Issue

Vol. 16 (2024)

A Solvent-Free Covalent Organic Framework Single-Ion Conductor Based on Ion–Dipole Interaction for All-Solid-State Lithium Organic Batteries

https://doi.org/10.1007/s40820-024-01485-3
Zhongping Li
Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei‑Ro, Seodaemun‑Gu, Seoul 03722, Republic of Korea
Kyeong‑Seok Oh
Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei‑Ro, Seodaemun‑Gu, Seoul 03722, Republic of Korea
Jeong‑Min Seo
School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST‑Gil, Eonyang‑Eup, Ulju‑Gun, Ulsan 44919, Republic of Korea
Wenliang Qin
Henan Key Laboratory of Functional Salt Materials, Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou 450007, People’s Republic of China
Soohyoung Lee
Department of Battery Conflation Engineering, Yonsei University, 50, Yonsei‑Ro, Seodaemun‑Gu, Seoul 03772, Republic of Korea
Lipeng Zhai
Henan Key Laboratory of Functional Salt Materials, Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou 450007, People’s Republic of China
Changqing Li
School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST‑Gil, Eonyang‑Eup, Ulju‑Gun, Ulsan 44919, Republic of Korea
Jong‑Beom Baek
School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST‑Gil, Eonyang‑Eup, Ulju‑Gun, Ulsan 44919, Republic of Korea
Sang‑Young Lee
Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei‑Ro, Seodaemun‑Gu, Seoul 03722, Republic of Korea

Corresponding Author: Sang‑Young Lee

syleek@yonsei.ac.kr

Nano-Micro Letters, Vol. 16 (2024), Article Number: 265

Abstract

Single-ion conductors based on covalent organic frameworks (COFs) have garnered attention as a potential alternative to currently prevalent inorganic ion conductors owing to their structural uniqueness and chemical versatility. However, the sluggish Li+ conduction has hindered their practical applications. Here, we present a class of solvent-free COF single-ion conductors (Li-COF@P) based on weak ion–dipole interaction as opposed to traditional strong ion–ion interaction. The ion (Li+ from the COF)–dipole (oxygen from poly(ethylene glycol) diacrylate embedded in the COF pores) interaction in the Li-COF@P promotes ion dissociation and Li+ migration via directional ionic channels. Driven by this single-ion transport behavior, the Li-COF@P enables reversible Li plating/stripping on Li-metal electrodes and stable cycling performance (88.3% after 2000 cycles) in organic batteries (Li metal anode||5,5’-dimethyl-2,2’-bis-p-benzoquinone (Me2BBQ) cathode) under ambient operating conditions, highlighting the electrochemical viability of the Li-COF@P for all-solid-state organic batteries.


Highlights:


1 A class of solvent-free covalent organic framework (COF) single-ion conductors (Li-COF@P) has been designed via ion–dipole interaction as opposed to traditional ion–ion interaction, promoting ion dissociation and Li+ migration through directional ionic channels.
2 The Li-COF@P enabled long cycle life (88.3% after 2000 cycles) in all-solid-state Li organic batteries (ASSLOBs) under ambient operating conditions, which outperformed those of previously reported ASSOLBs.
3 This Li-COF@P strategy holds promise as a viable alternative to the currently prevalent inorganic solid electrolytes.

