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Synthesis of Radical Polymers and their Application as an Organic Radical Battery

Research Project

Project/Area Number 17350061
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Polymer chemistry
Research InstitutionWaseda University

Principal Investigator

NISHIDE Hiroyuki  Waseda University, Faculty of Science and Engineering, Professor, 理工学術院, 教授 (90120930)

Co-Investigator(Kenkyū-buntansha) SUGA Takeo  Waseda University, Faculty of Science and Engineering, Research Associate, 理工学術院, 助手 (10409659)
村田 英則  早稲田大学, 理工学術院, 助手 (50367075)
Project Period (FY) 2005 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥14,900,000 (Direct Cost: ¥14,900,000)
Fiscal Year 2006: ¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 2005: ¥9,200,000 (Direct Cost: ¥9,200,000)
KeywordsRadical polymer / Nitroxide / Redox / Secondary battery / Electrode-active material / Electron transfer process / Photocrosslinking / 機能性高分子化学 / 高分子合成 / 電気・磁気的性質 / 電池 / 高分子機能材料
Research Abstract

(1) Main chain structure and its redox-activity A polyether derivative bearing the redox-active 2,2,6,6-tetramethylpiperidinyl-N-oxy (TEMPO) moiety was insoluble, but slightly swollen in the electrolyte solution. The glass transition temperature (T_g) was below room temperature, and more flexible than the polymethacrylate derivatives. The cell performance fabricated with this polymer was maintained even with a higher radical polymer loading in the composite electrode, which revealed the flexible polyether backbone could contribute to its higher compatibility with the electrolyte solution and the current collector, and could also serve as a matrix for rapid electron transfer.
Photocrosslinking was chosen as a method for providing tunable solubility of the radical polymer, increasing mechanical toughness of the film, improving design flexibility and enabling patterning of the device. A photocrosslinked TEMPO-substituted polynorbomene was obtained using a bis(azide) crosslinker, which was … More carefully designed to eliminate side reactions on the nitroxide moiety. The obtained radical thin film exhibited a rapid and reversible redox at 3.58 V vs. Li/Li^+ and served as a cathode-active material even without any current collector. This approach facilitated battery manufacture via a wet, printable, and rollable process, leading to an organic-based, flexible paper battery.
(2) Electron transfer process of the radical polymer film and fabrication of the composite electrode A radical film obtained by photocrosslinking of the poly(TEMPO-substituted norbomene) displayed the redox behavior with a narrow peak-to-peak separation, resulting from the surface-confined redox species, which supported the rapid and quantitative electron transfer within 250 nm thickness. A SEM image of the radical polymer/carbon composite electrode also showed the carbon nanofiber was fully covered with the polymer (ca. 100 nm thickness) and suggested the electron can be transferred by the electron-hopping mechanism within the polymer layer.
(3) N-type radical polymers and their application as a totally organic-derived secondary battery Cyclic voltammetry, in-situ electrolytic ESR and UV/vis spectroscopy revealed that the reversible p-type redox of poly[4-(N-t-butyl-N-oxylamino)styrene], attributed to the oxoammonium cation formation and n-type redox of poly(nitroxylstyrene) o-substituted with trifluoromethyl group corresponding to the aminoxy anion formation, was tuned by the electronic effects of substituent groups. P-and n-type redox switching with chemical modification also promises a potential application of these polymers as cathode-and anode-active materials in all-organic batteries. Poly(galvinoxylstyrene) exhibited a reversible redox at 3.15 V vs. Li/Li+ under basic conditions, attributed to the n-type redox reaction between the galvinoxyl radical and galvinoxylate anion. A test cell fabricated with this polymer anode and poly(TEMPO-substituted norbornene) cathode, displayed stable charge-discharge curves at a plateau voltage of 0.66 V, which agreed well with the difference of the formal redox potentials for both radical polymers.
Through this study, the redox activity of the radical polymers has been correlated with their chemical structures and an all-organic-based battery was constructed, for the first time, with both radical polymers. Less

Report

(3 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • Research Products

    (21 results)

All 2007 2006 2005

All Journal Article (14 results) Book (2 results) Patent(Industrial Property Rights) (5 results)

  • [Journal Article] Cathode- and Anode-Active Poly(nitroxylstyrene)s for Rechargeable Batteries : P- and N-Type Redox Switching via Substituent Effects2007

    • Author(s)
      T.Suga, Y.-J.Pu, S.Kasatori, H.Nishide
    • Journal Title

      Macromolecules (In press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Photo-crosslinked Nitroxide Polymer Cathode-Active Materials for Application in an Organic-Based Paper Battery2007

    • Author(s)
      T.Suga, H.Konishi, H.Nishide
    • Journal Title

      Chemical Communications (In press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Nitroxide-Substituted Polyether as a New Material for Batteries2007

    • Author(s)
      T.Suga, K.Yoshimura, H.Nishide
    • Journal Title

      Macromolecular Symposia (In press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] 有機ラジカル電池 : 主鎖分子設計と電荷輸送2007

