Citation: Le Li, Shaofeng Jia, Shi Yue, Yuanyuan Yang, Chao Tan, Conghui Wang, Hengwei Qiu, Yongqiang Ji, Minghui Cao, Zige Tai, Dan Zhang. Vanadium doping inhibit the Jahn−Teller effect of Mn³⁺ for high-performance aqueous zinc ion battery[J]. Chinese Chemical Letters, ;2025, 36(10): 111009. doi: 10.1016/j.cclet.2025.111009 shu

Vanadium doping inhibit the Jahn−Teller effect of Mn³⁺ for high-performance aqueous zinc ion battery

Le Li ^{a, f} ,
Shaofeng Jia ^a ,
Shi Yue ^a ,
Yuanyuan Yang ^a ,
Chao Tan ^b ,
Conghui Wang ^b ,
Hengwei Qiu ^c ,
Yongqiang Ji ^e ,
Minghui Cao ^d ,
Zige Tai ^f ,
Dan Zhang ^{b, f, *,}

a.
Shaanxi Key Laboratory of Industrial Automation, School of Mechanical Engineering, Shaanxi University of Technology, Hanzhong 723001, China
b.
Shaanxi Key Laboratory of Catalysis, School of Chemistry and Environment Science, Shaanxi University of Technology, Hanzhong 723001, China
c.
State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, School of New Energy, North China Electric Power University, Beijing 102206, China
d.
School of Electronic and Information Engineering, Qingdao University, Qingdao 266071, China
e.
Institute of Physics, Henan Academy of Sciences, Zhengzhou 450046, China
f.
School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an 710072, China

zhangdan@snut.edu.cn

Received Date: 8 December 2024
Revised Date: 25 February 2025
Accepted Date: 26 February 2025
Available Online: 27 February 2025

Figures(5)