Keywords

Solid organic single-ion conductors Solvent-free covalent organic frameworks All-solid-state Li organic batteries Ion–dipole interaction Pore functionalization
Li, Zhongping, Kyeong‑Seok Oh, Jeong‑Min Seo, Wenliang Qin, Soohyoung Lee, Lipeng Zhai, Changqing Li, Jong‑Beom Baek, and Sang‑Young Lee. 2024. “A Solvent-Free Covalent Organic Framework Single-Ion Conductor Based on Ion–Dipole Interaction for All-Solid-State Lithium Organic Batteries”. Nano-Micro Letters 16 (August):265. https://doi.org/10.1007/s40820-024-01485-3.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. C. Yang, Z. Suo, Hydrogel ionotronics. Nat. Rev. Mater. 3, 125–142 (2018). https://doi.org/10.1038/s41578-018-0018-7
  2. H.J. Kim, B. Chen, Z. Suo, R.C. Hayward, Ionoelastomer junctions between polymer networks of fixed anions and cations. Science 367, 773–776 (2020). https://doi.org/10.1126/science.aay8467
  3. W. Zhang, D.H. Seo, T. Chen, L. Wu, M. Topsakal et al., Kinetic pathways of ionic transport in fast-charging lithium titanate. Science 367, 1030–1034 (2020). https://doi.org/10.1126/science.aax3520
  4. C.S. Rustomji, Y. Yang, T.K. Kim, J. Mac, Y.J. Kim et al., Liquefied gas electrolytes for electrochemical energy storage devices. Science 356, al4263 (2017). https://doi.org/10.1126/science.aal4263
  5. Q. Zhao, S. Stalin, C.-Z. Zhao, L.A. Archer, Designing solid-state electrolytes for safe, energy-dense batteries. Nat. Rev. Mater. 5, 229–252 (2020). https://doi.org/10.1038/s41578-019-0165-5
  6. C. Fang, J. Li, M. Zhang, Y. Zhang, F. Yang et al., Quantifying inactive lithium in lithium metal batteries. Nature 572, 511–515 (2019). https://doi.org/10.1038/s41586-019-1481-z
  7. J. Zheng, Q. Zhao, T. Tang, J. Yin, C.D. Quilty et al., Reversible epitaxial electrodeposition of metals in battery anodes. Science 366, 645–648 (2019). https://doi.org/10.1126/science.aax6873
  8. J. Janek, W.G. Zeier, A solid future for battery development. Nat. Energy 1, 16141 (2016). https://doi.org/10.1038/nenergy.2016.141
  9. M. Winter, B. Barnett, K. Xu, Before Li ion batteries. Chem. Rev. 118, 11433–11456 (2018). https://doi.org/10.1021/acs.chemrev.8b00422
  10. Y. An, X. Han, Y. Liu, A. Azhar, J. Na et al., Progress in solid polymer electrolytes for lithium-ion batteries and beyond. Small 18, e2103617 (2022). https://doi.org/10.1002/smll.202103617
  11. T. Zhou, X. Huang, N. Ding, Z. Lin, Y. Yao et al., Porous polyelectrolyte frameworks: synthesis, post-ionization and advanced applications. Chem. Soc. Rev. 51, 237–267 (2022). https://doi.org/10.1039/d1cs00889g
  12. D. Luo, M. Li, Q. Ma, G. Wen, H. Dou et al., Porous organic polymers for Li-chemistry-based batteries: functionalities and characterization studies. Chem. Soc. Rev. 51, 2917–2938 (2022). https://doi.org/10.1039/d1cs01014j
  13. P.J. Waller, F. Gándara, O.M. Yaghi, Chemistry of covalent organic frameworks. Acc. Chem. Res. 48, 3053–3063 (2015). https://doi.org/10.1021/acs.accounts.5b00369
  14. J. Li, X. Jing, Q. Li, S. Li, X. Gao et al., Bulk COFs and COF nanosheets for electrochemical energy storage and conversion. Chem. Soc. Rev. 49, 3565–3604 (2020). https://doi.org/10.1039/d0cs00017e
  15. S.-Y. Ding, W. Wang, Covalent organic frameworks (COFs): from design to applications. Chem. Soc. Rev. 42, 548–568 (2013). https://doi.org/10.1039/c2cs35072f
