Citation: Ziling Jiang, Chen Liu, Jie Yang, Xia Li, Chaochao Wei, Qiyue Luo, Zhongkai Wu, Lin Li, Liping Li, Shijie Cheng, Chuang Yu. Designing F-doped Li₃InCl₆ electrolyte with enhanced stability for all-solid-state lithium batteries in a wide voltage window[J]. Chinese Chemical Letters, ;2025, 36(6): 109741. doi: 10.1016/j.cclet.2024.109741 shu

Designing F-doped Li₃InCl₆ electrolyte with enhanced stability for all-solid-state lithium batteries in a wide voltage window

Ziling Jiang ^{a, 1} ,
Chen Liu ^{a, 1} ,
Jie Yang ^a ,
Xia Li ^{b, *,} ,
Chaochao Wei ^a ,
Qiyue Luo ^a ,
Zhongkai Wu ^a ,
Lin Li ^a ,
Liping Li ^{c, *,} ,
Shijie Cheng ^a ,
Chuang Yu ^{a, *,}

a.
State Key Laboratory of Advanced Electromagnetic Engineering and Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
b.
Innovation Center for Chemical Science, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
c.
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China

cyu2020@hust.edu.cn

xiali@suda.edu.cn

lipingli@jlu.edu.cn

Received Date: 12 January 2024
Revised Date: 2 February 2024
Accepted Date: 6 March 2024
Available Online: 8 March 2024

Figures(4)

