Citation: Congcong Zhang, Yinan Liu, Pengrui Bao, Yun Zheng, Yingying Shen, Yike Huang, Pingshan Jia, Zhiyuan Zhang, Kunye Yan, Rong Chen, Yuhao Li, Junpo Guo, Huaiyu Shao. Synergy enhancement mechanism of fluorine-doping and oxygen-defect for high-capacity F/O-CoO anode material[J]. Chinese Chemical Letters, ;2026, 37(8): 111212. doi: 10.1016/j.cclet.2025.111212 shu

Synergy enhancement mechanism of fluorine-doping and oxygen-defect for high-capacity F/O-CoO anode material

Congcong Zhang ^{a, 1} ,
Yinan Liu ^{a, 1} ,
Pengrui Bao ^b ,
Yun Zheng ^a ,
Yingying Shen ^a ,
Yike Huang ^a ,
Pingshan Jia ^a ,
Zhiyuan Zhang ^a ,
Kunye Yan ^a ,
Rong Chen ^a ,
Yuhao Li ^b ,
Junpo Guo ^{b, *,} ,
Huaiyu Shao ^{a, *,}

a.
Institute of Applied Physics and Materials Engineering, University of Macau, Macau SAR 999078, China
b.
Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China

hshao@um.edu.mo

guojunpo@htu.edu.cn

Received Date: 12 February 2025
Revised Date: 9 April 2025
Accepted Date: 15 April 2025
Available Online: 15 April 2025

Figures(5)

