Citation: Liang Ming, Miao Deng, Siwu Li, Ziling Jiang, Lin Li, Ziyu Lu, Qiyue Luo, Jie Yang, Zhonghui Cui, Chuang Yu. Reviving the ionic conductivity of air-instable solid-state electrolytes via a facile heat treatment[J]. Chinese Chemical Letters, ;2026, 37(7): 111114. doi: 10.1016/j.cclet.2025.111114 shu

Reviving the ionic conductivity of air-instable solid-state electrolytes via a facile heat treatment

Liang Ming ^{a, b, 1} ,
Miao Deng ^{a, b, 1} ,
Siwu Li ^{c, *,} ,
Ziling Jiang ^{a, b} ,
Lin Li ^{a, b} ,
Ziyu Lu ^{a, b} ,
Qiyue Luo ^{a, b} ,
Jie Yang ^{a, b} ,
Zhonghui Cui ^{d, *,} ,
Chuang Yu ^{a, b, *,}

a.
School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
b.
State Key Laboratory of Advanced Electromagnetic Engineering and Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
c.
Academy of Advanced Interdisciplinary Research, Xidian University, Xi’an 710071, China
d.
Zhejiang Intelligent Transportation Technology Innovation Center, Ningbo 315000, China

lisiwu@xidian.edu.cn

zhonghui.cui@gmail.com

cyu2020@hust.edu.cn

Received Date: 21 December 2024
Revised Date: 13 March 2025
Accepted Date: 18 March 2025
Available Online: 18 March 2025

Figures(5)

