Citation: Jiaojiao Deng, Haocheng Li, Fei Zheng, Qingsong Weng, Yu Bai, Xiaoliang Yu, Qianlin Zhang, Qinghua Liang, Baohua Li. A “breathable” 3D lithium host with MnO₂ nanoflake array for long-lifespan anode-free lithium metal batteries[J]. Chinese Chemical Letters, ;2026, 37(3): 110681. doi: 10.1016/j.cclet.2024.110681 shu

A “breathable” 3D lithium host with MnO₂ nanoflake array for long-lifespan anode-free lithium metal batteries

Jiaojiao Deng ^a ,
Haocheng Li ^b ,
Fei Zheng ^c ,
Qingsong Weng ^c ,
Yu Bai ^c ,
Xiaoliang Yu ^{c, *,} ,
Qianlin Zhang ^{a, *,} ,
Qinghua Liang ^{d, *,} ,
Baohua Li ^e

a.
Graphene Composite Research Center, College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, China
b.
School of Mechanical Engineering, Beijing Institute of Technology, Beijing 100081, China
c.
Department of Mechanical Engineering and Research Institute for Smart Energy, The Hong Kong Polytechnic University, Hong Kong 999077, China
d.
Key Laboratory of Rare Earth, Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou 341000, China
e.
Shenzhen Key Laboratory on Power Battery Safety Research and Shenzhen Geim Graphene Center, Tsinghua Shenzhen International Graduate School, Shenzhen 518055, China

xiaoliang.yu@polyu.edu.hk

zhql@szu.edu.cn

qhliang@gia.cas.cn

Received Date: 17 October 2024
Revised Date: 25 November 2024
Accepted Date: 25 November 2024
Available Online: 26 November 2024

Figures(4)

