Citation: Yuetong Gao, Tong Mu, Xinyue Hu, Yang Pang, Chengji Zhao. Facile synthesis of all-carbon fluorinated backbone polymers containing sulfide linkage as proton exchange membranes for fuel cells[J]. Chinese Chemical Letters, ;2025, 36(6): 110763. doi: 10.1016/j.cclet.2024.110763 shu

Facile synthesis of all-carbon fluorinated backbone polymers containing sulfide linkage as proton exchange membranes for fuel cells

Key Laboratory of High Performance Plastics, Ministry of Education, College of Chemistry, Jilin University, Changchun 130012, China

zhaochengji@jlu.edu.cn

Received Date: 25 October 2024
Revised Date: 11 December 2024
Accepted Date: 12 December 2024
Available Online: 13 December 2024

Figures(4)

Aryl-ether bonds are facile to attack by oxidizing radicals, thus stimulating the exploitation of ether-free polymers as proton exchange membranes (PEMs) for the long-lasting operation of fuel cells. In this study, a novel class of PEMs derived from all-carbon fluorinated backbone polymers containing sulfide-linked alkyl sulfonic acid side chains have been developed through a straightforward and effective synthetic procedure. The sulfide-linked alkyl sulfonate groups were tethered to the poly(triphenylene pentafluorophenyl) backbone through a quantified and site-specific para-fluoro-thiol click reaction. Owing to the existence of obvious phase separation morphology between hydrophobic main chain and hydrophilic sulfonate groups in the side chains, resulting PEMs demonstrated favorable proton conductivity of 142.5 mS/cm at 80 ℃, while maintaining excellent dimensional stability with an in-plane swelling ratio of <17% as well as a through-plane swelling ratio of <25%. They also exhibit elevated thermal decomposition temperatures (T_d5_% exceeding 300 ℃) alongside high tensile strength (>50 MPa). Furthermore, the ether-free full-carbon fluorinated main chain and the -S- group in the side chain, which serves as an effective free-radical scavenger, providing good chemical stability during Fenton's test. The PEMs achieved a maximum power density of 407 mW/cm² in a single H₂/air fuel cell, and an open-circuit voltage decline rate of 0.275 mV/h in a durability test at 30% RH and 80 ℃. Concurrently, the hydrogen crossover current density is only 1/3 of that of Nafion 212. These findings reveal that the resulted PEMs display considerable antioxidative properties along with commendable performance, with prospective applications in proton exchange membrane fuel cells.
- All-carbon backbone,
- Proton exchange membrane,
- Fuel cells,
- Facile synthesis,
- Low hydrogen permeability
1. [1]
  I. Staffell, D. Scamman, A. Velazquez Abad, et al., Energy Environ. Sci. 12 (2019) 463–491. doi: 10.1039/c8ee01157e
2. [2]
  K. Espegren, S. Damman, P. Pisciella, I. Graabak, A. Tomasgard, Int. J. Hydrog. Energy 46 (2021) 23125–23138. doi: 10.1016/j.ijhydene.2021.04.143
