Citation: Huixin Chen, Chen Zhao, Hongjun Yue, Guiming Zhong, Xiang Han, Liang Yin, Ding Chen. Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries[J]. Chinese Chemical Letters, ;2025, 36(1): 109650. doi: 10.1016/j.cclet.2024.109650 shu

Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries

Huixin Chen ^{a, b, f} ,
Chen Zhao ^{b, f} ,
Hongjun Yue ^{b, f, *,} ,
Guiming Zhong ^{b, d, f} ,
Xiang Han ^{c, *,} ,
Liang Yin ^e ,
Ding Chen ^{a, *,}

a.
State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body, College of Mechanical and Vehicle Engineering, Hunan University, Changsha 410082, China
b.
CAS key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
c.
College of Materials Science and Engineering, Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China
d.
Laboratory of Advanced Spectro-electrochemistry and Li-ion Batteries, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
e.
Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
f.
Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare Earth Materials, Haixi institutes, Chinese Academy of Sciences, Xiamen 361021, China

hjyue@fjirsm.ac.cn

hanxiang@njfu.edu.cn

chending@hnu.edu.cn

Received Date: 21 January 2024
Accepted Date: 7 February 2024
Available Online: 10 February 2024

Figures(4)

Phosphorus-based anode is a promising anode for sodium-ion batteries (SIBs) due to its high specific capacity, however, suffers from poor electronic conductivity and unfavorable electrochemical reversibility. Incorporating metals such as copper (Cu) into phosphorus has been demonstrated to not only improve the electronic conductivity but also accommodate the volume change during cycling, yet the underline sodiation mechanism is not clear. Herein, take a copper phosphide and reduced graphene oxide (CuP₂/C) composite as an example, which delivers a high reversible capacity of > 900 mAh/g. Interestingly, it is revealed that the native oxidation PO components of the CuP₂/C composite show higher electrochemical reversibility than the bulk CuP₂, based on a quantitative analysis of high-resolution solid-state ³¹P NMR, ex-situ XPS and synchrotron X-ray diffraction characterization techniques. The sodiation products Na₃PO₄ and Na₄P₂O₇ derived from PO could react with Na-P alloys and regenerate to PO during charge process, which probably accounts for the high reversible capacity of the CuP₂/C anode. The findings also illustrate that the phosphorus transforms into nanocrystalline Na₃P and NaP alloys, which laterally shows crystallization-amorphization evolution process during cycling.
- CuP₂/C composite,
- POx component,
- Reaction mechanism,
- Solid-state NMR,
- Sodium-ion batteries
1. [1]
  N.T. Aristote, K. Zou, A. Di, et al., Chin. Chem. Lett. 33 (2022) 730–742. doi: 10.1016/j.cclet.2021.08.049
2. [2]
  C. Ma, X. Wang, J. Lan, et al., Adv. Funct. Mater. 33 (2022) 2211821.
3. [3]
  J. He, A. Bhargav, L. Su, et al., Nat. Commun. 14 (2023) 6568. doi: 10.1038/s41467-023-42383-3
4. [4]
  Na-Ion batteries K. Kubota, S. Komaba, S. Passerini, D. Bresser, A. Moretti, A. Varzi, Encyclopedia of Electrochemistry Wiley-VCH Verlag GmbH & Co KGaA, Weinheim, 2020, pp. 1–64.
5. [5]
  N. Yabuuchi, K. Kubota, M. Dahbi, et al., Chem. Rev. 114 (2014) 11636–11682. doi: 10.1021/cr500192f
6. [6]
  H. Wang, H. Chen, C. Chen, et al., Chin. Chem. Lett. 34 (2023) 107465. doi: 10.1016/j.cclet.2022.04.063
7. [7]
  B. Qin, M. Wang, S. Wu, et al., Chin. Chem. Lett. 35 (2024) 108921. doi: 10.1016/j.cclet.2023.108921
8. [8]
  H. Tan, D. Chen, X. Rui, et al., Adv. Funct. Mater. 29 (2019) 1808745. doi: 10.1002/adfm.201808745
9. [9]
