Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Design of Fluorinated Electrolytes Enabling Solvation Structure Control for High-Stability Lithium Metal Batteries

불소화 전해액의 용매화 구조 제어를 통한 고안정성 리튬금속전지 개발

  • Yewon Park (School of Chemical Engineering, Pusan National University) ;
  • Jae Bin Park (School of Chemical Engineering, Pusan National University) ;
  • Ah Reum Choi (School of Chemical Engineering, Pusan National University) ;
  • Jae Hong Choi (Department of Smart Green Technology Engineering, and Department of Nanotechnology Engineering, Pukyong National University) ;
  • Mirim Oh (Department of Smart Green Technology Engineering, and Department of Nanotechnology Engineering, Pukyong National University) ;
  • Pilgun Oh (Department of Smart Green Technology Engineering, and Department of Nanotechnology Engineering, Pukyong National University) ;
  • Jin Hong Lee (School of Chemical Engineering, Pusan National University)
  • 박예원 (부산대학교 응용화학공학부) ;
  • 박재빈 (부산대학교 응용화학공학부) ;
  • 최아름 (부산대학교 응용화학공학부) ;
  • 최재홍 (부경대학교 나노융합공학과) ;
  • 오미림 (부경대학교 나노융합공학과) ;
  • 오필건 (부경대학교 나노융합공학과) ;
  • 이진홍 (부산대학교 응용화학공학부)
  • Received : 2025.08.28
  • Accepted : 2025.09.03
  • Published : 2025.10.10
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Abstract

We developed a new localized high concentration electrolyte (LHCE) by incorporating a non-solvating fluorinated ether solvent, 1,1,2,3,3,3-hexafluoropropyl methyl ether (F6PME). The introduction of F6PME effectively suppresses the amount of free solvent molecules and induces the formation of an anion-rich solvation structure, which promotes the generation of a robust and stable solid electrolyte interphase (SEI) layer via preferential anion decomposition. Consequently, the F6PME-based electrolyte delivers superior electrochemical stability (≈ 5.0 V), significantly reduced leakage current (12.7 ㎂), and a high lithium-ion transference number (t+ = 0.61). The Li||NCM83 cells with optimized electrolyte exhibit a high reversible capacity of 178.49 mAh g-1 after 100 cycles at 0.5 C/0.5 C within the voltage range of 2.75~4.5 V. As a result, this work highlights the crucial role of F6PME in tailoring the solvation structure, improving interfacial stability, and extending cycle life, thereby offering an effective electrolyte design strategy for high-performance LMBs.

본 연구에서는 비해리성 불소화 용매인 1,1,2,3,3,3-hexafluoropropyl methyl ether (F6PME)를 도입하여 신규 국소 고농도 전해액(localized high concentration electrolyte, LHCE)을 설계하였다. F6PME는 전해액 내 자유 용매를 억제하고 다량의 음이온(anion-rich)이 포함된 용매화 구조를 형성하여 음이온 분해로 인한 안정적인 solid electrolyte interphase (SEI) 층의 형성을 촉진한다. 그 결과, F6PME 전해액은 우수한 전기화학적 안정성(≈ 5.0 V), 낮은 누설 전류(12.7 ㎂), 높은 리튬 이온 전이 수(t+ = 0.61)를 나타냈다. 게다가, 해당 전해액을 적용한 Li||NCM83 전지는 0.5 C/0.5 C의 율속 조건과 2.75~4.5 V의 전압 범위 조건에서 100 회 사이클링 후에도 178.49 mAh g-1의 높은 비용량을 유지하였다. 따라서 본 연구는 F6PME가 전해액의 용매화 구조를 효과적으로 제어하여 전지 구동 시 계면 안정성과 장기 사이클 수명을 향상시킬 수 있음을 입증하였으며, 차세대 리튬 금속 전지용 전해액 개발에 기여할 수 있음을 제안한다.

Keywords

Acknowledgement

이 성과는 부산대학교 BK21 FOUR 대학원혁신사업비(2024-2025)의 지원을 받아 수행되었음.

