Preparation and Characterization of Sulfonated Poly (Arylene Ether Sulfone) Random Copolymer-Polyolefin Pore-filling Separators with Metal Ion Trap Capability for Li-ion Secondary Battery

리튬이온 이차전지용 금속이온 선택성 술폰화 폴리아릴렌에테르술폰 공중합체-폴리올레핀 함침격리막 제조 및 특성

  • Jeong, Yeon Tae (Future Technology Research Laboratory, Korea Electric Power Research Institute) ;
  • Ahn, Juhee (Dept. of Energy Eng., Dankook University) ;
  • Lee, Chang Hyun (Dept. of Energy Eng., Dankook University)
  • 정연태 (한전전력연구원 창의미래연구소) ;
  • 안주희 (단국대학교 융합기술대학 에너지공학과) ;
  • 이창현 (단국대학교 융합기술대학 에너지공학과)
  • Received : 2016.08.24
  • Accepted : 2016.08.29
  • Published : 2016.08.31


Lithium ion secondary battery (LISB) is an energy conversion system operated via charging-discharging cycle based on Lithium ion migration. LISB has a lot of advantages such as high energy density, low self-discharge rate, and a relatively high lifetime. Recently, increasing demands of electric vehicles have been encouraging the development of LISB with high capacity. Unfortunately, it causes some critical safety issues. It includes dendrite formation on negative electrode, resulting in electric shortage problems and battery explosion. Also, the elevated temperatures occurred during the LISB operation induces thermal shrinkage of polyolefin (e.g., polyethylene and polypropylene) separators. Consequently, the low thermal stability leads to decay of LISB performances and the reduction of lifetime. In this study, sulfonated poly (arylene ether sulfone) (SPAES) random copolymers were used as key materials to prepare polyolefin pore-filling separator. The resulting separators were evaluated in the term of metal ion chelation capability associated with dendrite formation, $Li^+$ ion conductivity and thermal durability.


Supported by : 한국에너지기술평가원(KETEP)