The Jahn-Teller effect of Mn³⁺ brings drastic structural changes to MnO₂-based materials and accelerates the destruction and deactivation of the internal structure of the materials, thus leading to severe capacity fading and phase change of MnO₂-based materials in aqueous zinc ion batteries (AZIBs). Here, this study doped high valent vanadium ions into MnO₂ (VMO-x) to inhibit manganese's Jahn−Teller effect. Through a series of characterizations, such as X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM), it was discovered that the introduction of vanadium ions effectively increased the interlayer spacing of MnO₂, facilitating the transport of ions into the interlayer. Additionally, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) demonstrated vanadium doped could effectively adjust the electronic structure, decreasing the average oxidation state of manganese, thereby inhibiting the Jahn−Teller effect and significantly enhancing the stability of the VMO-x cathode. The theoretical calculation showed that introducing vanadium ions enhanced the interaction between the main material and Zn²⁺, optimized its electron transport capacity, and led to better electrical conductivity and reaction kinetics of the VMO-5. Benefiting from this, the VMO-5 cathode exhibited an outstanding capacity of 283 mAh/g and maintained a capacity retention rate of 79% after 2000 cycles, demonstrating excellent electrochemical performance. Furthermore, the mechanism of H⁺/Zn²⁺ co-intercalation/deintercalation was demonstrated through mechanism analysis. Finally, the test results of the pouch cell demonstrated the excellent flexibility and safety exhibited by the VMO-5 make it have great potential in flexible devices. This work presented a novel approach to doping high valence metal ions into manganese-based electrodes for AZIBs.
- Aqueous zinc ion batteries,
- Vanadium doping,
- Jahn−Teller effect,
- VMO-x cathodes,
- Electrochemical performance
1. [1]
  G. Offer, Y. Patel, A. Hales, et al., Nature 582 (2020) 485–487. doi: 10.1038/d41586-020-01813-8
2. [2]
  K. Deng, Q. Zeng, D. Wang, et al., Energy Storage Mater. 32 (2020) 425–447. doi: 10.1016/j.ensm.2020.07.018
3. [3]
  Y. Yang, L. Xu, C. Yan, et al., Energy Lab 1 (2023) 220011.
4. [4]
  Y. Ning, Y. Zhang, B. Zhu, et al., Process Saf. Environ. 187 (2024) 810–819. doi: 10.1016/j.psep.2024.05.013
5. [5]
  F. Wu, L. Zhao, L. Wang, et al., Nano Energy 134 (2025) 110534. doi: 10.1016/j.nanoen.2024.110534
6. [6]
  Z. Bao, C. Lu, Q. Liu, et al., Nat. Commun. 15 (2024) 1934. doi: 10.1038/s41467-024-46317-5
7. [7]
  Y. Wang, S. Wei, Z.-H. Qi, et al., Proc. Nat. Acad. Sci. U. S. A. 120 (2023) e2217208120. doi: 10.1073/pnas.2217208120
8. [8]
  Y. Kong, N.A. Gadelhak, S. Chen, et al., Mater. Lab 2 (2023) 220055.
9. [9]
  S. Jia, L. Li, Y. Shi, et al., Nanoscale 16 (2024) 1539–1576. doi: 10.1039/d3nr04996e
10. [10]
  B. Hu, X. Yang, D. Li, et al., Ceram. 50 (2024) 8421–8428.
11. [11]
  B. Hu, C. Xu, M.K. Aslam, et al., Chem. Eng. J. 389 (2020) 123534. doi: 10.1016/j.cej.2019.123534
12. [12]
  X. Li, Y. Sun, L. Zhou, et al., Mater. Horiz. 11 (2024) 4133–4143. doi: 10.1039/d4mh00544a
13. [13]
  Q. He, J. Bai, M. Xue, et al., J. Energy Chem. 97 (2024) 361–370. doi: 10.1016/j.jechem.2024.05.051
14. [14]
  J. Huang, Z. Wang, M. Hou, et al., Nat. Commun. 9 (2018) 2906. doi: 10.1038/s41467-018-04949-4
15. [15]
  X. Zhao, F. Zhang, H. Li, et al., Energy Environ. Sci. 17 (2024) 3629–3640. doi: 10.1039/d4ee00341a
16. [16]
  F. Li, Y. Liu, G. Wang, et al., J. Mater. Chem. A 9 (2021) 9675–9684. doi: 10.1039/d0ta12009j
17. [17]
  H. Yao, H. Yu, Y. Zheng, et al., Angew. Chem. Int. Ed. 62 (2023) e202315257. doi: 10.1002/anie.202315257
18. [18]
  L. Huang, L. Yi, Y. Chen, et al., J. Alloys Compd. 946 (2023) 169386. doi: 10.1016/j.jallcom.2023.169386
19. [19]
  O. Nisar, W. Qin, J. Zhang, et al., Mater. Lab 3 (2024) 230023.
20. [20]
  F. Kataoka, T. Ishida, K. Nagita, et al., ACS Appl. Energy Mater. 3 (2020) 4720–4726. doi: 10.1021/acsaem.0c00357
21. [21]
  X. Pu, X. Li, L. Wang, et al., ACS Appl. Mater. Interfaces 14 (2022) 21159–21172. doi: 10.1021/acsami.2c02220
22. [22]
  Z. Zheng, G. Yang, J. Yao, et al., Appl. Surf. Sci. 592 (2022) 153335. doi: 10.1016/j.apsusc.2022.153335
23. [23]
  B. Hu, X. Yang, D. Li, et al., J. Alloys Compd. 1008 (2024) 176801. doi: 10.1016/j.jallcom.2024.176801
24. [24]
  T. Zhou, L. Xie, Q. Han, et al., Coord. Chem. Rev. 498 (2024) 215461. doi: 10.1016/j.ccr.2023.215461
25. [25]
  T. Zhou, L. Zhu, L. Xie, et al., Small 18 (2022) 2107102. doi: 10.1002/smll.202107102
26. [26]