The quest for sustainable and efficient energy storage solutions has led to significant advancements in the field of solid-state batteries, with a particular focus on solid-state electrolytes (SSEs) especially highly ionic conductive sulfide and halide materials. However, the air instability of these SSEs not only limits their mass production but also poses environmental and safety risks. Herein, the damage of humid-air exposure on the structure and electrochemical properties of Li_5.5PS_4.5Cl_0.8Br_0.7 and Li₃InCl₆ is evaluated, and a subsequent heat treatment is proposed and proven effective to recover the damage, whose mechanisms are pinpointed through XRD data with Retvield refinement. For the exposed samples, a lattice contraction occurs as the hydrolysis reaction caused by H₂O from humid air severely damages the structure, which impedes lithium-ion transport. After heat treatment, a lattice rearrangement can rebuild sufficient lithium-ion pathway in the material, leading to the greatly improved ionic conductivity. As a result, the treated electrolytes provide greatly promoted ionic conductivity (from 0.95 mS/cm to 1.8 mS/cm for Li₃InCl₆, from 1.24 S/cm to 7.04 S/cm for Li_5.5PS_4.5Cl_0.8Br_0.7). More importantly, ASSBs employed with the treated electrolytes achieve outstanding long-term cycling and rate performance, even guarantee considerable capacity output of ~217 and ~159 mAh/g under extreme conditions of 60 and –20 ℃, illustrating significantly improved electrochemical reaction kinetics and the impressive reliability of the heat treatment method.
- All-solid-state lithium batteries,
- Sulfide electrolyte,
- Halide electrolyte,
- Ionic conductivity,
- Air stability
1. [1]
  Y. Ding, Z.P. Cano, A. Yu, J. Lu, Z. Chen, Electrochem. Energy Rev. 2 (2019) 1–28.
2. [2]
  M. Li, J. Lu, Z. Chen, K. Amine, Adv. Mater. 30 (2018) 1800561. doi: 10.1002/adma.201800561
3. [3]
  Y. Chen, Y. Kang, Y. Zhao, et al., J. Energy Chem. 59 (2021) 83–99. doi: 10.3390/membranes11020083
4. [4]
  J. Duan, X. Tang, H. Dai, et al., Electrochem. Energy Rev. 3 (2019) 1–42.
5. [5]
  Y.S. Meng, V. Srinivasan, K. Xu, Science 378 (2022) eabq3750. doi: 10.1126/science.abq3750
6. [6]
  Q. Zhao, S. Stalin, C.Z. Zhao, L.A. Archer, Nat. Rev. Mater. 5 (2020) 229–252. doi: 10.1038/s41578-019-0165-5
7. [7]
  H. Zhu, S. Li, L. Peng, et al., Nano Energy 125 (2024) 109571. doi: 10.1016/j.nanoen.2024.109571
8. [8]
  C. Yu, L. van Eijck, S. Ganapathy, M. Wagemaker, Electrochim. Acta 215 (2016) 93–99. doi: 10.1016/j.electacta.2016.08.081
9. [9]
  T. Asano, A. Sakai, S. Ouchi, et al., Adv. Mater. 30 (2018) 1803075. doi: 10.1002/adma.201803075
10. [10]
  X. Li, J. Liang, N. Chen, et al., Angew. Chem. Int. Ed. 58 (2019) 16427–16432. doi: 10.1002/anie.201909805
11. [11]
  C. Wang, K. Fu, S.P. Kammampata, et al., Chem. Rev. 120 (2020) 4257–4300. doi: 10.1021/acs.chemrev.9b00427
12. [12]
  C. Yu, S. Ganapathy, J. Hageman, L. van Eijck, et al., ACS Appl. Mater. Interfaces 10 (2018) 33296–33306. doi: 10.1021/acsami.8b07476
13. [13]
  S. Chen, C. Yu, C. Wei, et al., Energy Mater. Adv. 4 (2023) 0019. doi: 10.34133/energymatadv.0019
14. [14]
  Q. Guo, F. Xu, L. Shen, et al., Energy Mate. Adv. 2022 (2022) 9753506.
15. [15]
  R. Guo, K. Zhang, W. Zhao, et al., Energy Mater. Adv. 4 (2023) 0022. doi: 10.34133/energymatadv.0022
16. [16]
  F. Zhao, J. Liang, C. Yu, et al., Adv. Energy Mater. 10 (2020) 1903422. doi: 10.1002/aenm.201903422
17. [17]
  J. Liang, X. Li, C. Wang, et al., Energy Mater. Adv. 4 (2023) 0021. doi: 10.34133/energymatadv.0021
18. [18]
  Q. Luo, L. Ming, D. Zhang, et al., Energy Mater. Adv. 4 (2023) 0065. doi: 10.34133/energymatadv.0065
19. [19]
  M.K. Tufail, P. Zhai, M. Jia, N. Zhao, X. Guo, Energy Mater. Adv. 4 (2023) 0015. doi: 10.34133/energymatadv.0015
20. [20]
  X.K. Liu, Y.X. Zhou, F.H. Mi, X.L. Ma, C.W. Sun, Energy Storage Mater. 72 (2024) 103737. doi: 10.1016/j.ensm.2024.103737
21. [21]
  K. Tuo, C. Sun, S. Liu, Electrochem. Energy Rev. 6 (2023) 17. doi: 10.1007/s41918-023-00179-5
22. [22]
  K. Tuo, C. Sun, C.A. López, M.T. Fernández-Díaz, J.A. Alonso, J. Mater. Chem. A 11 (2023) 15651–15662. doi: 10.1039/d3ta02781c
23. [23]
  X. Li, J. Liang, J. Luo, et al., Energy Environ. Sci. 12 (2019) 2665–2671. doi: 10.1039/c9ee02311a
24. [24]
  Y. Cai, C. Li, Z. Zhao, D. Mu, B. Wu, ChemElectroChem 9 (2022) 2101479.
25. [25]
  F. Liu, L. Gao, Z. Zhang, et al., Energy Storage Mater 64 (2024) 103072. doi: 10.1016/j.ensm.2023.103072
26. [26]
  K. Tuo, F. Yin, C. Sun, ACS Sustain Chem. Engin. 12 (2024) 7012–7025. doi: 10.1021/acssuschemeng.4c00365
27. [27]
  D. Yang, J. Li, C. Liu, W. Xing, J. Zhu, J. Energy Chem. 82 (2023) 122–138. doi: 10.61935/aedmr.1.1.2023.p122
28. [28]
  Z.Q. Wang, Z.Y. Xiong, X.J. Ma, et al., Org. Electron. 44 (2017) 110–114. doi: 10.21062/ujep/x.2017/a/1213-2489/mt/17/1/110
29. [29]
  Z. Jiang, Y. Xiao, L. Li, et al., ChemSusChem 18 (2025) e202401664. doi: 10.1002/cssc.202401664
30. [30]
  Y. Sun, K. Suzuki, K. Hara, et al., J. Power Sources 324 (2016) 798–803. doi: 10.1016/j.jpowsour.2016.05.100
31. [31]
  T. Ohtomo, A. Hayashi, M. Tatsumisago, K. Kawamoto, J. Solid State Electrochem. 17 (2013) 2551–2557. doi: 10.1007/s10008-013-2149-5
32. [32]
  G. Liu, D. Xie, X. Wang, et al., Energy Storage Mater. 17 (2019) 266–274. doi: 10.1016/j.ensm.2018.07.008
33. [33]
  J. Liang, X. Li, Y. Zhao, et al., Adv. Energy Mater. 9 (2019) 1902125. doi: 10.1002/aenm.201902125
34. [34]
  W.D. Jung, M. Jeon, S.S. Shin, et al., ACS Omega 5 (2020) 26015–26022. doi: 10.1021/acsomega.0c03453
35. [35]
  K.H. Park, D.Y. Oh, Y.E. Choi, et al., Adv. Mater. 28 (2016) 1874–1883. doi: 10.1002/adma.201505008
36. [36]
  L. Li, J. Yao, R. Xu, et al., Energy Storage Mater. 63 (2023) 103016. doi: 10.1016/j.ensm.2023.103016
37. [37]
  R. Song, J. Yao, R. Xu, et al., Adv. Energy Mater. 13 (2023) 2203631. doi: 10.1002/aenm.202203631
38. [38]
  H. Yan, J. Yao, Z. Ye, et al., Chin. Chem. Lett. 36 (2025) 109568. doi: 10.1016/j.cclet.2024.109568
39. [39]
  C. Yu, S. Ganapathy, N.J. de Klerk, et al., J. Am. Chem. Soc. 138 (2016) 11192–11201. doi: 10.1021/jacs.6b05066
40. [40]
  W. Li, J. Liang, M. Li, et al., Chem. Mater. 32 (2020) 7019–7027. doi: 10.1021/acs.chemmater.0c02419
41. [41]
  Y. Ni, C. Huang, H. Liu, Y. Liang, L.Z. Fan, Adv. Funct. Mater. 32 (2022) 2205998. doi: 10.1002/adfm.202205998
42. [42]
  A. Mills, S. Kalnaus, W.Y. Tsai, et al., ACS Energy Lett. 9 (2024) 2677–2684. doi: 10.1021/acsenergylett.3c02813
43. [43]
  L. Li, Z. Jiang, J. Yang, et al., Adv. Funct. Mater. 35 (2025) 2410008. doi: 10.1002/adfm.202410008
44. [44]
  Y.T. Chen, M.A.T. Marple, D.H.S. Tan, et al., J. Mater. Chem. A 10 (2022) 7155–7164. doi: 10.1039/d1ta09846b
45. [45]
  Y. Nikodimos, C.J. Huang, B.W. Taklu, W.N. Su, B.J. Hwang, Energy Environ. Sci. 15 (2022) 991–1033. doi: 10.1039/d1ee03032a
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