Textile Science and Engineering (한국섬유공학회지)

The Korean Fiber Society (한국섬유공학회)
권호 표지
DOI QR코드

DOI QR Code

Effect of Two-step UV-Crosslinking on the Crystallinity and Lithium-Ion Conductivity of PEO-Based Solid Electrolyte Film

2단계 자외선 가교가 PEO 고체 전해질막의 결정화도와 리튬이온 전도도에 미치는 영향

  • Seung Jin Ryu (Department of Materials Design Engineering, Kumoh National Institute of Technology) ;
  • Jeong Hwan Kim (Department of Materials Design Engineering, Kumoh National Institute of Technology) ;
  • Wonho Lee (Department of Polymer Science and Engineering, Kumoh National Institute of Technology) ;
  • Jinho Jang (Department of Materials Design Engineering, Kumoh National Institute of Technology)
  • 류승진 (국립금오공과대학교 화학소재공학부 소재디자인공학전공) ;
  • 김정환 (국립금오공과대학교 화학소재공학부 소재디자인공학전공) ;
  • 이원호 (국립금오공과대학교 재료공학부 고분자공학전공) ;
  • 장진호 (국립금오공과대학교 화학소재공학부 소재디자인공학전공)
  • Received : 2025.08.08
  • Accepted : 2025.08.24
  • Published : 2025.08.31
⟨ Previous Next ⟩

Abstract

Two-step photo-crosslinking of PEO film was applied to enhance the ionic conductivity of the solid polymer electrolytes (SPEs) through the decreased crystallinity by the solution crosslinking and subsequent solid crosslinking. The UV irradiation energy, the concentration of photoinitiators and lithium salts were adjusted to optimize the SPE crosslinking. In particular, the PEO films containing LiPF6 or LiTFSI were cast via a solution process using acetonitrile as a solvent, both polymer films and polymer solutions were crosslinked under 365 nm LED-UV irradiation. The tensile toughness of the crosslinked SPE containing LiPF6 increased nearly seven folds from 0.5 GPa up to 3.4 GPa. Also XRD crystallinity of the two-step crosslinked SPE decreased from 71% up to 10% surprisingly. Maximum ionic conductivity of 1.1×10-3 mS/cm at 25 ℃ was obtained by two-step crosslinking of SPE containing LiTFSI at an EO:Li ratio of 10:1. The SPEs also exhibited similar ionic conductivity to the gel polymer electrolyte containing 100 wt% liquid electrolyte. These findings support the two-step crosslinking as a viable route for the development of high-performance SPEs with superior mechanical strength.

Keywords

Acknowledgement

이 연구는 국립금오공과대학교 대학 연구과제비로 지원되었음(2024~2026).