Transition metal oxides are regarded as promising alternatives to graphite anode material due to their high theoretical capacities. However, their low conductivity, large volume change and fragile structure during battery operation hamper large-scale applications. Herein, we synthesize F-doping and oxygen defect CoO composite (F/O-CoO) through a facile hydrothermal and following annealing process. Benefiting from the synergy of F-doping and oxygen defect, the F/O-CoO anode material delivers a high reversible capacity of 1112 mAh/g at 0.5 C and capacity retention of 609 mAh/g (79.1%) at 2 C after 400 cycles, as well as a rate capacity of 449 mAh/g at 5 C. This superior capacity enhancement is attributed to the enrichment of oxygen defect and necessary substitution of lattice oxygen atom by F, which play an important role in improving electrical conductivity and thus reducing polarization. DFT calculation provides a further explanation that F doping can reduce the Li⁺ adsorption energy and the bandgap energy of F/O-CoO material, as well as increase Li⁺ storage sites and Li⁺/e^- conductivity.
- F/O-CoO,
- Anode material,
- Capacity enhancement,
- Li⁺/e⁻ conductivity,
- Polarization,
- Bandgap energy
1. [1]
  Y. Lei, D. Han, J. Dong, et al., Energy Storage Mater. 24 (2020) 319–328. doi: 10.1016/j.ensm.2019.07.043
2. [2]
  J.X. Wu, Y.L. Cao, H.M. Zhao, et al., Carbon Energy 1 (2019) 57–76. doi: 10.1002/cey2.2
3. [3]
  P. Liu, H. Wang, T. Huang, et al., Chin. Chem. Lett. 35 (2024) 108330. doi: 10.1016/j.cclet.2023.108330
4. [4]
  Y. Li, Y.X. Lu, P. Adelhelm, et al., Chem. Soc. Rev. 48 (2019) 4655–4687. doi: 10.1039/c9cs00162j
5. [5]
  W. Zhang, L. Wang, G. Ding, et al., Chin. Chem. Lett. 34 (2023) 107328. doi: 10.1016/j.cclet.2022.03.051
6. [6]
  Y. Yan, X. Zhao, H. Dou, et al., Chin. Chem. Lett. 32 (2021) 910–913. doi: 10.1016/j.cclet.2020.07.021
7. [7]
  M. Ahmad, Y.Y. Shi, A. Nisar, et al., J. Mater. Chem. 21 (2011) 7723–7729. doi: 10.1039/c1jm10720h
8. [8]
  Y.M. Lin, P.R. Abel, A. Heller, C.B. Mullins, J. Phys. Chem. Lett. 2 (2011) 2885–2891. doi: 10.1021/jz201363j
9. [9]
  H. Guan, X. Wang, H.Q. Li, et al., Chem. Commun. 48 (2012) 4878–4880. doi: 10.1039/c2cc30843f
10. [10]
  J. Chen, Y. Wang, X. He, et al., Electrochim. Acta 142 (2014) 152–156. doi: 10.1016/j.electacta.2014.07.089
11. [11]
  N. Hu, Z. Tang, P.K. Shen, RSC Adv. 8 (2018) 26589–26595. doi: 10.1039/c8ra03599g
12. [12]
  C.C. Zhou, J.Z. Liu, S.Z. Guo, et al., ChemElectroChem 7 (2020) 1573–1580. doi: 10.1002/celc.201902117
13. [13]
  L.H. Wang, X.L. Teng, Y.F. Qin, Q. Li, Ceram. Int. 47 (2021) 5739–5746. doi: 10.1016/j.ceramint.2020.10.160
14. [14]
  M.V. Reddy, G. Prithvi, K.P. Loh, B.V.R. Chowdari, ACS Appl. Mater. Interfaces 6 (2014) 680–690. doi: 10.1021/am4047552
15. [15]
  Q. Li, Y. Zhao, H. Liu, et al., ACS Nano 13 (2019) 11921–11934. doi: 10.1021/acsnano.9b06005
16. [16]
  Y. Hu, Z. Li, Z. Hu, et al., Small 16 (2020) 2003643. doi: 10.1002/smll.202003643
17. [17]
  Z. Cai, Y. Bi, E. Hu, et al., Adv. Energy Mater. 8 (2018) 1701694. doi: 10.1002/aenm.201701694
18. [18]
  L. Fan, X. Guo, W. Li, et al., Chin. Chem. Lett. 34 (2023) 107447. doi: 10.1016/j.cclet.2022.04.045
19. [19]
  Y. Zhou, H. Xie, C. Wang, et al., J. Phys. Chem. C 121 (2017) 15589–15596. doi: 10.1021/acs.jpcc.7b04533
20. [20]
  Y. Zou, W. Zhang, N. Chen, et al., ACS Nano 13 (2019) 2062–2071.
21. [21]
  Y. Zhang, Y. Hu, Z. Wang, et al., Adv. Funct. Mater. 30 (2020) 2004172. doi: 10.1002/adfm.202004172
22. [22]
  D.L. Liu, C.H. Wang, Y.F. Yu, et al., Chem 5 (2019) 376–389. doi: 10.1504/ijcse.2019.103942
23. [23]
  M. Baek, D. Kim, K. Yong, ACS Appl. Mater. Interfaces 9 (2017) 2317–2325. doi: 10.1021/acsami.6b12555
24. [24]
  J. Sun, L. Xiao, S. Jiang, et al., Chem. Mater. 27 (2015) 4594–4603. doi: 10.1021/acs.chemmater.5b00885
25. [25]
  Y. Qin, Z. Jiang, L. Guo, et al., J. Mater. Chem. A 7 (2019) 21270–21279. doi: 10.1039/c9ta08394d
26. [26]
  Z. Wang, X. Zhang, Y. Sun, et al., J. Alloys Compd. 740 (2018) 446–451. doi: 10.1016/j.jallcom.2017.12.020
27. [27]
  M. Cui, X. Chen, Z. Wang, et al., J. Alloys Compd. 903 (2022) 163980. doi: 10.1016/j.jallcom.2022.163980
28. [28]
  Y. Wu, D. Chen, H. Xu, et al., Appl. Surf. Sci. 623 (2023) 157047. doi: 10.1016/j.apsusc.2023.157047
29. [29]
  W. Liu, Y. Chu, J. Zhou, et al., Small Sci. 3 (2023) 2300006. doi: 10.1002/smsc.202300006
30. [30]
  Q. Li, Y. Wang, J. Zeng, et al., Chin. Chem. Lett. 32 (2021) 3355–3358. doi: 10.1016/j.cclet.2021.03.063
31. [31]
  J. Song, Y. Chen, Y. Li, et al., J. Alloys Compd. 958 (2023) 170518. doi: 10.1016/j.jallcom.2023.170518
32. [32]
  P. Wang, Q. Cheng, C. Mao, et al., J. Power Sources 502 (2021) 229903. doi: 10.1016/j.jpowsour.2021.229903
33. [33]
  L. Chen, J. Chang, Y. Zhang, et al., Chem. Commun. 55 (2019) 3406–3409. doi: 10.1039/c9cc00555b
34. [34]
  J.S. Do, C.H. Weng, J. Power Sources 159 (2006) 323–327. doi: 10.1016/j.jpowsour.2006.04.054
35. [35]
  C.X. Hou, Y. Hou, Y.Q. Fan, et al., J. Mater. Chem. A 6 (2018) 6967–6976. doi: 10.1039/c8ta00975a
36. [36]
  X. Li, Q. Chu, M. Song, et al., Appl. Surf. Sci. 618 (2023) 156658. doi: 10.1016/j.apsusc.2023.156658
37. [37]
  J. Wang, H. Wang, F. Li, et al., J. Mater. Chem. A 7 (2019) 3024–3030. doi: 10.1039/c9ta00045c
38. [38]
  E. Peled, S. Menkin, J. Electrochem. Soc. 164 (2017) A1703. doi: 10.1149/2.1441707jes
39. [39]
  A.K. Rai, L.T. Anh, J. Gim, J. Kim, Ceram. Int. 39 (2013) 9325–9330. doi: 10.1016/j.ceramint.2013.05.049
40. [40]
  Y. Wang, T. Zhou, K. Jiang, et al., Adv. Energy Mater. 4 (2014) 1400696. doi: 10.1002/aenm.201400696
41. [41]
  T. Katayama, A. Chikamatsu, Y. Hirose, et al., J. Mater. Chem. C 2 (2014) 5350–5356. doi: 10.1039/C4TC00558A
42. [42]
  J. Ahn, D.C. Chen, G.Y. Chen, Adv. Energy Mater. 10 (2020) 2001671. doi: 10.1002/aenm.202001671
43. [43]
  P. Poizot, S. Laruelle, S. Grugeon, et al., Nature 407 (2000) 496–499. doi: 10.1038/35035045
44. [44]
  L.J. Zhang, P. Hu, X.Y. Zhao, et al., J. Mater. Chem. 21 (2011) 18279–18283. doi: 10.1039/c1jm12990b
45. [45]
  N. Wu, J. Shen, X. Zhou, S. Li, et al., Adv. Energy Mater. 15 (2025) 2405729. doi: 10.1002/aenm.202405729
46. [46]
  Y. Chu, B. Xi, S. Xiong, Chin. Chem. Lett. 32 (2021) 1983–1987. doi: 10.1016/j.cclet.2020.10.024
47. [47]
  D. Yang, T. Lv, J. Song, et al., J. Phys. Chem. Solid 189 (2024) 111956. doi: 10.1016/j.jpcs.2024.111956
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