle Scholar
  47. [47]
    Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 2004, 104, 4303–4418.CrossRefGoogle Scholar
  48. [48]
    Yamaki, J. I.; Tobishima, S. I.; Hayashi K.; Saito, K.; Nemoto, Y.; Arakawa, M. A consideration of the morphology of electrochemically deposited lithium in an organic electrolyte. J. Power Sources 1998, 74, 219–227.CrossRefGoogle Scholar
  49. [49]
    Lu, Y. Y.; Tu, Z. Y.; Archer, L. A. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 2014, 13, 961–969.CrossRefGoogle Scholar

Copyright information

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Xianshu Wang
    • 1
    • 2
  • Zhenghui Pan
    • 2
  • Yang Wu
    • 3
  • Xiaoyu Ding
    • 2
  • Xujia Hong
    • 1
  • Guoguang Xu
    • 2
  • Meinan Liu
    • 2
  • Yuegang Zhang
    • 2
    • 3
    • 4
    Email author
  • Weishan Li
    • 1
    • 4
    Email author
  1. 1.School of Chemistry and EnvironmentSouth China Normal UniversityGuangzhouChina
  2. 2.i-lab, Suzhou Institute of Nano-Tech and Nano-BionicsChinese Academy of SciencesSuzhouChina
  3. 3.Department of PhysicsTsinghua UniversityBeijingChina
  4. 4.Engineering Research Center of MTEES (Ministry of Education), Research Center of BMET (Guangdong Province), and Key Laboratory of ETESPG (GHEI)South China Normal UniversityGuangzhouChina

Personalised recommendations