  1. S. Megahed and B. Scrosati, "Lithium-ion rechargeable batteries", J. Power Sources, 51, 79 (1994).
  2. Y. Nishi, "Lithium ion secondary batteries; past 10 years and the future", J. Power Sources, 100, 101 (2001).
  3. Q. Wang, P. Ping, X. Zhao, G. Chu, J. Sun, and C. Chen, "Thermal runaway caused fire and explosion of lithium ion battery", J. Power Sources, 208, 210 (2012).
  4. K. Kang, Y. S. Meng, J. Breger, C. P. Grey, and G. Ceder, "Electrodes with high power and high capacity for rechargeable lithium batteries", Science, 311, 977 (2006).
  5. J. Vetter, P. Novak, M. Wagner, C. Veit, K. C. Moller, J. Besenhard, M. Winter, M. Wohlfahrt- Mehrens, C. Vogler, and A. Hammouche, "Ageing mechanisms in lithium-ion batteries", J. Power Sources, 147, 269 (2005).
  6. J. W. Fergus, "Recent developments in cathode materials for lithium ion batteries", J. Power Sources, 195, 939 (2010).
  7. D. Aurbach, B. Markovsky, G. Salitra, E. Markevich, Y. Talyossef, M. Koltypin, L. Nazar, B. Ellis, and D. Kovacheva, "Review on electrode-electrolyte solution interactions, related to cathode materials for Li-ion batteries", J. Power Sources, 165, 491 (2007).
  8. Y. Wang and G. Cao, "Developments in nanostructured cathode materials for high performance lithium-ion batteries", Adv. Mater., 20, 2251 (2008).
  9. B. Scrosati, "Recent advances in lithium ion battery materials", Electrochim. Acta, 45, 2461 (2000).
  10. M. S. Whittingham, "Lithium batteries and cathode materials", Chem. Rev., 104, 4271 (2004).
  11. C. Zhan, J. Lu, A. J. Kropf, T. Wu, A. N. Jansen, Y. K. Sun, X. Qiu, and K. Amine, "Mn (II) deposition on anodes and its effects on capacity fade in spinel lithium manganate-carbon systems", Nat. Commun., 4, 2437 (2013).
  12. S. Komaba, N. Kumagai, and Y. Kataoka, "Influence of manganese (II), cobalt (II), and nickel (II) additives in electrolyte on performance of graphite anode for lithium-ion batteries", Electrochim. Acta, 47, 1229 (2002).
  13. J. M. Kim, C. Kim, S. Yoo, J. H. Kim, J. H. Kim, J. M. Lim, S. Park, and S. Y. Lee, "Agarose-biofunctionalized, dual-electrospun heteronanofiber mats: toward metal-ion chelating battery separator membranes", J. Mater. Chem. A, 3, 10687 (2015).
  14. C. H. Lee, K. S. Lee, O. Lane, J. E. McGrath, Y. Chen, S. Wi, S. Y. Lee, and Y. M. Lee, "Solvent-assisted thermal annealing of disulfonated poly (arylene ether sulfone) random copolymers for low humidity polymer electrolyte membrane fuel cells", RSC Adv., 2, 1025 (2012).
  15. F. Wang, M. Hickner, Y. S. Kim, T. A. Zawodzinski, and J. E. McGrath, "Direct polymerization of sulfonated poly (arylene ether sulfone) random (statistical) copolymers: candidates for new proton exchange membranes", J. Membr. Sci., 197, 231 (2002).
  16. M. Sumner, W. Harrison, R. Weyers, Y. Kim, J. McGrath, J. Riffle, A. Brink, and M. Brink, "Novel proton conducting sulfonated poly (arylene ether) copolymers containing aromatic nitriles", J. Membr. Sci., 239, 199 (2004).
  17. Y. Li, F. Wang, J. Yang, D. Liu, A. Roy, S. Case, J. Lesko, and J. E. McGrath, "Synthesis and characterization of controlled molecular weight disulfonated poly (arylene ether sulfone) copolymers and their applications to proton exchange membranes", Polymer, 47, 4210 (2006).
  18. Y. Li, R. A. VanHouten, A. E. Brink, and J. E. McGrath, "Purity characterization of 3, 3'-disulfonated-4, 4'-dichlorodiphenyl sulfone (SDCDPS) monomer by UV-vis spectroscopy", Polymer, 49, 3014 (2008).
  19. M. Sankir, V. Bhanu, W. Harrison, H. Ghassemi, K. Wiles, T. Glass, A. Brink, M. Brink, and J. McGrath, "Synthesis and characterization of 3, 3'- disulfonated 4, 4'-dichlorodiphenyl sulfone (SDCDPS) monomer for proton exchange membranes (PEM) in fuel cell applications", J. Appl. Polym. Sci., 100, 4595 (2006).
  20. G. H. Li, C. H. Lee, Y. M. Lee, and C. G. Cho, "Preparation of poly (vinyl phosphate-b-styrene) copolymers and its blend with PPO as proton exchange membrane for DMFC applications", Solid State Ion., 177, 1083 (2006).
  21. T. Yamaguchi, F. Miyata, and S. I. Nakao, "Polymer electrolyte membranes with a pore filling structure for a direct methanol fuel cell", Adv. Mater., 15, 1198 (2003).
  22. Y. M. Lee and B. Oh, "The role of microporous separator in lithium ion secondary battery", Membr. J., 7, 123 (1997).
  23. D. H. Yu, M. A. Jeong, J. W. Rhim, H. S. Byun, C. H. Jeong, Y. M. Lee, M. S. Seo, and S. Y. Nam, "Preparation and characterization of microporous PVdF membrane for Li-ion rechargeable battery", Membr. J., 17, 233 (2007).
  24. D. H. Yu, M. A. Jeong, J. W. Rhim, H. S. Byun, H. O. Yoo, J. M. Kim, M. S. Seo, and S. Y. Nam, "Preparation and characterization of PVdF-HFP microporous membranes for Li-ion rechargeable battery", Membr. J., 17, 359 (2007).