  H. Xiao, X. Du, R. Li, et al., Chem. Eng. J. 489 (2024) 151312. doi: 10.1016/j.cej.2024.151312
27. [27]
  J. Xu, Q. Gao, Y. Xia, et al., J. Colloid Interf. Sci. 598 (2021) 419–429. doi: 10.1016/j.jcis.2021.04.057
28. [28]
  J. Dai, C. Yang, Y. Xu, et al., Adv. Mater. 35 (2023) 2303732. doi: 10.1002/adma.202303732
29. [29]
  J. Yang, Y. Yang, J. Lan, et al., J. Electroanal. Chem. 843 (2019) 22–30. doi: 10.1016/j.jelechem.2019.04.073
30. [30]
  L. Yang, Y. Zhu, F. Zeng, et al., Energy Storage Mater. 65 (2024) 103162. doi: 10.1016/j.ensm.2023.103162
31. [31]
  Y. Liu, T. Wang, Y. Sun, et al., Chem. Eng. J. 484 (2024) 149501. doi: 10.1016/j.cej.2024.149501
32. [32]
  Y. Xiao, J. Ren, M. Li, et al., Chem. Eng. J. 474 (2023) 145801. doi: 10.1016/j.cej.2023.145801
33. [33]
  Y. Wang, Y. Zhang, G. Gao, et al., Nano-Micro Lett. 15 (2023) 219. doi: 10.1007/s40820-023-01194-3
34. [34]
  X. Cheng, Z. Xiang, C. Yang, et al., Adv. Funct. Mater. 34 (2024) 2311412. doi: 10.1002/adfm.202311412
35. [35]
  X. Hu, Y. Liao, M. Wu, et al., J. Colloid Interface Sci. 674 (2024) 297–305. doi: 10.1016/j.jcis.2024.06.152
36. [36]
  S. Cui, D. Zhang, Y. Gan, Adv. Energy Mater. 14 (2024) 2302655. doi: 10.1002/aenm.202302655
37. [37]
  D. Li, Q. Gao, H. Zhang, et al., Appl. Surf. Sci. 510 (2020) 145458. doi: 10.1016/j.apsusc.2020.145458
38. [38]
  M. Xie, X. Zhang, R. Wang, et al., Chem. Eng. J. 494 (2024) 152908. doi: 10.1016/j.cej.2024.152908
39. [39]
  M. Xie, R. Wang, N. Wang, et al., J. Mater. Chem. A 11 (2023) 21927–21936. doi: 10.1039/d3ta04837c
40. [40]
  A. Zhang, X. Yin, I. Saadoune, et al., Small 20 (2024) 2402811. doi: 10.1002/smll.202402811
41. [41]
  A. Zhang, R. Zhao, Y. Wang, et al., Angew. Chem. Int. Ed. 62 (2023) e202313163. doi: 10.1002/anie.202313163
42. [42]
  Y. Zhao, S. Zhang, Y. Zhang, et al., Energy Environ. Sci. 17 (2024) 1279–1290. doi: 10.1039/D3EE01659E
43. [43]
  X. Zhao, F. Zhang, H. Li, et al., Energy Environ. Sci. 17 (2024) 3629–3640. doi: 10.1039/d4ee00341a
44. [44]
  N. Jiang, Y. Zeng, Q. Yang, et al., Energy Environ. Sci. 17 (2024) 8904–8914. doi: 10.1039/d4ee02871f
45. [45]
  C. Zuo, F. Chao, M. Li, et al., Adv. Energy Mater. 13 (2023) 2301014. doi: 10.1002/aenm.202301014
46. [46]
  Y. Chen, Z. Lu, T. Chen, et al., J. Electroanal. Chem. 929 (2023) 117084. doi: 10.1016/j.jelechem.2022.117084
47. [47]
  D. Wang, Z. Liu, X.W. Gao, et al., J. Energy Storage 72 (2023) 108740. doi: 10.1016/j.est.2023.108740
48. [48]
  H. Chen, W. Ma, J. Guo, et al., J. Alloys Compd. 932 (2023) 167688. doi: 10.1016/j.jallcom.2022.167688
49. [49]
  N. Li, Z. Hou, S. Liang, et al., Chem. Eng. J. 452 (2023) 139408. doi: 10.1016/j.cej.2022.139408
50. [50]
  M. Li, C. Liu, J. Meng, et al., Adv. Funct. Mater. 34 (2024) 2405659. doi: 10.1002/adfm.202405659
51. [51]
  P. Chomkhuntod, K. Hantanasirisakul, S. Duangdangchote, et al., J. Mater. Chem. A 10 (2022) 5561–5568. doi: 10.1039/d1ta09968j
52. [52]
  S. Zhou, X. Wu, H. Du, et al., J. Colloid Interf. Sci. 623 (2022) 456–466. doi: 10.1016/j.jcis.2022.05.018
53. [53]
  B. Cao, H. Liu, P. Zhang, et al., Adv. Funct. Mater. 31 (2021) 2102126. doi: 10.1002/adfm.202102126
54. [54]
  Z. Wang, Y. Fang, J. Shi, et al., Adv. Energy Mater. 14 (2024) 2303739. doi: 10.1002/aenm.202303739
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2. [2]
  Ningning Zhao , Yuyan Liang , Wenjie Huo , Xinyan Zhu , Zhangxing He , Zekun Zhang , Youtuo Zhang , Xianwen Wu , Lei Dai , Jing Zhu , Ling Wang , Qiaobao Zhang . Separator functionalization enables high-performance zinc anode via ion-migration regulation and interfacial engineering. Chinese Chemical Letters, 2024, 35(9): 109332-. doi: 10.1016/j.cclet.2023.109332
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4. [4]
  Liang Ming , Dan Liu , Qiyue Luo , Chaochao Wei , Chen Liu , Ziling Jiang , Zhongkai Wu , Lin Li , Long Zhang , Shijie Cheng , Chuang Yu . Si-doped Li₆PS₅I with enhanced conductivity enables superior performance for all-solid-state lithium batteries. Chinese Chemical Letters, 2024, 35(10): 109387-. doi: 10.1016/j.cclet.2023.109387
5. [5]
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10. [10]
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11. [11]
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12. [12]
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沈阳化工大学材料科学与工程学院沈阳 110142

Vanadium doping inhibit the Jahn−Teller effect of Mn3+ for high-performance aqueous zinc ion battery

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通讯作者: 陈斌, bchen63@163.com

Vanadium doping inhibit the Jahn−Teller effect of Mn³⁺ for high-performance aqueous zinc ion battery