Citation: Qian Wang, Dong Yang, Wenxing Xin, Yongqi Wang, Wenchang Han, Wengxiang Yan, Chunman Yang, Fei Wang, Yiyong Zhang, Ziyi Zhu, Xue Li. Modulation of desolvation barriers and inhibition of lithium dendrites based on lithophilic electrolyte additives for lithium metal anode[J]. Chinese Chemical Letters, ;2025, 36(6): 110669. doi: 10.1016/j.cclet.2024.110669 shu

Modulation of desolvation barriers and inhibition of lithium dendrites based on lithophilic electrolyte additives for lithium metal anode

Qian Wang ^a ,
Dong Yang ^b ,
Wenxing Xin ^a ,
Yongqi Wang ^a ,
Wenchang Han ^a ,
Wengxiang Yan ^a ,
Chunman Yang ^a ,
Fei Wang ^c ,
Yiyong Zhang ^{a, *,} ,
Ziyi Zhu ^{a, *,} ,
Xue Li ^{a, *,}

a.
National local joint engineering research center for Lithium-ion Batteries and Materials Preparation Technology, Key Laboratory of Advanced Batteries Materials of Yunnan Province, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
b.
School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
c.
State Key Laboratory of Chemo/Biosensing and Chemometrics College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China

zhangyiyong2018@kust.edu.cn

zyzhu23@kust.edu.cn

Lixue@kust.edu.cn

Received Date: 17 October 2024
Revised Date: 14 November 2024
Accepted Date: 21 November 2024
Available Online: 23 November 2024

Figures(6)

Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries, attributed to its high theoretical specific capacity and low electrochemical potential. However, safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries. Current research efforts primarily focus on altering the solvated structure of Li⁺ by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier, expedite the desolvation process, and suppress the growth of lithium dendrites. Nevertheless, an integrated approach that combines the advantages of these two strategies remains elusive. In this study, we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process, reduce the nucleation barrier of Li⁺, and modulate its solvated structure. This approach enhanced the inorganic compound content in the solid electrolyte interphase (SEI) on lithium foil surfaces, leading to stable Li⁺ deposition and stripping. Specifically, LiCu cells demonstrated excellent cycle life and Coulombic efficiency (97.28% and 98.59%, respectively) at 0.5 mA/cm²@0.5 mAh/cm² and 1 mA/cm²@1 mAh/cm² for 410 and 240 cycles, respectively. LiLi symmetrical cells showed no short circuit at 1 mA/cm²@1 mAh/cm² for 1150 h, and LiLFP full cells retained 68.9% of their capacity (104.6 mAh/g) after 250 cycles at N/P (1.1:1.0) with a current density of 1 C.
- Lithium metal anode,
- Electrolyte additives,
- Lithophilic metal layer,
- Lithium ion desolvation,
- Lithium dendrites
1. [1]
  A.S. Mohd Razif, N.F. Ab Aziz, M.Z.A. Ab Kadir, K. Kamil, Energy Strat. Rev. 52 (2024) 101346. doi: 10.1016/j.esr.2024.101346
2. [2]
  C. Zhang, Y. Yang, X. Liu, et al., Innovation 4 (2023) 100518.
3. [3]
  P. Greim, A.A. Solomon, C. Breyer, Nat. Commun. 11 (2020) 11. doi: 10.1038/s41467-019-13872-1
4. [4]
  J.A. Lowe, D. Bernie, Philos. T. R. Soc. A 376 (2018) 20170263. doi: 10.1098/rsta.2017.0263
5. [5]
  D. Mitchell, M.R. Allen, J.W. Hall, et al., Philos. T. R. Soc. A 376 (2018) 20180066. doi: 10.1098/rsta.2018.0066
6. [6]
  G.N. Lewis, F.G. Keyes, J. Am. Chem. Soc. 35 (1913) 340–344. doi: 10.1021/ja02193a004
7. [7]
  M. Armand, J.M. Tarascon, Nature 451 (2008) 652–657. doi: 10.1038/451652a
8. [8]
  D.D. Sarma, A.K. Shukla, ACS Energy Lett. 3 (2018) 2841–2845. doi: 10.1021/acsenergylett.8b01966
9. [9]
  P.P. Lopes, V.R. Stamenkovic, Science 369 (2020) 923–924. doi: 10.1126/science.abd3352
10. [10]
  D.T. Wrublewski, Sci. Technol. Libr. 39 (2020) 51–67. doi: 10.1080/0194262x.2020.1717405
11. [11]
  Y.K. Sun, ACS Energy Lett. 2 (2017) 2694–2695. doi: 10.1021/acsenergylett.7b01027
12. [12]
  X.Q. Zhang, C.Z. Zhao, J.Q. Huang, Q. Zhang, Engineering 4 (2018) 831–847. doi: 10.1016/j.eng.2018.10.008
13. [13]
  F.X. Wu, J. Maier, Y. Yu, Chem. Soc. Rev. 49 (2020) 1569–1614. doi: 10.1039/c7cs00863e
14. [14]
  C. Xu, K. Zhang, D. Zhang, et al., Nano Energy 68 (2020) 104318. doi: 10.1016/j.nanoen.2019.104318
15. [15]
  X. Yang, F. Su, M. Hou, et al., Dalton Trans. 50 (2021) 7041–7047. doi: 10.1039/d1dt00807b
16. [16]
  Z. Yao, Y. Kang, M. Hou, et al., Adv. Funct. Mater. 32 (2022) 2111919. doi: 10.1002/adfm.202111919
17. [17]
  S. Xin, X. Zhang, L. Wang, et al., Sci. China Chem. 67 (2024) 13–42. doi: 10.1007/s11426-023-1908-9
18. [18]
  M.N. Obrovac, Curr. Opin. Electrochem. 9 (2018) 8–17. doi: 10.1016/j.coelec.2018.02.002
19. [19]
  Z.Y. Feng, W.J. Peng, Z.X. Wang, et al., Int. J. Miner. Metall. Mater. 28 (2021) 1549–1564. doi: 10.1007/s12613-021-2335-x
20. [20]
  X. Lei, Y. Wang, J. Wang, et al., Small Methods 8 (2024) 2300754. doi: 10.1002/smtd.202300754
21. [21]
  Y. Zhang, T.T. Zuo, J. Popovic, et al., Mater. Today 33 (2020) 56–74. doi: 10.1016/j.mattod.2019.09.018
22. [22]
  M. Qi, L. Xie, Q. Han, et al., J. Energy Storage 47 (2022) 103641. doi: 10.1016/j.est.2021.103641
23. [23]
  Q.J. Shao, S.D. Zhu, J. Chen, Nano Res. 16 (2023) 8097–8138. doi: 10.1007/s12274-022-5227-0
24. [24]
  C.M. Yang, F. Wang, D. You, et al., Chem. Eng. J. 496 (2024) 153812. doi: 10.1016/j.cej.2024.153812
25. [25]
  J. Liu, F. Wang, H. Wei, et al., Chin. Chem. Lett. (2024), doi:10.1016/j.cclet.2024.110475. doi: 10.1016/j.cclet.2024.110475
26. [26]
  P. Xu, X. Lin, Z. Sun, et al., J. Energy Chem. 72 (2022) 186–194. doi: 10.1016/j.jechem.2022.04.025
27. [27]
  S.S.H. Zaidi, X. Li, Adv. Energy Mater. 13 (2023) 2300985. doi: 10.1002/aenm.202300985
28. [28]
  R. Bhattacharyya, B. Key, H. Chen, et al., Nat. Mater. 9 (2010) 504–510. doi: 10.1038/nmat2764
29. [29]
  S. Chandrashekar, N.M. Trease, H.J. Chang, et al., Nat. Mater. 11 (2012) 311–315. doi: 10.1038/nmat3246
30. [30]
  D. Lu, Y. Shao, T. Lozano, et al., Adv. Energy Mater. 5 (2015) 1400993. doi: 10.1002/aenm.201400993
31. [31]
  K.N. Wood, E. Kazyak, A.F. Chadwick, et al., ACS Cent. Sci. 2 (2016) 790–801. doi: 10.1021/acscentsci.6b00260
32. [32]
  X.Q. Xu, X.B. Cheng, F.N. Jiang, et al., SusMat 2 (2022) 435–444. doi: 10.1002/sus2.74
33. [33]
  K. Huang, S. Song, Z. Xue, et al., Energy Storage Mater. 55 (2023) 301–311. doi: 10.1016/j.ensm.2022.12.003
34. [34]
  P. Xu, X. Lin, X. Hu, et al., Energy Storage Mater. 28 (2020) 188–195. doi: 10.1016/j.ensm.2020.02.030
35. [35]
  T. Liu, Q. Hu, X. Li, et al., J. Mater. Chem. A 7 (2019) 20911–20918. doi: 10.1039/c9ta05335b
36. [36]
  Z. Jia, H. Lyu, W. Wang, et al., J. Alloys Compd. 936 (2023) 168108. doi: 10.1016/j.jallcom.2022.168108
37. [37]
  J. Fu, X. Ji, J. Chen, et al., Angew. Chem. Int. Ed. 59 (2020) 22194–22201. doi: 10.1002/anie.202009575
38. [38]
  Q.K. Zhang, S.Y. Sun, M.Y. Zhou, et al., Angew. Chem. Int. Ed. 62 (2023) e202306889. doi: 10.1002/anie.202306889
39. [39]
  Q.K. Zhang, X.Q. Zhang, J. Wan, et al., Nat. Energy 8 (2023) 725–735. doi: 10.1038/s41560-023-01275-y
40. [40]
  J. Zhong, Z.X. Wang, S.W. Wang, et al., Appl. Surf. Sci. 622 (2023) 156968. doi: 10.1016/j.apsusc.2023.156968
41. [41]
  W. Liu, P. Liu, D. Mitlin, Adv. Energy Mater. 10 (2020) 2002297. doi: 10.1002/aenm.202002297
42. [42]
  U. Pal, D. Rakov, B.Y. Lu, et al., Energy Environ. Sci. 15 (2022) 1907–1919. doi: 10.1039/d1ee02929k
43. [43]
  F. Zhao, P. Zhai, Y. Wei, et al., Adv. Sci. 9 (2022) 2103930. doi: 10.1002/advs.202103930
44. [44]
  D. Yang, X. Wang, Q. Wang, et al., Energy Storage Mater. 72 (2024) 103719. doi: 10.1016/j.ensm.2024.103719
45. [45]
  Z. Wang, L.P. Hou, Q.K. Zhang, et al., Chin. Chem. Lett. 35 (2024) 108570. doi: 10.1016/j.cclet.2023.108570
46. [46]
  Q. Zhang, S. Liu, Z. Lin, et al., Nano Energy 74 (2020) 104860. doi: 10.1016/j.nanoen.2020.104860
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4. [4]
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