Citation: Yongchao Shi, Wenda Zhang, Ligang Xu, Chenjie Lou, Shengru Han, Jie Liu, Chengxin Xu, Huajie Luo, Xiaojun Kuang, Jipeng Fu, Haiyan Zheng, Mingxue Tang. Structural changes and reaction pathway during alloying−dealloying of violet phosphorus[J]. Chinese Chemical Letters, ;2026, 37(6): 111077. doi: 10.1016/j.cclet.2025.111077 shu

Structural changes and reaction pathway during alloying−dealloying of violet phosphorus

Yongchao Shi ^{a, 1} ,
Wenda Zhang ^{a, b, 1} ,
Ligang Xu ^a ,
Chenjie Lou ^a ,
Shengru Han ^c ,
Jie Liu ^a ,
Chengxin Xu ^{a, b} ,
Huajie Luo ^d ,
Xiaojun Kuang ^{b, e} ,
Jipeng Fu ^{f, *,} ,
Haiyan Zheng ^{a, *,} ,
Mingxue Tang ^{a, d, *,}

a.
Center for High Pressure Science and Technology Advanced Research, Beijing 100193, China
b.
College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China
c.
Beijing Computational Science Research Center, Beijing 100193, China
d.
School of Materials Science and Engineering & Key Laboratory of Advanced Materials and Devices for Post-Moore Chips, Ministry of Education, University of Science and Technology Beijing, Beijing 100083, China
e.
Guangxi Key Laboratory of Electrochemical and Magnetochemical Function Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, China
f.
Key Laboratory of Rare Earth Optoelectronic Materials and Devices of Zhejiang Province, Institute of Optoelectronic Materials and Devices, China Jiliang University, Hangzhou 310018, China

fujipeng@cjlu.edu.cn

haiyan.zheng@hpstar.ac.cn

mingxue.tang@hpstar.ac.cn

Received Date: 5 January 2025
Revised Date: 2 March 2025
Accepted Date: 12 March 2025
Available Online: 12 March 2025

Figures(5)