  J. Ge, C. Ma, Y. Wan, et al., Adv. Funct. Mater. 33 (2023) 2305803. doi: 10.1002/adfm.202305803
10. [10]
  F.H. Yang, H. Gao, J. Chen, et al., Small Methods 1 (2017) 1700216. doi: 10.1002/smtd.201700216
11. [11]
  S.O. Kim, A. Manthiram, ACS Appl. Mater. Interfaces 9 (2017) 16221–16227. doi: 10.1021/acsami.7b02826
12. [12]
  Y. Kim, Y. Kim, A. Choi, et al., Adv. Mater. 26 (2014) 4139–4144. doi: 10.1002/adma.201305638
13. [13]
  W. Li, X. Li, J. Liao, et al., Energy Storage Mater. 20 (2019) 380–387. doi: 10.1016/j.ensm.2019.04.034
14. [14]
  Y. Kim, Y. Park, A. Choi, et al., Adv. Mater. 25 (2013) 3045–3049. doi: 10.1002/adma.201204877
15. [15]
  J. Qian, X. Wu, Y. Cao, et al., Angew. Chem. Int. Ed. 52 (2013) 4633–4636. doi: 10.1002/anie.201209689
16. [16]
  J. Sun, H.W. Lee, M. Pasta, et al., Nat. Nanotechnol. 10 (2015) 980–985. doi: 10.1038/nnano.2015.194
17. [17]
  W.J. Li, S.L. Chou, J.Z. Wang, et al., Nano Lett. 13 (2013) 5480–5484. doi: 10.1021/nl403053v
18. [18]
  Q. Liu, Z. Hu, Y. Liang, et al., Angew. Chem. Int. Ed. 59 (2020) 5159–5164. doi: 10.1002/anie.201913683
19. [19]
  Y. Lu, P. Zhou, K. Lei, et al., Adv. Energy Mater. 7 (2017) 1601973. doi: 10.1002/aenm.201601973
20. [20]
  L. Ran, B. Luo, I.R. Gentle, et al., ACS Nano 14 (2020) 8826–8837. doi: 10.1021/acsnano.0c03432
21. [21]
  T. Wang, K. Zhang, M. Park, et al., ACS Nano 14 (2020) 4352–4365. doi: 10.1021/acsnano.9b09869
22. [22]
  X. Wang, K. Chen, G. Wang, et al., ACS Nano 11 (2017) 11602–11616. doi: 10.1021/acsnano.7b06625
23. [23]
  C. Zhao, H. Chen, H. Liu, et al., J. Mater. Chem. A 9 (2021) 6274–6283. doi: 10.1039/D0TA12141J
24. [24]
  P. Nakhanivej, X. Yu, S.K. Park, et al., Nat. Mater. 18 (2019) 156–162. doi: 10.1038/s41563-018-0230-2
25. [25]
  A.Y. Kim, M.K. Kim, K. Cho, et al., ACS Appl. Mater. Interfaces 8 (2016) 19514–19523. doi: 10.1021/acsami.6b05973
26. [26]
  Q. Li, Z. Li, Z. Zhang, et al., Adv. Energy Mater. 6 (2016) 1600376. doi: 10.1002/aenm.201600376
27. [27]
  F.P. Zhao, N. Han, W.J. Huang, et al., J. Mater. Chem. A 3 (2015) 21754–21759. doi: 10.1039/C5TA05781G
28. [28]
  S. Kaushik, J. Hwang, K. Matsumoto, et al., ChemElectroChem 5 (2018) 1340–1344. doi: 10.1002/celc.201800206
29. [29]
  S.O. Kim, A. Manthiram, Chem. Commun. 52 (2016) 4337–4340. doi: 10.1039/C5CC10585D
30. [30]
  S. Chen, F. Wu, L. Shen, et al., ACS Nano 12 (2018) 7018–7027. doi: 10.1021/acsnano.8b02721
31. [31]
  Y. Zhang, G. Wang, L. Wang, et al., Nano Lett. 19 (2019) 2575–2582. doi: 10.1021/acs.nanolett.9b00342
32. [32]
  Y. Yan, S. Xia, H. Sun, et al., Chem. Eng. J. 393 (2020) 124788. doi: 10.1016/j.cej.2020.124788
33. [33]
  I.J. Pickering, G.N. George, C.T. Dameron, et al., J. Am. Chem. Soc. 115 (1993) 9498–9505. doi: 10.1021/ja00074a014
34. [34]
  S. Hayashi, K. Hayamizu, B. Chem. Soc. Jap. 62 (1989) 3061–3068. doi: 10.1246/bcsj.62.3061
35. [35]
  S. Hayashi, K. Hayamizu, Chem. Phys. Lett. 161 (1989) 158–162. doi: 10.1016/0009-2614(89)85049-3
36. [36]
  C. Marino, M. El Kazzi, E.J. Berg, et al., Chem. Mater. 29 (2017) 7151–7158. doi: 10.1021/acs.chemmater.7b01128
37. [37]
  L.E. Marbella, M.L. Evans, M.F. Groh, et al., J. Am. Chem. Soc. 140 (2018) 7994–8004. doi: 10.1021/jacs.8b04183
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Unraveling the reaction mechanism of high reversible capacity CuP2/C anode with native oxidation POx component for sodium-ion batteries

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通讯作者: 陈斌, bchen63@163.com

Unraveling the reaction mechanism of high reversible capacity CuP₂/C anode with native oxidation PO_x component for sodium-ion batteries