Journal of the Korean Electrochemical Society (전기화학회지)

The Korean Electrochemical Society (한국전기화학회)
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Synthesis of Organic Radical Copolymers Based on Polystyrene and Their Performance for Batteries

폴리스티렌 기반 유기 라디칼 공중합체의 합성과 전지특성

  • Yang, Eui-Seok (Department of Engineering Chemistry, Chungbuk National University) ;
  • Ryu, Sang-Woog (Department of Engineering Chemistry, Chungbuk National University)
  • Received : 2016.10.07
  • Accepted : 2016.10.31
  • Published : 2016.11.30
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Abstract

In this study, homo and copolymers of 2,2,6,6-tetramethyl-4-piperidyl methacrylate(TMA) and synthesized styrene derivative, 2,2,6,6-tetramethylpiperidine-4-vinylbenzyl ether(TVBE) were obtained by radical polymerization and oxidized to produce corresponding polymer radicals. The polymer radicals were mixed with carbon black, binders and coated onto Al current collector. The battery performance is then characterized by fabricating coin cells. As results, the polystyrene based organic radicals show lower oxidize efficiency and discharge capacity than methacrylate based one. However, the former shows better capacities from discharge experiments performed at $60^{\circ}C$ which suggests a possible way to overcome the high temperature fade out of performance in usual organic radical batteries. Also as expected, an excellent C-rate performance is observed in all the cells consisted of organic polymer radicals.

본 실험에서는 2,2,6,6-tetramethyl-4-piperidyl methacrylate(TMA)와 합성된 스티렌 계열의 2,2,6,6-tetramethylpiperidine-4-vinylbenzyl ether(TVBE)으로 구성된 단독 및 공중합체를 합성하였으며 산화반응을 이용하여 고분자 라디칼로 변환시켰다. 제조된 고분자 라디칼은 카본블랙, 바인더와 함께 혼합되어 알루미늄 극판에 코팅되었으며 코인셀로 구성하여 전지특성을 평가하였다. 그 결과, 폴리스티렌 기반의 중합체는 폴리메타크릴레이트 기반의 재료에 비해 낮은 산화반응성과 낮은 방전용량을 보여주었다. 하지만 $60^{\circ}C$의 고온에서 실시된 방전실험에서는 폴리스티렌 기반에서 더욱 우수한 방전특성을 나타났다. 또한 예상대로 고분자 라디칼로 구성된 전지에서 우수한 율특성을 확인할 수 있었다.