  16. D. Zhu, G. Xu, M. Barnes, Y. Li, C.-P. Tseng et al., Covalent organic frameworks for batteries. Adv. Funct. Mater. 31, 2100505 (2021). https://doi.org/10.1002/adfm.202100505
  17. H. Wang, Z. Zeng, P. Xu, L. Li, G. Zeng et al., Recent progress in covalent organic framework thin films: fabrications, applications and perspectives. Chem. Soc. Rev. 48, 488–516 (2019). https://doi.org/10.1039/c8cs00376a
  18. R.-R. Liang, S.-Y. Jiang, A. Ru-Han, X. Zhao, Two-dimensional covalent organic frameworks with hierarchical porosity. Chem. Soc. Rev. 49, 3920–3951 (2020). https://doi.org/10.1039/d0cs00049c
  19. F. Meng, S. Bi, Z. Sun, B. Jiang, D. Wu et al., Synthesis of ionic vinylene-linked covalent organic frameworks through quaternization-activated Knoevenagel condensation. Angew. Chem. Int. Ed. Engl. 60, 13614–13620 (2021). https://doi.org/10.1002/anie.202104375
  20. D.A. Vazquez-Molina, G.S. Mohammad-Pour, C. Lee, M.W. Logan, X. Duan et al., Mechanically shaped two-dimensional covalent organic frameworks reveal crystallographic alignment and fast Li-ion conductivity. J. Am. Chem. Soc. 138, 9767–9770 (2016). https://doi.org/10.1021/jacs.6b05568
  21. C. Li, D.-D. Wang, G.S.H. Poon Ho, Z. Zhang, J. Huang et al., Anthraquinone-based silicate covalent organic frameworks as solid electrolyte interphase for high-performance lithium–metal batteries. J. Am. Chem. Soc 145, 24603–24614 (2023). https://doi.org/10.1021/jacs.3c06723
  22. Z. Meng, R.M. Stolz, K.A. Mirica, Two-dimensional chemiresistive covalent organic framework with high intrinsic conductivity. J. Am. Chem. Soc. 141, 11929–11937 (2019). https://doi.org/10.1021/jacs.9b03441
  23. Y. Hu, N. Dunlap, S. Wan, S. Lu, S. Huang et al., Crystalline lithium imidazolate covalent organic frameworks with high Li-ion conductivity. J. Am. Chem. Soc. 141, 7518–7525 (2019). https://doi.org/10.1021/jacs.9b02448
  24. G. Zhang, Y.-L. Hong, Y. Nishiyama, S. Bai, S. Kitagawa et al., Accumulation of glassy poly(ethylene oxide) anchored in a covalent organic framework as a solid-state Li+ electrolyte. J. Am. Chem. Soc. 141, 1227–1234 (2019). https://doi.org/10.1021/jacs.8b07670
  25. H. Xu, S. Tao, D. Jiang, Proton conduction in crystalline and porous covalent organic frameworks. Nat. Mater. 15, 722–726 (2016). https://doi.org/10.1038/nmat4611
  26. L. Yao, C. Ma, L. Sun, D. Zhang, Y. Chen et al., Highly crystalline polyimide covalent organic framework as dual-active-center cathode for high-performance lithium-ion batteries. J. Am. Chem. Soc. 144, 23534–23542 (2022). https://doi.org/10.1021/jacs.2c10534
  27. S. Xu, M. Richter, X. Feng, Vinylene-linked two-dimensional covalent organic frameworks: synthesis and functions. Acc. Mater. Res. 2, 252–265 (2021). https://doi.org/10.1021/accountsmr.1c00017
  28. W. Gong, Y. Ouyang, S. Guo, Y. Xiao, Q. Zeng et al., Covalent organic framework with multi-cationic molecular chains for gate mechanism controlled superionic conduction in all-solid-state batteries. Angew. Chem. Int. Ed. 62, e202302505 (2023). https://doi.org/10.1002/anie.202302505
  29. D. Guo, D.B. Shinde, W. Shin, E. Abou-Hamad, A.-H. Emwas et al., Foldable solid-state batteries enabled by electrolyte mediation in covalent organic frameworks. Adv. Mater. 34, e2201410 (2022). https://doi.org/10.1002/adma.202201410
  30. K. Jeong, S. Park, G.Y. Jung, S.H. Kim, Y.-H. Lee et al., Solvent-free, single lithium-ion conducting covalent organic frameworks. J. Am. Chem. Soc. 141, 5880–5885 (2019). https://doi.org/10.1021/jacs.9b00543