    • Author(s)
      須賀 健雄, 西出 宏之
    • Journal Title

      超分子研究会アニュアルレビュー 27

      Pages: 12-13

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Cathode-and Anode-Active Poly(nitroxylstyrene)s for Rechargeable Batteries : P and N-Type Redox Switching via Substituent Effects2007

    • Author(s)
      T.Suga, Y.-J.Pu, S.Kasatori, H.Nishide
    • Journal Title

      Macromolecules, (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Photo-Crosslinked Nitroxide Polymer Cathode Leading to an Organic-Based Paper Battery2007

    • Author(s)
      T.Suga, H.Konishi, H.Nishide
    • Journal Title

      Chem.Commun. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Nitroxide-Substituted Polyether as a New Material for Batteries2007

    • Author(s)
      T.Suga, K.Yoshimura, H.Nishide
    • Journal Title

      Macromol.Symp. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Cathode- and Anode-Active Poly(nitroxylstyrene)s for Rechargeable Batteries : P and N-Type Redox Switching via Substituent Effects2007

    • Author(s)
      T.Suga, Y.-J.Pu, S.Kasatori, H.Nishide
    • Journal Title

      Macromolecules in press

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Photo-Crosslinked Nitroxide Polymer Cathode Leading to an Organic-Based Paper Battery2007

    • Author(s)
      T.Suga, H.Konishi, H.Nishide
    • Journal Title

      Chemical Communications in press

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Nitroxide-Substituted Polvether as a New Material for Batteries2007

    • Author(s)
      T.Suga, K.Yoshimura, H.Nishide
    • Journal Title

      Macromolecular Symposia in press

    • Related Report
      2006 Annual Research Report
  • [Journal Article] 有機ラジカル電池;主鎖分子設計と電荷輸送2007

    • Author(s)
      須賀 健雄, 西出 宏之
    • Journal Title

      超分子研究会アニュアルレビュー 27

      Pages: 12-12

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Organic Radical Battery2005

    • Author(s)
      H.Nishide, T.Suga
    • Journal Title

      Electrochem. Soc. Interface 14・4

      Pages: 30-30

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Organic Radical Battery2005

    • Author(s)
      H.Nishide, T.Suga
    • Journal Title

      Electrochem.Soc.Interface, 14

      Pages: 30-34

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Organic Radical Battery2005

    • Author(s)
      H.Nishide, T.Suga
    • Journal Title

      Electrochem.Soc.Interface 14

      Pages: 30-34

    • Related Report
      2005 Annual Research Report
  • [Book] 電池革新が拓く次世代電源 2章「有機ラジカル電池・原理と応用・」2006

    • Author(s)
      須賀 健雄, 西出 宏之
    • Publisher
      エヌ・ティー・エス、東京
    • Related Report
      2005 Annual Research Report
  • [Book] 電池革新が拓く次世代電源2章有機ラジカル電池-原理と応用-2005

    • Author(s)
      須賀 健雄
    • Publisher
      エヌ・テイー・エス
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 電極活物質、電池および重合体2007

    • Inventor(s)
      西出宏之, 藤長将司, 岩佐繁之
    • Industrial Property Rights Holder
      日本電気株式会社, 早稲田大学
    • Patent Publication Number
      2007-035375
    • Filing Date
      2007-02-08
    • Related Report
      2006 Annual Research Report
  • [Patent(Industrial Property Rights)] 電極活物質、電池および重合体2005

    • Inventor(s)
      西出宏之, 藤長将司, 岩佐繁之
    • Industrial Property Rights Holder
      西出宏之, 藤長将司, 岩佐繁之
    • Industrial Property Number
      2005-214817
    • Filing Date
      2005
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 電極活物質、電池および重合体2005

    • Inventor(s)
      西出 宏之, 藤長 将司, 岩佐 繁之
    • Industrial Property Rights Holder
      早稲田大学, 日本電気
    • Industrial Property Number
      2005-214817
    • Filing Date
      2005-07-25
    • Related Report
      2005 Annual Research Report
  • [Patent(Industrial Property Rights)] ノルボルネン系架橋共重合体及びその製造方法2005

    • Inventor(s)
      西出 宏之, 須賀 健雄, 多田 健太郎
    • Industrial Property Rights Holder
      早稲田大学, 東洋合成工業
    • Industrial Property Number
      2005-255740
    • Filing Date
      2005-09-02
    • Related Report
      2005 Annual Research Report
  • [Patent(Industrial Property Rights)] 二次電池用活物質層及びその形成方法並びに・2005

    • Inventor(s)
      西出 宏之, 須賀 健雄, 多田 健太郎
    • Industrial Property Rights Holder
      早稲田大学, 東洋合成工業
    • Industrial Property Number
      2005-356814
    • Filing Date
      2005-12-09
    • Related Report
      2005 Annual Research Report

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Published: 2005-04-01   Modified: 2016-04-21  

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