Citation: Fengfeng Han, Lirong Zhang, Qi Jin, Yufei Zhang, Zhiguo Zhang, Liu Liu, Lu Li, Xinzhi Ma, Xitian Zhang, Lili Wu. Strong interaction between high-entropy alloy catalysts and solvent molecules facilitating the polysulfide conversion in lean-electrolyte lithium-sulfur batteries[J]. Chinese Chemical Letters, ;2026, 37(11): 111814. doi: 10.1016/j.cclet.2025.111814 shu

Strong interaction between high-entropy alloy catalysts and solvent molecules facilitating the polysulfide conversion in lean-electrolyte lithium-sulfur batteries

Fengfeng Han ^{a, 1} ,
Lirong Zhang ^{a, 1} ,
Qi Jin ^a ,
Yufei Zhang ^a ,
Zhiguo Zhang ^b ,
Liu Liu ^c ,
Lu Li ^a ,
Xinzhi Ma ^a ,
Xitian Zhang ^{a, *,} ,
Lili Wu ^{a, *,}

a.
Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, School of Physics and Electronic Engineering, Harbin Normal University, Harbin 150025, China
b.
Department of Physics, Harbin Institute of Technology, Harbin 150001, China
c.
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China

xtzhangzhang@hotmail.com

wll790107@hotmail.com

Received Date: 3 July 2025
Revised Date: 1 September 2025
Accepted Date: 9 September 2025
Available Online: 9 September 2025

Figures(7)