  31. X. Li, Q. Hou, W. Huang, H.-S. Xu, X. Wang et al., Solution-processable covalent organic framework electrolytes for all-solid-state Li–organic batteries. ACS Energy Lett. 5, 3498–3506 (2020). https://doi.org/10.1021/acsenergylett.0c01889
  32. G. Zhao, Z. Mei, L. Duan, Q. An, Y. Yang et al., COF-based single Li+ solid electrolyte accelerates the ion diffusion and restrains dendrite growth in quasi-solid-state organic batteries. Carbon Energy 5, e248 (2023). https://doi.org/10.1002/cey2.248
  33. X. Li, K.P. Loh, Recent progress in covalent organic frameworks as solid-state ion conductors. ACS Mater. Lett. 1, 327–335 (2019). https://doi.org/10.1021/acsmaterialslett.9b00185
  34. S. Yuan, X. Li, J. Zhu, G. Zhang, P. Van Puyvelde et al., Covalent organic frameworks for membrane separation. Chem. Soc. Rev. 48, 2665–2681 (2019). https://doi.org/10.1039/c8cs00919h
  35. H.S. Sasmal, H.B. Aiyappa, S.N. Bhange, S. Karak, A. Halder et al., Superprotonic conductivity in flexible porous covalent organic framework membranes. Angew. Chem. Int. Ed. 57, 10894–10898 (2018). https://doi.org/10.1002/anie.201804753
  36. M.C. Senarathna, H. Li, S.D. Perera, J. Torres-Correas, S.D. Diwakara et al., Highly flexible dielectric films from solution processable covalent organic frameworks. Angew. Chem. Int. Ed. 62, e202312617 (2023). https://doi.org/10.1002/anie.202312617
  37. F. Biedermann, H.-J. Schneider, Experimental binding energies in supramolecular complexes. Chem. Rev. 116, 5216–5300 (2016). https://doi.org/10.1021/acs.chemrev.5b00583
  38. S. Bai, B. Kim, C. Kim, O. Tamwattana, H. Park et al., Permselective metal-organic framework gel membrane enables long-life cycling of rechargeable organic batteries. Nat. Nanotechnol. 16, 77–84 (2021). https://doi.org/10.1038/s41565-020-00788-x
  39. R. Bouchet, S. Maria, R. Meziane, A. Aboulaich, L. Lienafa et al., Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries. Nat. Mater. 12, 452–457 (2013). https://doi.org/10.1038/nmat3602
  40. K. Jeong, S. Park, S.-Y., Lee Revisiting polymeric single lithium-ion conductors as an organic route for all-solid-state lithium ion and metal batteries. J. Mater. Chem. A 7, 1917–1935 (2019). https://doi.org/10.1039/C8TA09056D
  41. K.-S. Oh, S. Park, J.-S. Kim, Y. Yao, J.-H. Kim et al., Electrostatic covalent organic frameworks as on-demand molecular traps for high-energy Li metal battery electrodes. ACS Energy Lett. 8, 2463–2474 (2023). https://doi.org/10.1021/acsenergylett.3c00600
  42. K.-S. Oh, J.-H. Kim, S.-H. Kim, D. Oh, S.-P. Han et al., Single-ion conducting soft electrolytes for semi-solid lithium metal batteries enabling cell fabrication and operation under ambient conditions. Adv. Energy Mater. 11, 2170151 (2021). https://doi.org/10.1002/aenm.202170151
  43. D.H. Kim, Y.-H. Lee, Y.B. Song, H. Kwak, S.-Y. Lee et al., Thin and flexible solid electrolyte membranes with ultrahigh thermal stability derived from solution-processable Li argyrodites for all-solid-state Li-ion batteries. ACS Energy Lett. 5, 718–727 (2020). https://doi.org/10.1021/acsenergylett.0c00251
  44. H. Chen, H. Tu, C. Hu, Y. Liu, D. Dong et al., Cationic covalent organic framework nanosheets for fast Li-ion conduction. J. Am. Chem. Soc. 140, 896–899 (2018). https://doi.org/10.1021/jacs.7b12292
