Self-doping inspired zwitterionic pendant design of radical polymers toward a rocking-chair-type organic cathode-active material

Il Seok Chae, Masafumi Koyano, Kenichi Oyaizu, Hiroyuki Nishide*


研究成果: Article査読

35 被引用数 (Scopus)


'Self-doping' inspired high-density redox copolymers were designed and prepared via free radical copolymerization of 2,2,6,6-tetramethyl-4-piperidyl methacrylate and vinylsulfonic acid (VSA) with a view to preventing a change in salt concentration during the one-electron oxidation of the nitroxide radicals to N-oxoammonium cations in a polymer layer. A copolymer composition of TEMPO-sulfonate anionic group = 1/1 for density-maximized charge neutralization was achieved by controlling the feed ratio of the copolymerization. The formation of copolymers was evidenced by 2D nuclear Overhauser enhanced spectroscopy (NOESY) and diffusion ordered spectroscopy (DOSY) NMR. Poly(TEMPO methacrylate-stat-VSA) was considered to have the alternating tendency due to the acid-base interaction in the comonomers, which were supported not only by the single crystal structure of the 2,2,6,6-tetramethyl-4-piperidyl methacrylate and VSA complex, but also by the 1H-1H correlation in NOE signals. In an aqueous electrolyte with 0.5 M NaCl, the copolymer electrode showed a redox response near 0.66 V (vs. Ag/AgCl), and the excellent cycle performance during 1000 cycles. During the one-electron oxidation of the nitroxide radical, anionic sulfonate groups led to charge compensation of the N-oxoammonium cation. Consequently, the copolymer electrode exhibited the cation migration, which was evidenced by mass-transfer analysis using an electrochemical quartz crystal microbalance (EQCM) technique. The copolymer could be applied as an aqueous electrolyte-type organic rechargeable device. Moreover, this design proposes the ultimate principle toward the strategy of maximizing energy density in organic charge storage devices.

ジャーナルJournal of Materials Chemistry A
出版ステータスPublished - 2013 1月 28

ASJC Scopus subject areas

  • 化学 (全般)
  • 再生可能エネルギー、持続可能性、環境
  • 材料科学(全般)


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