The design of an efficient catalyst is crucial for sulfur reduction reaction (SRR) in lean electrolyte lithium-sulfur (Li–S) batteries. However, most existing catalysts primarily focus on polysulfide-catalyst interactions and generally demonstrate high activity only with an excessive electrolyte. In this study, we propose high-entropy alloy (HEA) composite to enhance the SRR under lean-electrolyte conditions by optimizing the solvent-catalyst interaction. As evidenced by in situ spectroscopy, nuclear magnetic resonance (NMR), density functional theory (DFT) calculations, and experimental investigations, the strong interaction between the solvent and HEA catalysts enables the Li–S battery to achieve a high capacity of 1007.9 mAh/g with a low E/S ratio of 10 µL/mg, and capacity retention of 77% after 200 cycles at lower E/S ratio of 4.5 µL/mg. The enhanced SRR performance in lean electrolyte conditions is primarily attributed to d–d electron interactions among the constituent metals and the presence of multiple active sites with optimized energy barriers in the HEA catalysts. This work underscores the significance of solvent-catalyst interactions in regulating the SRR of lean electrolyte Li–S battery and offers insights into the rational design of HEA catalysts to advance Li−S batteries.
- Catalyst-solvent interactions,
- Li–S batteries,
- Lean electrolyte,
- Sulfur reduction reaction,
- High entropy alloy
1. [1]
  X. Fan, Y. Liu, J. Tan, et al., J. Mater. Chem. A 10 (2022) 7653–7659. doi: 10.1039/d1ta10444f
2. [2]
  Z. Jin, T. Lin, H. Jia, et al., ACS Nano 15 (2021) 7318–7327. doi: 10.1021/acsnano.1c00556
3. [3]
  Q. Pang, J. Tang, H. Huang, et al., Adv. Mater. 27 (2015) 6021–6028. doi: 10.1002/adma.201502467
4. [4]
  D. Yang, J. Wang, C. Lou, et al., ACS Energy Lett. 9 (2024) 2083–2091. doi: 10.1021/acsenergylett.4c00771
5. [5]
  Q. Gong, D. Yang, H. Yang, et al., ACS Nano 18 (2024) 28382–28393. doi: 10.1021/acsnano.4c11068
6. [6]
  F. Han, L. Fan, Z. Zhang, et al., Small 20 (2024) 2307950. doi: 10.1002/smll.202307950
7. [7]
  Z.X. Chen, Q. Cheng, X.Y. Li, et al., J. Am. Chem. Soc. 145 (2023) 16449–16457. doi: 10.1021/jacs.3c02786
8. [8]
  K. Chen, Y. Zhu, Z. Huang, et al., ACS Nano 18 (2024) 34791–34802. doi: 10.1021/acsnano.4c11701
9. [9]
  C. Li, J. Yu, D. Yang, et al., J. Am. Chem. Soc. 147 (2025) 8250–8259. doi: 10.1021/jacs.4c15408
10. [10]
  Z. Wang, Y. Li, H. Ji, et al., Adv. Mater. 34 (2022) 2203699. doi: 10.1002/adma.202203699
11. [11]
  Y.W. Song, J.L. Qin, C.X. Zhao, et al., J. Energy Chem. 64 (2022) 568–573. doi: 10.1016/j.jechem.2021.05.023
12. [12]
  K. Chen, Y. Zhang, Z. Fan, et al., Adv. Funct. Mater. 35 (2025) 2500574. doi: 10.1002/adfm.202500574
13. [13]
  Z. Sun, S. Vijay, H.H. Heenen, et al., Adv. Energy Mater. 10 (2020) 1904010. doi: 10.1002/aenm.201904010
14. [14]
  D. Meggiolaro, M. Agostini, S. Brutti, ACS Energy Lett. 8 (2023) 1300–1312. doi: 10.1021/acsenergylett.2c02493
15. [15]
  X. Leng, K. Yang, L. Sun, et al., Angew. Chem. Int. Ed. 64 (2025) e202416992. doi: 10.1002/anie.202416992
16. [16]
  Z. Li, L. Yu, C.X. Bi, et al., SusMat 4 (2024) e191. doi: 10.1002/sus2.191
17. [17]
  Y.W. Song, L. Shen, N. Yao, et al., Chem 8 (2022) 3031–3050. doi: 10.1016/j.chempr.2022.07.004
18. [18]
  C. Li, D. Yang, J. Yu, et al., Adv. Energy Mater. 14 (2024) 2303551. doi: 10.1002/aenm.202303551
19. [19]
  Z. Li, H. Jiang, N.C. Lai, et al., Chem. Mater. 31 (2019) 10186–10196. doi: 10.1021/acs.chemmater.9b03885
20. [20]
  M. Zhao, B.Q. Li, X.Q. Zhang, et al., ACS Cent. Sci. 6 (2020) 1095–1104. doi: 10.1021/acscentsci.0c00449
21. [21]
  W. Bi, C. Li, D. Yang, et al., Energy Environ. Sci. 18 (2025) 1929–1940. doi: 10.1039/d4ee04689g
22. [22]
  Y. Fei, G. Li, Adv. Funct. Mater. 34 (2024) 2312550. doi: 10.1002/adfm.202312550
23. [23]
  L. Kong, L. Yin, F. Xu, et al., J. Energy Chem. 55 (2021) 80–91. doi: 10.1016/j.jechem.2020.06.054
24. [24]
  B. Han, X. Cao, X. Liu, et al., Adv. Funct. Mater. 35 (2025) 2415782. doi: 10.1002/adfm.202415782
25. [25]
  A. Gupta, A. Manthiram, J. Mater. Chem. A 9 (2021) 13242–13251. doi: 10.1039/d1ta02779d
26. [26]