References

  1. S. Y. Sun, X. Q. Zhang, Y. N. Wang, J. L. Li, Z. Zheng, and J. Q. Huang, Understanding the transport mechanism of lithium ions in solid-electrolyte interphase in lithium metal batteries with liquid electrolytes, Mater. Today, 77, 39-65 (2024).
  2. S. Yuan, K. Ding, X. Zeng, D. Bin, Y. Zhang, P. Dong, and Y. Wang, Advanced nonflammable organic electrolyte promises safer li‐metal batteries: From solvation structure perspectives, Adv. Mater., 35, 2206228 (2023).
  3. X. Feng, M. Ouyang, X. Liu, L. Lu, Y. Xia, and X. He, Thermal runaway mechanism of lithium ion battery for electric vehicles: A review, Energy Storage Mater., 10, 246-267 (2018).
  4. S. Yuan, T. Kong, Y. Zhang, P. Dong, Y. Zhang, X. Dong, Y. Wang, and Y. Xia, Advanced electrolyte design for high‐energy‐density Li‐metal batteries under practical conditions, Angew. Chem., Int. Ed., 60, 25624-25638 (2021).
  5. L. Fan, S. Wei, S. Li, Q. Li, and Y. Lu, Recent progress of the solid‐state electrolytes for high‐energy metal‐based batteries, Adv. Energy Mater., 8, 1702657 (2018).
  6. B. Jagger and M. Pasta, Solid electrolyte interphases in lithium metal batteries, Joule, 7, 2228-2244 (2023).
  7. X. B. Cheng, R. Zhang, C. Z. Zhao, and Q. Zhang, Toward safe lithium metal anode in rechargeable batteries: A review, Chem. Rev., 117, 10403-10473 (2017).
  8. S. Jiao, X. Ren, R. Cao, M. H. Engelhard, Y. Liu, D. Hu, D. Mei, J. Zheng, W. Zhao, Q. Li, N. Liu, B. D. Adams, C. Ma, J. Liu, J.-G. Zhang, and W. Xu, Stable cycling of high-voltage lithium metal batteries in ether electrolytes, Nat. Energy, 3, 739-746 (2018).
  9. Z. Wang, H. Wang, S. Qi, D. Wu, J. Huang, X. Li, C. Wang, and J. Ma, Structural regulation chemistry of lithium ion solvation for lithium batteries, EcoMat, 4, e12200 (2022).
  10. Y. Chen, Z. Yu, P. Rudnicki, H. Gong, Z. Huang, S. C. Kim, J.-H. Lai, X. Kong, J. Qin, Y. Cui, and Z. Bao, Steric effect tuned ion solvation enabling stable cycling of high-voltage lithium metal battery, J. Am. Chem. Soc., 143, 18703-18713 (2021).
  11. P. Lai, Y. Zhang, B. Huang, X. Deng, H. Hua, Q. Chen, S. Zhao, J. Dai, P. Zhang, and J. Zhao, Revealing the evolution of solvation structure in low-temperature electrolytes for lithium batteries, Energy Storage Mater., 67, 103314 (2024).
  12. J. Liu, B. Yuan, L. Dong, S. Zhong, Y. Ji, Y. Liu, J. Han, C. Yang, and W. He, Constructing low‐solvation electrolytes for next‐generation lithium‐ion batteries, Batteries Supercaps., 5, e202200256 (2022).
  13. Z. Wu, R. Li, S. Zhang, L. lv, T. Deng, H. Zhang, R. Zhang, J. Liu, S. Ding, L. Fan, L. Chen, and X. Fan, Deciphering and modulating energetics of solvation structure enables aggressive high-voltage chemistry of Li metal batteries, Chem, 9, 650-664 (2023).
  14. M. S. Kim, Z. Zhang, P. E. Rudnicki, Z. Yu, J. Wang, H. Wang, S. T. Oyakhire, Y. Chen, S. C. Kim, W. Zhang, D. T. Boyle, X. Kong, R. Ku, Z. Huang, W. Huang, S. F. Bent, L.-W. Wang, J. Qin, Z. Bao, and Y. Cui, Suspension electrolyte with modified Li+ solvation environment for lithium metal batteries, Nat. Mater., 21, 445-454 (2022).
  15. X. Ren, L. Zou, X. Cao, M. H. Engelhard, W. Liu, S. D. Burton, H. Lee, C. Niu, B. E. Matthews, Z. Zhu, C. Wang, B. W. Arey, J. Xiao, J. Liu, J.-G. Zhang, and W. Xu, Enabling high-voltage lithium-metal batteries under practical conditions, Joule, 3, 1662-1676 (2019).
  16. Y. Wang, Z. Li, Y. Hou, Z. Hao, Q. Zhang, Y. Ni, Y. Lu, Z. Yan, K. Zhang, Q. Zhao, F. Li, and J. Chen, Emerging electrolytes with fluorinated solvents for rechargeable lithium-based batteries, Chem. Soc. Rev., 52, 2713-2763 (2023).