  45. Y. Cao, M. Wang, H. Wang, C. Han, F. Pan et al., Covalent organic framework for rechargeable batteries: mechanisms and properties of ionic conduction. Adv. Energy Mater. 12, 2200057 (2022). https://doi.org/10.1002/aenm.202200057
  46. Z. Zhu, M. Hong, D. Guo, J. Shi, Z. Tao et al., All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode. J. Am. Chem. Soc. 136, 16461–16464 (2014). https://doi.org/10.1021/ja507852t
  47. H. Fei, Y. Liu, Y. An, X. Xu, G. Zeng et al., Stable all-solid-state potassium battery operating at room temperature with a composite polymer electrolyte and a sustainable organic cathode. J. Power. Sources 399, 294–298 (2018). https://doi.org/10.1016/j.jpowsour.2018.07.124
  48. B. Kim, H. Kang, K. Kim, R.Y. Wang, M.J. Park, All-solid-state lithium-organic batteries comprising single-ion polymer nanop electrolytes. ChemSusChem 13, 2271–2279 (2020). https://doi.org/10.1002/cssc.202000117
  49. W. Li, L. Chen, Y. Sun, C. Wang, Y. Wang et al., All-solid-state secondary lithium battery using solid polymer electrolyte and anthraquinone cathode. Solid State Ion. 300, 114–119 (2017). https://doi.org/10.1016/j.ssi.2016.12.013
  50. Y. Shi, Y. Chen, Y. Liang, J. Andrews, H. Dong et al., Chemically inert covalently networked triazole-based solid polymer electrolytes for stable all-solid-state lithium batteries. J. Mater. Chem. A 7, 19691–19695 (2019). https://doi.org/10.1039/C9TA05885K
  51. M. Lécuyer, J. Gaubicher, A.-L. Barrès, F. Dolhem, M. Deschamps et al., A rechargeable lithium/quinone battery using a commercial polymer electrolyte. Electrochem. Commun. 55, 22–25 (2015). https://doi.org/10.1016/j.elecom.2015.03.010
  52. M. Lécuyer, M. Deschamps, D. Guyomard, J. Gaubicher, P. Poizot, Electrochemical assessment of indigo carmine dye in lithium metal polymer technology. Molecules 26, 3079 (2021). https://doi.org/10.3390/molecules26113079
  53. W. Wei, L. Li, L. Zhang, J. Hong, G. He, An all-solid-state Li-organic battery with quinone-based polymer cathode and composite polymer electrolyte. Electrochem. Commun. 90, 21–25 (2018). https://doi.org/10.1016/j.elecom.2018.03.006
  54. S. Muench, R. Burges, A. Lex-Balducci, J.C. Brendel, M. Jäger et al., Printable ionic liquid-based gel polymer electrolytes for solid state all-organic batteries. Energy Storage Mater. 25, 750–755 (2020). https://doi.org/10.1016/j.ensm.2019.09.011
  55. J. Zhang, Z. Chen, Q. Ai, T. Terlier, F. Hao et al., Microstructure engineering of solid-state composite cathode via solvent-assisted processing. Joule 5, 1845–1859 (2021). https://doi.org/10.1016/j.joule.2021.05.017
  56. F. Hao, X. Chi, Y. Liang, Y. Zhang, R. Xu et al., Taming active material-solid electrolyte interfaces with organic cathode for all-solid-state batteries. Joule 3, 1349–1359 (2019). https://doi.org/10.1016/j.joule.2019.03.017
  57. X. Zhou, Y. Zhang, M. Shen, Z. Fang, T. Kong et al., A highly stable Li-organic all-solid-state battery based on sulfide electrolytes. Adv. Energy Mater. 12, 2103932 (2022). https://doi.org/10.1002/aenm.202103932
  58. Z. Yang, F. Wang, Z. Hu, J. Chu, H. Zhan et al., Room-temperature all-solid-state lithium–organic batteries based on sulfide electrolytes and organodisulfide cathodes. Adv. Energy Mater. 11, 2102962 (2021). https://doi.org/10.1002/aenm.202102962
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE
Statistic
Read Counter : 2721 Download : 2010

Most read articles by the same author(s)