Citation: Qinyao Jiang, Binhao Wang, Zerui Yan, Sicheng Fan, Dafu Tang, Biwei Xiao, Qiulong Wei. Unraveling the pseudocapacitive sodium-ion storage mechanism of birnessite in organic electrolytes[J]. Chinese Chemical Letters, ;2025, 36(11): 110416. doi: 10.1016/j.cclet.2024.110416 shu

Unraveling the pseudocapacitive sodium-ion storage mechanism of birnessite in organic electrolytes

Qinyao Jiang ^a ,
Binhao Wang ^a ,
Zerui Yan ^a ,
Sicheng Fan ^a ,
Dafu Tang ^a ,
Biwei Xiao ^{b, *,} ,
Qiulong Wei ^{a, *,}

a.
Department of Materials Science and Engineering, Fujian Key Laboratory of Surface and Interface Engineering for High Performance Materials, College of Materials, Xiamen University, Xiamen 361005, China
b.
GRINM (Guangdong) Research Institute for Advanced Materials and Technology, Foshan 528051, China

xiaobiwei@grinm.com

qlwei@xmu.edu.cn

Received Date: 25 July 2024
Revised Date: 21 August 2024
Accepted Date: 5 September 2024
Available Online: 6 September 2024

Figures(5)

Earth-abundant, layered birnessite is promising cathode for electrochemical capacitors due to the presence of confined nanofluids in interlayers for rapid ion storage. Previous work has demonstrated the capacitive co-intercalation of water and K⁺ ions into birnessite in aqueous electrolytes, but in-depth quantitative investigations of the interactions between confined water and an external organic electrolyte are still lacking. In this work, we reveal the intercalation pseudocapacitance of hydrated birnessite (Na_0.4MnO₂·0.53H₂O) in sodium-based organic electrolytes via operando electrochemical quartz crystal microbalance (EQCM), and ex situ X-ray diffraction and Raman spectroscopy. The Na⁺ ions are completely desolvated at the Na_0.4MnO₂·0.53H₂O-organic electrolyte interfaces and intercalate into the interlayers, while the confined water does not co-extract. The net Na⁺ intercalation is a pseudocapacitive behavior without phase changes, displaying a high capacitive contribution of 85.6% at 1.0 mV/s. Additionally, EQCM results indicate the contributions of cation-dominated electric double layer (EDL) adsorption to the total charge storage. By replacing different solvents and anions in sodium-based organic electrolytes, we verify that Na⁺ pseudocapacitive intercalation dominates the charge storage properties.
- Pseudocapacitance,
- Sodium-ion storage,
- Interlayer confinement,
- Birnessite,
- EQCM
1. [1]
  C. Zhao, Q. Wang, Z. Yao, et al., Science 370 (2020) 708–711. doi: 10.1126/science.aay9972
2. [2]
  S.J. Shin, J.W. Gittins, C.J. Balhatchet, A. Walsh, A.C. Forse, Adv. Funct. Mater. (2023) 2308497. doi: 10.1002/adfm.202308497
3. [3]
  J. Feng, Y. Wang, Y. Xu, et al., Adv. Mater. 33 (2021) 2100887.
4. [4]
  Z. Xiong, P. Guo, Y. Yang, et al., Adv. Energy Mater. 12 (2022) 2103226.
5. [5]
  H. Chen, K. Chen, J. Yang, et al., J. Am. Chem. Soc. 23 (2024) 15751–15760. doi: 10.1021/jacs.4c01395
6. [6]
  J. Zhou, Q. Li, X. Hu, et al., Chin. Chem. Lett. 35 (2024) 109143.
7. [7]
  Y. Wang, Y. Liu, X. Huang, et al., Chin. Chem. Lett. 35 (2024) 109301.
8. [8]
  J. Ding, W. Hu, E. Paek, D. Mitlin, Chem. Rev. 14 (2018) 6457–6498. doi: 10.1021/acs.chemrev.8b00116
9. [9]
  S. Fleischmann, J.B. Mitchell, R. Wang, et al., Chem. Rev 14 (2020) 6738–6782. doi: 10.1021/acs.chemrev.0c00170
10. [10]
  G. Zhang, T. Xiong, L. Xia, et al., Batteries 12 (2022) 252. doi: 10.3390/batteries8120252
11. [11]
  W. van den Bergh, M. Stefik, Adv. Funct. Mater. 31 (2022) 2204126.
12. [12]
  C. Choi, D.S. Ashby, D.M. Butts, et al., Nat. Rev. Mater. 5 (2020) 5–19.
13. [13]
  M. Mateos, N. Makivic, Y. -S. Kim, B. Limoges, V. Balland, Adv. Energy Mater. 23 (2020) 2000332.
14. [14]
  W. Guo, C. Yu, S. Li, et al., Nano Energy 57 (2019) 459–472.
15. [15]
  T. Wang, X. Zhu, S.V. Savilov, S.M. Aldoshin, H. Xia, Funct. Mater. Lett. 14 (2021) 2130013.