The emerging anode-free lithium metal battery (AFLMB) is very promising for the next-generation electrochemical energy storage technology due to its remarkable high-energy density. However, the current development of AFLMB is seriously hampered by the low Coulombic efficiency and limited lifespan caused mainly by the uncontrolled dendritic lithium growth and significant volume change during Li plating/stripping on the traditional current collector. Here, we report the design of a “breathable” three-dimensional (3D) lithium host with MnO₂ nanoflake array for long-lifespan AFLMB. Specifically, a dense MnO₂ nanoflake array stretchably grown on carbon cloth by an easy solution dipping method is constructed as a 3D current collector for AFLMBs. Both experimental and theoretical studies underlined that the Li₂O/Mn nanoflake arrays produced spontaneously upon the initial lithiation can effectively guide uniform lithium nucleation and growth. Moreover, this unique 3D hierarchical structure expands/shrinks along with the lithium plating/stripping, accommodating the large volume expansion/shrinkage over the subsequent charge/discharge processes. As such, a dendrite-free lithium structure was achieved even at a high capacity of 10 mAh/cm². More importantly, the as-constructed AFLMB with this current collector exhibits impressive cycling stability with 64% capacity retained after 200 cycles. This study offers new insights into constructing highly efficient 3D protective layers for metal anodes toward the practical feasibility of anode-free batteries.
- Lithium metal battery,
- Anode free,
- Nanoflake array,
- Mechanical breathing,
- Cycling stability
1. [1]
  J. Liu, Z. Bao, Y. Cui, et al., Nat. Energy 4 (2019) 180–186. doi: 10.1038/s41560-019-0338-x
2. [2]
  P. Albertus, S. Babinec, S. Litzelman, A. Newman, Nat. Energy 3 (2018) 16–21.
3. [3]
  J. Qian, B.D. Adams, J. Zheng, et al., Adv. Funct. Mater. 26 (2016) 7094–7102. doi: 10.1002/adfm.201602353
4. [4]
  S. Nanda, A. Gupta, A. Manthiram, Adv. Energy Mater. 11 (2021) 2000804. doi: 10.1002/aenm.202000804
5. [5]
  S. Ding, Z. Fang, L. Zhang, et al., J. Colloid Interface Sci. 672 (2024) 543–551. doi: 10.1016/j.jcis.2024.06.043
6. [6]
  L. Sheng, Q. Wang, X. Liu, et al., Nat. Commun. 13 (2022) 172. doi: 10.1038/s41467-021-27841-0
7. [7]
  C. Liao, R. Zou, J. Zhu, et al., Small 20 (2024) 2305085. doi: 10.1002/smll.202305085
8. [8]
  J. Xiao, Science 366 (2019) 426–427. doi: 10.1126/science.aay8672
9. [9]
  Y. Liu, D. Lin, Z. Liang, et al., Nat. Commun. 7 (2016) 10992. doi: 10.1038/ncomms10992
10. [10]
  S. Liu, K. Jiao, J. Yan, Energy Storage Mater 54 (2023) 689–712. doi: 10.1016/j.ensm.2022.11.021
11. [11]
  Z. Wang, L.P. Hou, Z. Li, et al., Carbon Energy 5 (2022) e283.
12. [12]
  S. Zhang, B. Cheng, Y. Fang, et al., Chin. Chem. Lett. 33 (2022) 3951–3954. doi: 10.1016/j.cclet.2021.11.024
13. [13]
  J.X. Guo, F. Jiang, N.L. Shen, et al., ACS Energy Lett. 9 (2024) 4800–4809. doi: 10.1021/acsenergylett.4c01583
14. [14]
  J. Qian, W.A. Henderson, W. Xu, et al., Nat. Commun. 6 (2015) 6362. doi: 10.1038/ncomms7362
15. [15]
  G. Huang, J. Han, F. Zhang, et al., Adv. Mater. 31 (2019) 1805334. doi: 10.1002/adma.201805334
16. [16]
  P. Xue, S. Liu, X. Shi, et al., Adv. Mater. 30 (2018) 1804165. doi: 10.1002/adma.201804165
17. [17]
  C. Wang, C. Yang, Y. Du, et al., Adv. Funct. Mater. 33 (2023) 2303427. doi: 10.1002/adfm.202303427
18. [18]
  Y.S. Feng, Y.N. Li, P. Wang, et al., Angew. Chem. Int. Ed. 62 (2023) e202310132. doi: 10.1002/anie.202310132
19. [19]
  Y.L. Ye, Y. Zhou, H. Ye, F.F. Cao, J. Energy Chem. 101 (2025) 744–750. doi: 10.1016/j.jechem.2024.09.063
20. [20]
  Y. Zhao, Z. Liu, Z. Li, et al., Energy Mater. 2 (2022) 200034.
21. [21]
  Y. Gu, W.W. Wang, Y.J. Li, et al., Nat. Commun. 9 (2018) 1339. doi: 10.1038/s41467-018-03466-8
22. [22]
  X.B. Cheng, S.J. Yang, Z. Liu, et al., Adv. Mater. 36 (2024) 2307370. doi: 10.1002/adma.202307370
23. [23]
  G. Zheng, S.W. Lee, Z. Liang, et al., Nat. Nanotechnol. 9 (2014) 618–623. doi: 10.1038/nnano.2014.152
24. [24]
  J. Yang, T. Feng, C. Zhi, et al., J. Colloid Interface Sci. 599 (2021) 819–827. doi: 10.1016/j.jcis.2021.04.067
25. [25]
  J. Yan, F.Q. Liu, J. Gao, et al., Adv. Funct. Mater. 31 (2021) 2007255. doi: 10.1002/adfm.202007255
26. [26]
  M. Su, Y. Chen, S. Wang, H. Wang, Chin. Chem. Lett. 34 (2023) 107553. doi: 10.1016/j.cclet.2022.05.067
27. [27]
  V. Tucureanu, A. Matei, A.M. Avram, Crit. Rev. Anal. Chem. 46 (2016) 502–520. doi: 10.1080/10408347.2016.1157013
28. [28]
  B. Manoj, A.G. Kunjomana, Int. J. Electrochem. Sci. 7 (2012) 3127–3134. doi: 10.1016/S1452-3981(23)13940-X
29. [29]
  H. Sun, G. Xin, T. Hu, et al., Nat. Commun. 5 (2014) 4526. doi: 10.1038/ncomms5526
30. [30]
  L. Li, A.R.O. Raji, J.M. Tour, Adv. Mater. 25 (2013) 6298–6302. doi: 10.1002/adma.201302915
31. [31]
  Q. Li, H. Li, Q. Xia, et al., Nat. Mater. 20 (2021) 76–83. doi: 10.1038/s41563-020-0756-y
32. [32]
  O. Tamwattana, H. Park, J. Kim, et al., ACS Energy Lett. 6 (2021) 4416–4425. doi: 10.1021/acsenergylett.1c02224
33. [33]
  L. Lin, L. Suo, Y.S. Hu, et al., Adv. Energy Mater. 11 (2021) 2003709. doi: 10.1002/aenm.202003709
34. [34]
  P. Liang, H. Sun, C.L. Huang, et al., Adv. Mater. 34 (2022) 2207361. doi: 10.1002/adma.202207361
35. [35]
  S.S. Zhang, X. Fan, C. Wang, Electrochim. Acta 258 (2017) 1201–1207. doi: 10.1016/j.electacta.2017.11.175
36. [36]
  A.A. Assegie, C.C. Chung, M.C. Tsai, et al., Nanoscale 11 (2019) 2710–2720. doi: 10.1039/c8nr06980h
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8. [8]
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10. [10]
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18. [18]
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沈阳化工大学材料科学与工程学院沈阳 110142

A “breathable” 3D lithium host with MnO2 nanoflake array for long-lifespan anode-free lithium metal batteries

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通讯作者: 陈斌, bchen63@163.com

A “breathable” 3D lithium host with MnO₂ nanoflake array for long-lifespan anode-free lithium metal batteries