3. [3]
  M. Adamski, T.J.G. Skalski, B. Britton, et al., Angew. Chem. Int. Ed. 56 (2017) 9058–9061. doi: 10.1002/anie.201703916
4. [4]
  H. Tang, K. Geng, L. Wu, et al., Nat. Energy 7 (2022) 153–162. doi: 10.1038/s41560-021-00956-w
5. [5]
  I. Salmeron-Sanchez, P. Mansouri Bakvand, A. Shirole, et al., Chem. Eng. J. 474 (2023) 145879. doi: 10.1016/j.cej.2023.145879
6. [6]
  E.H. Majlan, D. Rohendi, W.R.W. Daud, T. Husaini, M.A. Haque, Renew. Sust. Energ. Rev. 89 (2018) 117–134. doi: 10.1016/j.rser.2018.03.007
7. [7]
  Y. Wang, D.F. Ruiz Diaz, K.S. Chen, Z. Wang, X.C. Adroher, Mater. Today 32 (2020) 178–203. doi: 10.1016/j.mattod.2019.06.005
8. [8]
  K. Jiao, J. Xuan, Q. Du, et al., Nature 595 (2021) 361–369. doi: 10.1038/s41586-021-03482-7
9. [9]
  K. Oh, K. Ketpang, H. Kim, S. Shanmugam, J. Membr. Sci. 507 (2016) 135–142. doi: 10.1016/j.memsci.2016.02.027
10. [10]
  M.D.T. Nguyen, S. Yang, D. Kim, J. Power Sources 328 (2016) 355–363. doi: 10.1016/j.jpowsour.2016.08.041
11. [11]
  S. Yang, Y. Ahn, D. Kim, J. Mater. Chem. A 5 (2017) 2261–2270. doi: 10.1039/C6TA07456A
12. [12]
  C. Wang, H.Q. Li, Z. Wang, et al., Int. J. Hydrogen Energy 45 (2020) 29738–29748. doi: 10.1016/j.ijhydene.2019.09.108
13. [13]
  V.D.C. Tinh, V.D. Thuc, D. Kim, J. Membr. Sci. 634 (2021) 119430. doi: 10.1016/j.memsci.2021.119430
14. [14]
  G. Wang, J. Li, H. Li, et al., Chin. Chem. Lett. 34 (2023) 107497. doi: 10.1016/j.cclet.2022.05.011
15. [15]
  Z. Zhao, Q. Dai, S. Huang, et al., Chin. Chem. Lett. 35 (2024) 109231. doi: 10.1016/j.cclet.2023.109231
16. [16]
  X. Liu, Y. Zhang, S. Deng, et al., Chin. Chem. Lett. 30 (2019) 299–304. doi: 10.1016/j.cclet.2018.09.021
17. [17]
  J. Li, N. Cui, D. Liu, et al., Int. J. Hydrogen Energy 50 (2024) 606–617. doi: 10.1016/j.ijhydene.2023.08.334
18. [18]
  T. Li, S. Chai, B. Liu, C. Zhao, H. Li, J. Polym. Sci. 61 (2023) 2796–2814. doi: 10.1002/pol.20230405
19. [19]
  N.R. Kang, T.H. Pham, P. Jannasch, ACS Macro Lett. 8 (2019) 1247–1251. doi: 10.1021/acsmacrolett.9b00615
20. [20]
  H. Nederstedt, P. Jannasch, J. Membr. Sci. 647 (2022) 120270. doi: 10.1016/j.memsci.2022.120270
21. [21]
  P. Zuo, Y. Li, A. Wang, et al., Angew. Chem. Int. Ed. 59 (2020) 9564–9573. doi: 10.1002/anie.202000012
22. [22]
  H. Lin, Y. Ma, X. Wang, et al., J. Membr. Sci. 695 (2024) 122479. doi: 10.1016/j.memsci.2024.122479
23. [23]
  T. Weissbach, T.J. Peckham, S. Holdcroft, J. Membr. Sci. 498 (2016) 94–104. doi: 10.1016/j.memsci.2015.10.004
24. [24]
  Y. Park, D. Kim, J. Membr. Sci. 566 (2018) 1–7. doi: 10.1016/j.memsci.2018.08.063
25. [25]
  M.J. Parnian, S. Rowshanzamir, A.K. Prasad, S.G. Advani, J. Membr. Sci. 556 (2018) 12–22. doi: 10.1016/j.memsci.2018.03.083
26. [26]
  X. Liu, Y. Li, M. Li, et al., J. Membr. Sci. 629 (2021) 119282. doi: 10.1016/j.memsci.2021.119282