References

  1. S. G. Jo, S. J. Seo, S. K. Kang, I. C. Na, S. Kunze, M. S. Song, S. Hwang, S. P. Woo, S. H. Kim, W. B. Kim, and J. W. Lim, "Thermal Runaway Mechanism in Ni‐Rich Cathode Full Cells of Lithium‐Ion Batteries: The Role of Multidirectional Crosstalk", Adv. Mater., 2024, 36, 2402024. https://doi.org/10.1002/adma.202402024
  2. H. D. Lim, J. H. Park, H. J. Shin, J. W. Jeong, J. T. Kim, K. W. Nam, H. G. Jung, and K. Y. Chung, "A Review of Challenges and Issues Concerning Interfaces for All-Solid-State Batteries", Energy Storage Mater., 2020, 25, 224−250. https://doi.org/10.1016/j.ensm.2019.10.011
  3. X. Wang, X. Hao, Y. Xia, Y. Liang, X. Xia, and J. Tu, "A Polyacrylonitrile (PAN)-Based Double-Layer Multifunctional Gel Polymer Electrolyte for Lithium-Sulfur Batteries", J. Membr. Sci., 2019, 582, 37−47. https://doi.org/10.1016/j.memsci.2019.03.048
  4. B. Liang, S. Tang, Q. Jiang, C. Chen, X. Chen, S. Li, and X. Yan, "Preparation and Characterization of PEO-PMMA Polymer Composite Electrolytes Doped with Nano-Al2O3", Electrochim. Acta, 2019, 169, 334−341. https://doi.org/10.1016/j.electacta.2015.04.039
  5. S. H. Nam, H. M. Seong, Y. S. Kim, K. I. Kim, C. B. Kim, S. M. Kwon, and S. J. Park, "All Fluorine-Free Lithium-Ion Batteries with High-Rate Capability", Chem. Eng. J., 2024, 497, 154790. https://doi.org/10.1016/j.cej.2024.154790
  6. A. Arya and A. L. Sharma, "Polymer Electrolytes for Lithium Ion Batteries: A Critical Study", Ionics, 2017, 23, 497−540. https://doi.org/10.1007/s11581-016-1908-6
  7. W. H. Meyer, "Polymer Electrolytes for Lithium-Ion Batteries", Adv. Mater., 1998, 10, 439−448. https://doi.org/10.1002/(SICI)1521-4095(199804)10:6<439::AID-ADMA439>3.0.CO;2-I
  8. X. Lu, Y. Wang, X. Xu, B. Yan, T. Wu, and L. Lu, "Polymer‐Based Solid-State Electrolytes for High-Energy-Density Lithium-Ion Batteries-Review", Adv. Energy Mater., 2023, 13, 2301746. https://doi.org/10.1002/aenm.202301746
  9. X. Zeng, X. Liu, H. Zhu, J. Zhu, J. Lan, Y. Yu, Y.-S. Lee, and X. Yang, "Advanced Crosslinked Solid Polymer Electrolytes: Molecular Architecture, Strategies, and Future Perspectives", Adv. Energy Mater., 2024, 14, 2402671. https://doi.org/10.1002/aenm.202402671
  10. Z. Li, J. Fu, X. Zhou, S. Gui, L. Wei, H. Yang, H. Li, and X. Guo, "Ionic Conduction in Polymer-Based Solid Electrolytes", Adv. Sci., 2023, 10, 2201718. https://doi.org/10.1002/advs.202201718
  11. H. Yang, G. V. Zhuang, and P. N. Ross, Jr., "Thermal Stability of LiPF6 Salt and Li-Ion Battery Electrolytes Containing LiPF6", J. Power Sources, 2006, 161, 573−579. https://doi.org/10.1016/j.jpowsour.2006.03.058
  12. S. Taminato, A. Tsuka, K. Sobue, D. Mori, Y. Takeda, O. Yamamoto, and N. Imanishi, "Stabilization of the Interface Between a PEO-Based Lithium Solid Polymer Electrolyte and a 4-Volt Class Cathode, LiCoO2, by the Addition of LiPF6 as a Lithium Salt", Batteries, 2024, 10, 140. https://doi.org/10.3390/batteries10040140
  13. V. Aravindan, J. Gnanaraj, S. Madhavi, and H. K. Liu, "Lithium-Ion Conducting Electrolyte Salts for Lithium Batteries", Chem. Eur. J., 2011, 17, 14326−14346. https://doi.org/10.1002/chem.201101486
  14. S. H. Wang, S. S. Hou, P. L. Kuo, and H. Teng, "Poly(ethylene oxide)-co-Poly(propylene oxide)-Based Gel Electrolyte with High Ionic Conductivity and Mechanical Integrity for Lithium-Ion Batteries", ACS Appl. Mater. Interfaces, 2013, 5, 8477−8485. https://doi.org/10.1021/am4019115
  15. X. Zhang, J. Xie, F. Shi, D. Lin, Y. Liu, W. Liu, A. Pei, Y. Gong, H. Wang, K. Liu, Y. Xiang, and Y. Cui, "Vertically Aligned and Continuous Nanoscale Ceramic-Polymer Interfaces in Composite Solid Polymer Electrolytes for Enhanced Ionic Conductivity", Nano Letters, 2018, 18, 3829−3838. https://doi.org/10.1021/acs.nanolett.8b01111
  16. M. S. Mustafa, H. O. Ghareeb, S. B. Aziz, M. A. Brza, S. Al-Zangana, J. M. Hadi, and M. F. Z. Kadir, "Electrochemical Characteristics of Glycerolized PEO-Based Polymer Electrolytes", Membranes, 2020, 10, 116. https://doi.org/10.3390/membranes10060116
  17. Z. Zhou, Y. Yuan, X. Tang, W. Liu, B. Yang, J. Wen, and L. Liu, "Enhancing Ionic Conductivity of Polyethylene Oxide-Based Solid-state Electrolytes Through Blending with a Small Amount of Polyacrylic Acid: A Polymer-Anion Synergistic Mechanism", J. Power Sourc., 2025, 644, 237132. https://doi.org/10.1016/j.jpowsour.2025.237132
  18. R. Khurana, J. L. Schaefer, L. A. Archer, and G. W. Coates, "Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries", J. Am. Chem. Soc., 2014, 136, 7395−7402. https://doi.org/10.1021/ja502133j
  19. N. Wang, Y. Wei, S. Yu, W. Zhang, X. Huang, B. Fan, H. Yuan, and Y. Tan, "A Flexible PEO-Based Polymer Electrolyte with Cross-Linked Network for High-Voltage All Solid-State Lithium-Ion Battery", J. Mater. Sci. Technol., 2024, 183, 206−214. https://doi.org/10.1016/j.jmst.2023.10.005
  20. S. K. Ghazali, F. S. S. Azim, N. Adrus, and J. Jamaluddin, "The Effectiveness of UV-LED Photopolymerisation Over Conventional UV-Mercury for Polyurethane Acrylate Coating", J. Photopolym. Sci. Technol., 2019, 32, 705−710. https://doi.org/10.2494/photopolymer.32.705
  21. J. K. Oh, S. H. Kim, K. I. Jung, J. Huh, H. W. Jung, and J. A. Bang, "Effect of Photo-Initiators on the Crosslinking Behavior of Organic Thin Films and Their Applicability to Flexible Display Encapsulation Layer", Polym. Korea, 2020, 44, 841−847. https://doi.org/10.7317/pk.2020.44.6.841
  22. J. H. Kim, "The Development of Polymer Electrolyte Membranes for Lithium Ion Battery by LED-UV Crosslinking of Poly(ethylene oxide)", M. S. Thesis, Kumoh Institute of Technology, Republic of Korea, 2024.
  23. M. Chintapalli, T. N. P. Le, N. R. Venkatesan, N. G. Mackay, A. A. Rojas, J. L. Thelen, X. C. Chen, D. Devaux, and N. P. Balsara, "Structure and Ionic Conductivity of Polystyrene-block-poly (ethylene oxide) Electrolytes in the High Salt Concentration Limit", Macromolecules, 2016, 49, 1770−1780. https://doi.org/10.1021/acs.macromol.5b02620
  24. S. Zheng, J. Huang, Y. Li, and Q. Guo, "A DSC Study of Miscibility and Phase Separation in Crystalline Polymer Blends of Phenolphthalein Poly(ether ether sulfone) and Poly(ethylene oxide)", J. Polym. Sci. Part B: Polym. Phys., 1997, 35, 1383−1392. https://doi.org/10.1002/(SICI)1099-0488(19970715)35:9<1383::AID-POLB8>3.0.CO;2-N