Achieving high energy densities for all-solid-state lithium batteries is restricted by the poor high voltage stability of solid electrolytes. Herein, F-doping strategy is successfully employed on Li₃InCl₆ to obtain enhanced voltage stability and electrode compatability towards bare LiNi_0.7Mn_0.2Co_0.1O₂ at high voltages. The optimized Li₃InCl_5.5F_0.5 electrolyte exhibits a decreased conductivity of 1.00 mS/cm, a wider voltage window, and improved electrochemical performance in solid-state batteries when cycled at upper cut-off voltages of 4.5 and 4.8 V (vs. Li⁺/Li⁰). The generation of more stable LiInF₄ phase in the cathode mixture of Li₃InCl_5.5F_0.5-based battery ensures superior electrochemical performances compared to the Li₃InCl₆-based battery. The former battery exhibits a higher discharge capacity of 218.9 mAh/g and coulombic efficiency of 86.7% for the first cycle, and retains 80.0% of its original value after 100 cycles when cycled in the range of 3.0–4.5 V (vs. Li⁺/Li⁰). In contrast, the Li₃InCl₆-based battery exhibits lower capacities and faster degradation under the same conditions due to the formation of InCl₃ phase with poor electrochemical stability. This work facilitates the advancement of high energy density solid-state battery technologies by utilizing high-voltage cathodes.
- Li₃InCl₆ electrolytes,
- F-doping,
- Stability,
- Electrochemical performance,
- Solid-state batteries
1. [1]
  S. Randau, D.A. Weber, O. Kötz, et al., Nat. Energy 5 (2020) 259–270. doi: 10.1038/s41560-020-0565-1
2. [2]
  P. Adeli, J.D. Bazak, K.H. Park, et al., Angew. Chem. Int. Ed. 58 (2019) 8681–8686. doi: 10.1002/anie.201814222
3. [3]
  T.K. Schwietert, V.A. Arszelewska, C. Wang, et al., Nat. Mater. 19 (2020) 428–435. doi: 10.1038/s41563-019-0576-0
4. [4]
  H. Wan, B. Zhang, S. Liu, et al., Adv. Energy Mater. (2023) 2303046.
5. [5]
  Z. Jiang, C. Liu, C. Wei, et al., Ind. Eng. Chem. Res. 62 (2023) 21546–21557. doi: 10.1021/acs.iecr.3c03758
6. [6]
  H. Wan, Z. Wang, W. Zhang, et al., Nature 623 (2023) 739–744. doi: 10.1038/s41586-023-06653-w
7. [7]
  L. Peng, S. Chen, C. Yu, et al., ACS Appl. Mater. Interfaces 14 (2022) 4179–4185. doi: 10.1021/acsami.1c21561
8. [8]
  M. Yang, H. Li, F. Wu, Energy Mater. Adv. 2022 (2022) 41. doi: 10.1097/hm9.0000000000000026
9. [9]
  N. Sun, Y. Song, Q. Liu, et al., Adv. Energy Mater. 12 (2022) 2200682. doi: 10.1002/aenm.202200682
10. [10]
  A. Zhang, J. Wang, R. Yu, et al., ACS Appl. Mater. Interfaces 15 (2023) 8190–8199. doi: 10.1021/acsami.2c21569
11. [11]
  Z. Wang, C. Zhao, S. Sun, et al., Matter 6 (2023) 1096–1124. doi: 10.1016/j.matt.2023.02.012
12. [12]
  C. Yu, G. Li, X. Guan, et al., PCCP 14 (2012) 12368–12377. doi: 10.1039/c2cp41881a
13. [13]
  C. Wang, K. Fu, S.P. Kammampata, et al., Chem. Rev. 120 (2020) 4257–4300. doi: 10.1021/acs.chemrev.9b00427
14. [14]
  Q. Guo, F. Xu, L. Shen, et al., Energy Mater. Adv. 2022 (2022) 8.
15. [15]
  C. Wei, X. Liu, C. Yu, et al., Chin. Chem. Lett. (2022) 107859.
16. [16]
  Q. Luo, L. Ming, D. Zhang, et al., Energy Mater. Adv. 4 (2023) 0065. doi: 10.34133/energymatadv.0065
17. [17]
  L. Peng, C. Yu, C. Wei, et al., Acta Phys. Chim. Sin. 39 (2023) 2211034.
18. [18]
  L. Ming, D. Liu, Q. Luo, et al., Chin. Chem. Lett. (2023) 109087.
19. [19]
  T. Chen, D. Zeng, L. Zhang, et al., J. Energy Chem. 59 (2021) 530–537. doi: 10.1016/j.jechem.2020.11.031
20. [20]
  S. Chen, C. Yu, C. Wei, et al., Energy Mater. Adv. 4 (2023) 1–10.
21. [21]
  X. Li, J. Liang, J. Luo, et al., Energy Environ. Sci. 12 (2019) 2671.
22. [22]
  S. Chen, C. Yu, Q. Luo, et al., Acta Phys. Chim. Sin. 39 (2023) 2210032.
23. [23]
  S. Chen, C. Yu, C. Wei, et al., Chin. Chem. Lett. 34 (2022) 107544.
24. [24]
  X. Luo, D. Cai, X. Wang, et al., ACS Appl. Mater. Interfaces 14 (2022) 29844–29855. doi: 10.1021/acsami.2c06216
25. [25]
  L. Zhou, C. Kwok, A. Shyamsunder, et al., Energy Environ. Sci. 13 (2020) 2056–2063. doi: 10.1039/d0ee01017k
26. [26]
  T. Ma, Z. Wang, D. Wu, et al., Energy Environ. Sci. 16 (2023) 2142–2152. doi: 10.1039/d3ee00420a
27. [27]
  K. Wang, Q. Ren, Z. Gu, et al., Nat. Commun. 12 (2021) 4410. doi: 10.1038/s41467-021-24697-2
28. [28]
  T. Asano, A. Sakai, S. Ouchi, et al., Adv. Mater. 30 (2018) 1803075. doi: 10.1002/adma.201803075
29. [29]
  S. Wang, Q. Bai, A.M. Nolan, et al., Angew. Chem. Int. Ed. 58 (2019) 8039–8043. doi: 10.1002/anie.201901938
30. [30]
  I. Kochetkov, T. Zuo, R. Ruess, et al., Energy Environ. Sci. 15 (2022) 3933. doi: 10.1039/d2ee00803c
31. [31]
  C. Wei, R. Wang, Z. Wu, et al., Chin. Chem. Lett. (2023) 108717. doi: 10.1016/j.cclet.2023.108717
32. [32]
  C. Wei, R. Wang, Z. Wu, et al., Chem. Engin. J. 476 (2023) 146531. doi: 10.1016/j.cej.2023.146531
33. [33]
  C. Yu, S. Ganapathy, E. van Eck, et al., J. Energy Chem. 38 (2019) 1–7. doi: 10.5539/ies.v12n5p1
34. [34]
  C. Wei, C. Liu, Y. Xiao, et al., Adv. Funct. Mater. (2024) 2314306. doi: 10.1002/adfm.202314306
35. [35]
  C. Wei, S. Chen, C. Yu, et al., Appl. Mater. Today 31 (2023) 101770. doi: 10.1016/j.apmt.2023.101770
36. [36]
  Z. Jiang, C. Yu, S. Chen, et al., Scripta Mater. 227 (2023) 115303. doi: 10.1016/j.scriptamat.2023.115303
37. [37]
  Z. Jiang, S. Chen, C. Wei, et al., Chin. Chem. Lett. (2023) 108561. doi: 10.1016/j.cclet.2023.108561
38. [38]
  X. Li, Q. Sun, Z. Wang, et al., J. Power Sources 456 (2020) 227997. doi: 10.1016/j.jpowsour.2020.227997
39. [39]
  Z. Chen, J. Meng, Y. Wang, et al., Electrochim. Acta 378 (2021) 138138. doi: 10.1016/j.electacta.2021.138138
40. [40]
  S. Zhang, F. Zhao, S. Wang, et al., Adv. Energy Mater. 11 (2021) 2100836. doi: 10.1002/aenm.202100836
41. [41]
  Y. Kim, S. Choi, J. Power Sources 567 (2023) 232962. doi: 10.1016/j.jpowsour.2023.232962
42. [42]
  X. Yang, Q. Yin, C. Wang, et al., Prog. Mater. Sci. 140 (2023) 101193. doi: 10.1016/j.pmatsci.2023.101193
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Designing F-doped Li₃InCl₆ electrolyte with enhanced stability for all-solid-state lithium batteries in a wide voltage window