27. [27]
  P. Wang, C. Cai, J. Tan, M. Pan, Int. J. Hydrogen Energy 46 (2021) 34867–34873. doi: 10.1016/j.ijhydene.2021.08.045
28. [28]
  L. Zhou, J. Zhu, M. Lin, et al., J. Energy Chem. 40 (2020) 57–64. doi: 10.1016/j.jechem.2019.02.013
29. [29]
  J. Wang, Y. Dai, R. Wan, et al., Chem. Eng. J. 413 (2021) 127541. doi: 10.1016/j.cej.2020.127541
30. [30]
  G. Delaittre, L. Barner, Polym. Chem. 9 (2018) 2679–2684. doi: 10.1039/c8py00287h
31. [31]
  S. Cai, C. Wang, Z. Tao, et al., Int. J. Hydrogen Energy 47 (2022) 9319–9330. doi: 10.1016/j.ijhydene.2021.12.263
32. [32]
  B. Xue, M.Z. Zhu, S.Q. Fu, et al., J. Membr. Sci. 673 (2023) 121263. doi: 10.1016/j.memsci.2022.121263
33. [33]
  L.H. Sperling, Introduction to Physical Polymer Science, 4th ed., John Wiley & Sons Inc., 2005, pp. 349–425.
34. [34]
  N. Chen, H.H. Wang, S.P. Kim, et al., Nat. Commun. 12 (2021) 2367. doi: 10.1038/s41467-021-22612-3
35. [35]
  F. Xu, Y. Chen, J. Li, et al., J. Membr. Sci. 664 (2022) 121045. doi: 10.1016/j.memsci.2022.121045
36. [36]
  D. Qiu, L. Peng, X. Lai, M. Ni, W. Lehnert, Renew. Sust. Energ. Rev. 113 (2019) 109289. doi: 10.1016/j.rser.2019.109289
37. [37]
  M. Mohammadi, S. Mehdipour-Ataei, Renew. Energ. 158 (2020) 421–430. doi: 10.1016/j.renene.2020.05.124
38. [38]
  M. Pan, C. Pan, C. Li, J. Zhao, Renew. Sust. Energ. Rev. 141 (2021) 110771. doi: 10.1016/j.rser.2021.110771
39. [39]
  L. Liu, Y. Wang, S. Liu, et al., J. Membr. Sci. 660 (2022) 120774. doi: 10.1016/j.memsci.2022.120774
40. [40]
  Y. Zhu, L. Ding, X. Liang, et al., Energy Environ. Sci. 11 (2018) 3472–3479. doi: 10.1039/c8ee02071j
41. [41]
  S. Zhang, X. Li, Y. Yang, et al., J. Membr. Sci. 698 (2024) 122587. doi: 10.1016/j.memsci.2024.122587
42. [42]
  S. Mu, C. Xu, Q. Yuan, et al., J. Appl. Polym. Sci. 129 (2013) 1586–1592. doi: 10.1002/app.38785
43. [43]
  H. Hou, M.L. Di Vona, P. Knauth, ChemSusChem 4 (2011) 1526–1536. doi: 10.1002/cssc.201000415
44. [44]
  T. Ban, M. Guo, Y. Wang, Y. Zhang, X. Zhu, J. Membr. Sci. 668 (2023) 121255. doi: 10.1016/j.memsci.2022.121255
45. [45]
  D. Zhao, J. Li, M.K. Song, et al., Adv. Energy Mater. 1 (2011) 203–211. doi: 10.1002/aenm.201000062
46. [46]
  C. He, K.F. Han, J.H. Yu, H. Zhu, Z.M. Wang, Eur. Polym. J. 74 (2016) 168–179. doi: 10.1016/j.eurpolymj.2015.11.024
47. [47]
  V.D.C. Tinh, V.D. Thuc, Y. Jeon, G.Y. Gu, D. Kim, J. Membr. Sci. 660 (2022) 120903. doi: 10.1016/j.memsci.2022.120903
48. [48]
  A.M. Baker, L. Wang, W.B. Johnson, A.K. Prasad, S.G. Advani, J. Phys. Chem. C 118 (2014) 26796–26802. doi: 10.1021/jp5078399
49. [49]
  W. Li, R. Zhang, X. Zhao, et al., J. Mater. Chem. A 11 (2023) 4547–4558. doi: 10.1039/d2ta08911d
50. [50]
  T. Vu Dong, V.D.C. Tinh, D. Kim, J. Power Sources 556 (2023) 232418. doi: 10.1016/j.jpowsour.2022.232418
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