Keywords

References

  1. V. Dang, J. Wang, S. Feng, C. Buron, A. Villamena, G. Wang, P. Kuppusamy, "Synthesis and characterization of a perchlorotriphenylmethyl(trityl) triester radical: A potential sensor for superoxideand oxygen in biological systems", Bioorganic & Medicinal Chemistry Letters, 17, 4062-4065 (2007). https://doi.org/10.1016/j.bmcl.2007.04.070
  2. H.C. Lin, C.C. Li, J.T. Lee, "Nitroxide polymer brushes grafted onto silica nanoparticles as cathodes for organic radical batteries", Journal of Power Sources, 196, 8098 (2011). https://doi.org/10.1016/j.jpowsour.2011.05.037
  3. L. Huiqiao, Z. Ying, X. Yongyao, "A study of nitroxide polyradical/activated carbon composite as the positive electrode material for electrochemical hybrid capacitor", Electrochim. Acta, 52, 2153 (2007). https://doi.org/10.1016/j.electacta.2006.08.031
  4. K. Nakahara, J. Iriyama, S. Iwasa, M. Suguro, M. Satoh, E. Cairns, "Al-laminated film packaged organic radical battery for high-power applications", Journal of Power Sources, 163, 1110 (2007). https://doi.org/10.1016/j.jpowsour.2006.10.003
  5. K. Nakahara, J. Iriyama, S. Iwasa, M. Suguro, M. Satoh, E. Cairns, "Cell properties for modified PTMA cathodes of organic radical batteries", Journal of Power Sources, 165, 398 (2007). https://doi.org/10.1016/j.jpowsour.2006.11.044
  6. K. Nakahara, S. Iwasa, M. Satoh, Y. Morioka, J. Iriyama, M. Suguro, E. Hasegawa, "Rechargeable batteries with organic radical cathodes", Chemical Physics Letters, 359, 351 (2002). https://doi.org/10.1016/S0009-2614(02)00705-4
  7. K. Koshika, M. Kitajima, K. Oyaizu, H. Nishide, "A rechargeable battery based on hydrophilic radical polymer electrode and its green assessment", Green Chemistry Letters and Reviews, 2, 169 (2009). https://doi.org/10.1080/17518250903251775
  8. Y.Y. Cheng, C.C. Li, J.T. Lee, "Electrochemical behavior of organic radical polymer cathodes in organic radical batteries with N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid electrolytes", Electrochim. Acta, 66, 332 (2012). https://doi.org/10.1016/j.electacta.2012.02.003
  9. S.H. Lee, J.K. Kim, G. Cheruvallya, J.W. Choi, J.H. Ahn, S. Chauhana, C.E. Son, "Electrochemical properties of new organic radical materials for lithium secondary batteries", Journal of Power Sources, 184, 503 (2008). https://doi.org/10.1016/j.jpowsour.2008.04.003
  10. S. Yoshihara, H. Katsuta, H. Isozumi, M. Kasai, K. Oyaizu, H. Nishide, "Designing current collector/composite electrode interfacial structure of organic radical battery", Journal of Power Sources, 196, 7806 (2011). https://doi.org/10.1016/j.jpowsour.2010.10.092
  11. J.K. Kim, G. Cheruvally, J.W. Choi, J.H. Ahn, S.H. Lee, D.S. Choi, C.E. Song, "Effect of radical polymer cathode thickness on the electrochemical performance of organic radical battery", Solid State Ionics, 178, 1546 (2007). https://doi.org/10.1016/j.ssi.2007.09.009
  12. K. Nakahara, S. Iwasa, J. Iriyama, Y. Morioka, M. Suguro, M. Satoh, E. Cairns, "Electrochemical and spectroscopic measurements for stable nitroxyl radicals", Electrochim. Acta, 52, 921 (2006). https://doi.org/10.1016/j.electacta.2006.06.028
  13. J.K. Kim, J.H. Ahn, G. Cheruvally, S. Chauhan, J.W. Choi, D.S. Kim, H.J. Ahn, S.H. Lee, C.E. Song, "Electrochemical Properties of Rechargeable Organic Radical Battery with PTMA Cathode", Met. Mater. Int., 15, 77 (2009). https://doi.org/10.1007/s12540-009-0077-9
  14. S. Komaba, T. Tanaka, T. Ozeki, T. Taki, H. Watanabe, H. Tachikawa, "Fast redox of composite electrode of nitroxide radical polymer and carbon with polyacrylate binder", Journal of Power Sources, 195, 6212 (2010). https://doi.org/10.1016/j.jpowsour.2009.10.078
  15. H. Nishide, S. Iwasa, Y.J. Pua, T. Suga, K. Nakahara, M. Satoh, "Organic radical battery: nitroxide polymers as a cathode-active material", Electrochim. Acta, 50, 827 (2004). https://doi.org/10.1016/j.electacta.2004.02.052
  16. Y.H. Wang, M.K. Hung, C.H. Lin, H.C. Lin, J.T. Lee, "Patterned nitroxide polymer brushes for thin-film cathodes in organic radical batteries", Chem. Commun., 47, 1249 (2011). https://doi.org/10.1039/C0CC02442B
  17. P. Nesvadba, L. Bugnon, P. Maire, P. Novak, "Synthesis of A Novel Spirobisnitroxide Polymer and its Evaluation in an Organic Radical Battery", Chem. Mater., 22, 783 (2010). https://doi.org/10.1021/cm901374u
  18. T. Miyazawa, T. Endo, M. Okawara, "Synthesis and Polymerization of 4-O-Vinylbenzyl-2,2,6,6-Tetramethylpiperidine", Journal of Polymer Science, 23, 1527 (1985).