  17. Y. Zhao, T. Zhou, M. Mensi, J. W. Choi, and A. Coskun, Electrolyte engineering via ether solvent fluorination for developing stable non-aqueous lithium metal batteries, Nat. Commun., 14, 299 (2023).
  18. L. Kim, T. Jang, and H. R. Byon, Fluorinated ether-based co-solvent electrolytes for lithium-metal batteries: High ionic conductivity and suppressed dissolution of fragmented anions, J. Power Sources, 576, 233237 (2023).
  19. P. Zhou, Y. Ou, Q. Feng, Y. Xia, H. Zhou, W. H. Hou, X. Song, Y. Lu, S. Yan, W. Zhang, Y. He, and K. Liu, Tuning the nucleophilicity of anion in lithium salt to enable an anion‐rich solvation sheath for stable lithium metal batteries, Adv. Funct. Mater., 35, 2416800 (2025).
  20. S. He, J. Xiong, H. Yuan, P. Zhu, W. Peng, X. Wang, and B. Xu, Anion-tuned fluorinated solvation sheath enables stable lithium metal batteries, ACS Appl. Mater. Interfaces, 16, 66662-66672 (2024).
  21. Z. Fan, J. Zhang, L. Wu, H. Yu, J. Li, K. Li, and Q. Zhao, Solvation structure dependent ion transport and desolvation mechanism for fast-charging Li-ion batteries, Chem. Sci., 15, 17161-17172 (2024).
  22. R. Xu, A. Hu, Z. Wang, K. Chen, J. Chen, W. Xu, G. Wu, F. Li, J. Wang, and J. Long, Tailoring anion-dominant solvation environment by steric-hindrance effect and competitive coordination for fast charging and stable cycling lithium metal batteries, J. Energy Chem., 105, 35-43 (2025).
  23. J. B. Park, T. Lee, S. Chae, A. R. Choi, Y. Park, S. Jo, P. Oh, S. H. Kwon, J.-H. Baik, B. G. Kim, and J. H. Lee, Designing bifunctional cosolvent-based electrolyte to optimize anion-cation associations for a stable electrode-electrolyte interphase in high-nickel li-metal batteries, Chem. Eng. J., 506, 160012 (2025).
  24. R. Qiao, Y. Zhao, S. Zhou, H. Zhang, F. Liu, T. Zhou, B. Sun, H. Fan, C. Li, Y. Zhang, F. Liu, X. Ding, J. Wook Choi, A. Coskun, and J. Song, Non-fluorinated electrolytes with micelle-like solvation for ultra-high-energy-density lithium metal batteries, Chem, 11, 102306 (2025).
  25. N. Piao, J. Wang, X. Gao, R. Li, H. Zhang, G. Hu, Z. Sun, X. Fan, H.-M. Cheng, and F. Li, Designing temperature-insensitive solvated electrolytes for low-temperature lithium metal batteries, J. Am. Chem. Soc., 146, 18281-18291 (2024).
  26. Y. Zou, F. Cheng, Y. Lu, Y. Xu, C. Fang, and J. Han, High performance low-temperature lithium metal batteries enabled by tailored electrolyte solvation structure, Small, 19, e2203394 (2023).
  27. H. A. Ishfaq, C. C. Cardona, E. Tchernychova, P. Johansson, R. Dominko, and S. D. Talian, Enhanced performance of lithium metal batteries via cyclic fluorinated ether based electrolytes, Energy Storage Mater., 69, 103375 (2024).
  28. L. Y. Lin and C. C. Chen, Accurate characterization of transference numbers in electrolyte systems, J. Power Sources, 603, 234236 (2024).
  29. S. Li, B. Chen, Z. Shi, Q. Tong, and J. Weng, Optimizing strategies for high Li+ transference number in solid state electrolytes for lithium batteries: A review, J. Energy Storage, 102, 114210 (2024).
  30. X. Min, L. Wang, Y. Wu, Z. Zhang, H. Xu, and X. He, Overcoming low-temperature challenges in LIBs: The role of anion-rich solvation sheath in strong solvents, J. Energy Chem., 106, 63-70 (2025).
  31. Z. Li, H. Rao, R. Atwi, B. M. Sivakumar, B. Gwalani, S. Gray, K. S. Han, T. A. Everett, T. A. Ajantiwalay, V. Murugesan, N. N. Rajput, and V. G. Pol, Non-polar ether-based electrolyte solutions for stable high-voltage non-aqueous lithium metal batteries, Nat. Commun., 14, 868 (2023).
  32. C. Chang, Y. Yao, R. Li, Z. Cong, L. Li, Z. H. Guo, W. Hu, and X. Pu, Stable lithium metal batteries enabled by localized high-concentration electrolytes with sevoflurane as a diluent, J. Mater. Chem., 10, 9001-9009 (2022).