This study reveals the unique electrochemical mechanism of violet phosphorus (VP) as an anode material for lithium-ion batteries. Using solid-state nuclear magnetic resonance (NMR) spectroscopy, we detail the alloying reaction mechanism of VP during lithiation. While alloying behavior in black and red phosphorus has been widely studied, intermediate phases remain poorly understood due to complex phase transitions. Our precise NMR assignments link specific signals in VP to distinct atomic sites. The results show that [P8] cage atoms preferentially react with lithium in the early stages, while [P9] cages provide structural support. VP layered structure allows lithium ions to first intercalate between layers, followed by alloying reactions. These findings offer new insights into VP alloying mechanism, advancing the fundamental understanding of its potential in next-generation energy storage systems.
- Violet phosphorus,
- Li-ion batteries,
- Solid-state NMR,
- Alloying process
1. [1]
  J.M. Tarascon, M. Armand, Nature 414 (2001) 359–367. doi: 10.1038/35104644
2. [2]
  Y. Gao, J. Liu, C. Lou, et al., Chin. Chem. Lett. 34 (2023) 108268. doi: 10.1016/j.cclet.2023.108268
3. [3]
  P.G. Bruce, S.A. Freunberger, L.J. Hardwick, J.M. Tarascon, Nat. Mater. 11 (2012) 19–29. doi: 10.1038/nmat3191
4. [4]
  J.B. Goodenough, K.S. Park, J. Am. Chem. Soc. 135 (2013) 1167–1176. doi: 10.1021/ja3091438
5. [5]
  A. Manthiram, ACS Cent. Sci. 3 (2017) 1063–1069. doi: 10.1021/acscentsci.7b00288
6. [6]
  Y. Fu, Q. Wei, G. Zhang, S. Sun, Adv. Energy Mater. 8 (2018) 1703058.
7. [7]
  R. Amine, A. Daali, X. Zhou, et al., Nano Energy 74 (2020) 104849. doi: 10.1016/j.nanoen.2020.104849
8. [8]
  C. Peng, H. Chen, G. Zhong, et al., Nano Energy 58 (2019) 560–567. doi: 10.1016/j.nanoen.2019.01.035
9. [9]
  T. Li, X. Huang, S. Lei, et al., Energy Mater. 3 (2023) 300018.
10. [10]
  X.L. Huang, F. Zhao, Y. Qi, et al., Energy Storage Mater. 42 (2021) 193–208. doi: 10.1016/j.ensm.2021.07.030
11. [11]
  Y. Wang, M. He, S. Ma, et al., J. Phys. Chem. Lett. 11 (2020) 2708–2716. doi: 10.1021/acs.jpclett.0c00746
12. [12]
  X. Chen, G. Xu, X. Ren, et al., J. Mater. Chem. A 5 (2017) 6581–6588. doi: 10.1039/C7TA00455A
13. [13]
  S. Liu, J. Feng, X. Bian, et al., Energy Environ. Sci. 10 (2017) 1222–1233. doi: 10.1039/C7EE00102A
14. [14]
  W.C. Chang, J.H. Wu, K.T. Chen, H.Y. Tuan, Adv. Sci. 6 (2019) 1970052. doi: 10.1002/advs.201970052
15. [15]
  H. Tian, J. Wang, G. Lai, et al., Chem. Soc. Rev. 52 (2023) 5388–5484. doi: 10.1039/d2cs01018f
16. [16]
  J. Bai, Z. Li, J. Feng, et al., J. Power Sources 609 (2024) 234713. doi: 10.1016/j.jpowsour.2024.234713
17. [17]
  C.M. Fung, C.C. Er, L.L. Tan, A.R. Mohamed, S.P. Chai, Chem. Rev. 122 (2022) 3879–3965. doi: 10.1021/acs.chemrev.1c00068
18. [18]
  Z. Chen, Y. Zhu, Q. Wang, et al., Electrochim. Acta 295 (2019) 230–236. doi: 10.1016/j.electacta.2018.10.062
19. [19]
  G.L. Xu, Z. Chen, G.M. Zhong, et al., Nano Lett. 16 (2016) 3955–3965. doi: 10.1021/acs.nanolett.6b01777
20. [20]
  Q. Qiu, C. Li, H. Liu, et al., J. Phys. Chem. C 125 (2021) 15200–15209. doi: 10.1021/acs.jpcc.1c04099
21. [21]
  F. Martini, S. Borsacchi, G. Barcaro, et al., J. Phys. Chem. Lett. 10 (2019) 5122–5127. doi: 10.1021/acs.jpclett.9b01788
22. [22]
  K. Hui, J. Fu, J. Liu, et al., Carbon Energy 3 (2021) 709–720. doi: 10.1002/cey2.130
23. [23]
  X. Feng, M. Tang, S. O'Neill, Y.Y. Hu, J. Mater. Chem. A 6 (2018) 22240–22247. doi: 10.1039/c8ta05433a
24. [24]
  L. Zhang, H. Huang, B. Zhang, et al., Angew. Chem. 132 (2020) 1090–1096. doi: 10.1002/ange.201912761
25. [25]
  D. Lu, J. Tan, M. Zhang, et al., J. Phys. Chem. Lett. 15 (2024) 8942–8948. doi: 10.1021/acs.jpclett.4c02000
26. [26]
  L. Zhang, H. Huang, Z. Lv, et al., ACS Appl. Electron. Mater. 3 (2021) 1043–1049. doi: 10.1021/acsaelm.0c00731
27. [27]
  Z. Yu, J. Song, M.L. Gordin, R. Yi, D. Tang, D. Wang, Adv. Sci. 2 (2015) 1400020. doi: 10.1002/advs.201400020
28. [28]
  X. Li, G. Chen, Z. Le, et al., Nano Energy 59 (2019) 464–471. doi: 10.1016/j.nanoen.2019.02.061
29. [29]
  M. Li, W. Li, Y. Hu, et al., Adv. Mater. 33 (2021) 2101259. doi: 10.1002/adma.202101259
30. [30]
  L. Zhu, K. Xu, Y. Fang, et al., Adv. Funct. Mater. 33 (2023) 2302444. doi: 10.1002/adfm.202302444
31. [31]
  W. Li, Z. Yang, M. Li, et al., Nano Lett. 16 (2016) 1546–1553. doi: 10.1021/acs.nanolett.5b03903
32. [32]
  R. Ma, L. Xiong, P. Jiao, et al., J. Am. Chem. Soc. 146 (2024) 23044–23053. doi: 10.1021/jacs.4c03691
33. [33]
  M. Mayo, K.J. Griffith, C.J. Pickard, A.J. Morris, Chem. Mater. 28 (2016) 2011–2021. doi: 10.1021/acs.chemmater.5b04208
34. [34]
  X. Wu, S. Wang, X. Lin, et al., J. Mater. Chem. A 2 (2014) 1006–1013. doi: 10.1039/C3TA13801A
35. [35]
  W. Wang, Y. Sun, B. Liu, S. Wang, M. Cao, Carbon 91 (2015) 56–65. doi: 10.1016/j.carbon.2015.04.041
36. [36]
  P. Barbaro, M. Di Vaira, M. Peruzzini, S.S. Costantini, P. Stoppioni, Angew. Chem. 120 (2008) 4497–4499. doi: 10.1002/ange.200800723
37. [37]
  S. Lange, P. Schmidt, T. Nilges, Inorg. Chem. 46 (2007) 4028–4035. doi: 10.1021/ic062192q
38. [38]
  T. Wiegand, H. Eckert, S. Grimme, D. Hoppe, M. Ruck, Chem. Eur. J. 17 (2011) 8739–8748. doi: 10.1002/chem.201003560
39. [39]
  J.E. Frerichs, J. Koppe, S. Engelbert, et al., Chem. Mater. 33 (2021) 3499–3514. doi: 10.1021/acs.chemmater.0c04392
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