  H. Pan, K.S. Han, M.H. Engelhard, et al., Adv. Funct. Mater. 28 (2018) 1707234. doi: 10.1002/adfm.201707234
27. [27]
  X. Liu, L. Yuan, X. Peng, et al., Chin. Chem. Lett. 36 (2025) 110369. doi: 10.1016/j.cclet.2024.110369
28. [28]
  A. Gupta, A. Bhargav, A. Manthiram, Chem. Mater. 33 (2021) 3457–3466. doi: 10.1021/acs.chemmater.1c00893
29. [29]
  H. Li, R. Meng, Y. Guo, et al., Angew. Chem. Int. Ed. 61 (2022) e202213863. doi: 10.1002/anie.202213863
30. [30]
  L. Yuan, X. Liu, X. Peng, et al., J. Colloid Interface Sci. 698 (2025) 138065. doi: 10.1016/j.jcis.2025.138065
31. [31]
  H. Li, D. Chao, B. Chen, et al., J. Am. Chem. Soc. 142 (2020) 2012–2022. 8 doi: 10.1021/jacs.9b11774
32. [32]
  S. Jing, X. Peng, S. Li, et al., Chin. Chem. Lett. 36 (2025) 110732. doi: 10.1016/j.cclet.2024.110732
33. [33]
  L. Li, J. Huang, Z. Liu, et al., Chem. Eng. Sci. 317 (2025) 122082. doi: 10.1016/j.ces.2025.122082
34. [34]
  X. Liu, J.Q. Huang, Q. Zhang, et al., Adv. Mater. 29 (2017) 1601759. doi: 10.1002/adma.201601759
35. [35]
  Z. Sun, J. Zhang, L. Yin, et al., Nat. Commun. 8 (2017) 14627. doi: 10.1038/ncomms14627
36. [36]
  H. Park, S. Lee, H. Kim, et al., Carbon Energy 6 (2024) e472. doi: 10.1002/cey2.472
37. [37]
  W. Cai, G. Li, K. Zhang, et al., Adv. Funct. Mater. 28 (2018) 1704865. doi: 10.1002/adfm.201704865
38. [38]
  J. Xu, S. An, X. Song, et al., Adv. Mater. 33 (2021) 2105178. doi: 10.1002/adma.202105178
39. [39]
  F. Han, L. Zhang, Q. Jin, et al., ACS Nano 19 (2025) 9182–9195. doi: 10.1021/acsnano.4c18642
40. [40]
  M. Zhao, B.Q. Li, H.J. Peng, et al., Angew. Chem. Int. Ed. 59 (2020) 12636–12652. doi: 10.1002/anie.201909339
41. [41]
  R. Fang, S. Zhao, Z. Sun, et al., Adv. Mater. 29 (2017) 1606823. doi: 10.1002/adma.201606823
42. [42]
  X. Peng, L. Yuan, S. Li, et al., J. Colloid Interface Sci. 700 (2025) 138455. doi: 10.1016/j.jcis.2025.138455
43. [43]
  Z. Han, S. Zhao, J. Xiao, et al., Adv. Mater. 33 (2021) 2105947. doi: 10.1002/adma.202105947
44. [44]
  Z. Lao, Z. Han, J. Ma, et al., Adv. Mater. 36 (2024) 2309024. doi: 10.1002/adma.202309024
45. [45]
  H. Li, Y. Han, H. Zhao, et al., Nat. Commun. 11 (2020) 5437. doi: 10.1038/s41467-020-19277-9
46. [46]
  C. Zhan, Y. Xu, L. Bu, et al., Nat. Commun. 12 (2021) 6261. doi: 10.1038/s41467-021-26425-2
47. [47]
  M. Wei, Y. Sun, J. Zhang, et al., Energy Environ. Sci. 16 (2023) 4009–4019. doi: 10.1039/d3ee01929b
48. [48]
  R.Q. Yao, Y.T. Zhou, H. Shi, et al., Adv. Funct. Mater. 31 (2021) 2009613. doi: 10.1002/adfm.202009613
49. [49]
  T.A.A. Batchelor, J.K. Pedersen, S.H. Winther, et al., Joule 3 (2019) 834–845. doi: 10.1016/j.joule.2018.12.015
50. [50]
  X. Zhao, H. Cheng, X. Chen, et al., J. Am. Chem. Soc. 146 (2024) 3010–3022. doi: 10.1021/jacs.3c08177
51. [51]
  H. Li, J. Lai, Z. Li, et al., Adv. Funct. Mater. 31 (2021) 2106715. doi: 10.1002/adfm.202106715
52. [52]
  Y. Wan, W. Wei, S. Ding, et al., Adv. Funct. Mater. 35 (2025) 2414554. doi: 10.1002/adfm.202414554
53. [53]
  K. Huang, J. Xia, Y. Lu, et al., Adv. Sci. 10 (2023) 2300094. doi: 10.1002/advs.202300094
54. [54]
  J. Zheng, X. Fan, G. Ji, et al., Nano Energy 50 (2018) 431–440. doi: 10.1016/j.nanoen.2018.05.065
55. [55]
  S. Bhattacharjee, U.V. Waghmare, S.C. Lee, Sci. Rep. 6 (2016) 35916. doi: 10.1038/srep35916
56. [56]
  S. Ming, K. Meng, C. Hou, et al., Phys. Chem. Chem. Phys. 25 (2023) 32979–32988. doi: 10.1039/d3cp04829b
57. [57]
  H. Huang, J. Zhao, H. Guo, et al., Adv. Mater. 36 (2024) 2313209. doi: 10.1002/adma.202313209
58. [58]
  T. Shi, Y. Liao, J. Kong, et al., Energy Storage Mater. 72 (2024) 103744. doi: 10.1016/j.ensm.2024.103744
59. [59]
  N. Li, K. Gao, K. Fan, et al., Energy Environ. Sci. 17 (2024) 5468–5479. doi: 10.1039/d4ee01463d
60. [60]
  X. Wang, C. Zhao, B. Liu, et al., Adv. Energy Mater. 12 (2022) 2201960. doi: 10.1002/aenm.202201960
61. [61]
  H. Shi, X. Zhao, Z.S. Wu, et al., Nano Energy 60 (2019) 743–751. doi: 10.1016/j.nanoen.2019.04.006
62. [62]
  J.J. Zhao, Z.X. Chen, Q. Cheng, et al., J. Mater. Chem. A 12 (2024) 21845–21852. doi: 10.1039/d4ta01997k
63. [63]
  Y. Liu, Y. Elias, J. Meng, et al., Joule 5 (2021) 2323–2364. doi: 10.1016/j.joule.2021.06.009
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