16. [16]
  L. Yan, X. Li, H. Pan, ACS Appl. Mater. Interfaces 16 (2024) 26280–26287. doi: 10.1021/acsami.4c04256
17. [17]
  I.I. Misnon, R.A. Aziz, N.K.M. Zain, et al., Mater. Res. Bull. 57 (2014) 221–230.
18. [18]
  S. Boyd, R. Dhall, J.M. LeBeau, V. Augustyn, J. Mater. Chem. A 44 (2018) 22266–22276. doi: 10.1039/c8ta08367c
19. [19]
  S. Boyd, K. Ganeshan, W. -Y. Tsai, et al., Nat. Mater. 20 (2021) 1689–1694. doi: 10.1038/s41563-021-01066-4
20. [20]
  S. Kim, S. Lee, K.W. Nam, et al., Chem. Mater. 28 (2016) 5488–5494. doi: 10.1021/acs.chemmater.6b02083
21. [21]
  E. Bendadesse, A.V. Morozov, A.M. Abakumov, et al., ACS Nano 16 (2022) 14907–14917. doi: 10.1021/acsnano.2c05784
22. [22]
  S.L. Kuo, N.L. Wu, J. Electrochem. Soc. 153 (2006) A1317. doi: 10.1149/1.2197667
23. [23]
  T. Lv, L. Suo, Curr. Opin. Electrochem. 29 (2021) 100818.
24. [24]
  K.W. Nam, S. Kim, E. Yang, et al., Chem. Mater. 27 (2015) 3721–3725. doi: 10.1021/acs.chemmater.5b00869
25. [25]
  Y. Jiang, S. Tan, Q. Wei, et al., J. Mater. Chem. A 6 (2018) 12259–12266. doi: 10.1039/c8ta02516a
26. [26]
  Y. Zhao, Q. Fang, X. Zhu, et al., J. Mater. Chem. A 8 (2020) 8969–8978. doi: 10.1039/d0ta01480j
27. [27]
  W. Gu, G. Lv, L. Liao, et al., J. Hazard. Mater. 338 (2017) 428–436.
28. [28]
  S. Zhu, W. Huo, X. Liu, Y. Zhang, Nanoscale Adv. 2 (2020) 37–54. doi: 10.1039/c9na00547a
29. [29]
  C. Julien, M. Massot, R. Baddour-Hadjean, et al., Solid State Ionics 159 (2003) 345–356.
30. [30]
  M. Najdoski, V. Koleva, A. Samet, J. Phys. Chem. C 118 (2014) 9636–9646. doi: 10.1021/jp4127122
31. [31]
  A.C. Alves, J.P. Correia, T.M. Silva, M.F. Montemor, Electrochim. Acta 454 (2023) 142418.
32. [32]
  W. Zuo, X. Liu, J. Qiu, et al., Nat. Commun. 12 (2021) 4903.
33. [33]
  T. Brezesinski, J. Wang, S.H. Tolbert, B. Dunn, Nat. Mater. 9 (2010) 146–151. doi: 10.1038/nmat2612
34. [34]
  J. Jin, R. Wang, K. Yu, et al., Sep. Purif. Technol. 353 (2025) 128290.
35. [35]
  R. Wang, J. He, C. Yan, et al., Adv. Mater. 36 (2024) 2402681. doi: 10.1002/adma.202402681
36. [36]
  J. Ko, C. Lai, J. Long, et al., ACS Appl. Mater. Interfaces 12 (2020) 14071–14078. doi: 10.1021/acsami.0c02020
37. [37]
  H. Yu, M. Aakyiir, S. Xu, J.D. Whittle, D. Losic, J. Ma, Today Energy 21 (2021) 100757.
38. [38]
  X. Shan, F. Guo, D.S. Charles, et al., Nat. Commun. 10 (2019) 4975.
39. [39]
  P. Xiong, R. Ma, N. Sakai, et al., ACS Appl. Mater. Interfaces 9 (2017) 6282–6291. doi: 10.1021/acsami.6b14612
40. [40]
  H.Y. Asl, A. Manthiram, Science 369 (2020) 140–141. doi: 10.1126/science.abc5454
41. [41]
  Y.K. Hsu, Y.C. Chen, Y.G. Lin, L.C. Chen, K.H. Chen, Chem. Commun. 47 (2011) 1252–1254.
42. [42]
  Q. Zhang, M.D. Levi, Q. Dou, et al., Adv. Energy Mater. 9 (2019) 1802707.
43. [43]
  L. Wang, Y. Lu, J. Liu, et al., Angew. Chem. Int. Ed. 52 (2013) 1964–1967. doi: 10.1002/anie.201206854
44. [44]
  J. Dai, Y. Zhu, H.A. Tahini, et al., Nat. Commun. 11 (2020) 5657.
45. [45]
  L. Gao, J. Chen, Q. Chen, X. Kong, Sci. Adv. 8 (2022) eabm4606.
46. [46]
  X. Li, Z. Ao, J. Liu, et al., ACS Nano 10 (2016) 11532–11540. doi: 10.1021/acsnano.6b07522
47. [47]
  C. Wu, Y. Yang, Y. Zhang, et al., Angew. Chem. Int. Ed. 63 (2024) e202406889.
48. [48]
  L. Sheng, D. Zhu, K. Yang, et al., Nano Lett. 24 (2024) 533–540. doi: 10.1021/acs.nanolett.3c01682
49. [49]
  H. Kim, J. Hong, G. Yoon, et al., Energy Environ. Sci. 8 (2015) 2963–2969.
50. [50]
  F. Zhao, S. Zeng, L. Duan, et al., J. Phys. Chem. C 124 (2020) 28431–28436. doi: 10.1021/acs.jpcc.0c10237
51. [51]
  Y. Ando, M. Okubo, A. Yamada, M. Otani, Adv. Funct. Mater. 30 (2020) 2000820.
52. [52]
  Z. Wen, W. Fang, F. Wang, et al., Angew. Chem. Int. Ed. 63 (2024) e202314876.
53. [53]
  H. He, J. Zhou, L. Yang, et al., J. Mater. Chem. A 12 (2024) 10279–10286. doi: 10.1039/d4ta00701h
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