New Type Polymer Electrolytes Based on Bis-Oxetane Monomer with Oligo (ethylene oxide) Units.

  • Miwa Yoshiyuki
    Ube Laboratory, Corporate Research & Development, Ube Ind. Ltd.
  • Tsutsumi Hiromori
    Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi University
  • Oishi Tsutomu
    Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Yamaguchi University

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A new procedure for preparing of polymer electrolytes based on ring-opening polymerization of bis-oxetane derivatives [1,9-bis(3-ethyl-3-oxetanyl)-2,5,8-trioxanonane (DDOE), 1,12-bis(3-ethyl-3-oxetanyl)-2,5,8,11-tetraoxadodecane (TrDOE), and 1,15-bis(3-ethyl-3-oxetanyl)-2,5,8,11,14-hexaoxapentadecane (TeDOE)] having oligo-ethylene oxide (EO) chain was carried out with lithium salts [LiPF6, LiBF4, and LiN(C2F5SO3)2] as a polymerization catalyst. Addition of a polar solvent such as acetone or acetonitrile (“retarding” solvent) to the monomer-lithium salt mixture was effective in regulating the polymerization rate. The polymer electrolytes were characterized by infrared spectroscopy, differential scanning calorimetory (DSC), dynamic mechanical spectroscopy, X-Ray diffraction measurement, and alternating current impedance spectroscopy. The polymer electrolytes obtained with LiBF4 were free-standing and dimensionally stable films and indicated high conductivity (2.8×10-5 S cm-1 at 30°C) as solvent-free polymer electrolytes. Conductivity of the poly(oxetane)–LiBF4 complexes was found to depend on the amount of LiBF4, the kind of “retarding” solvent (acetone or acetonitrile) and length of oligo-EO chain in the bis-oxetane monomer. Maximum conductivity of the complexes acquired from the LiBF4–acetone solution of DDOE, TrDOE, and TeDOE revealed 2.7×10-5, 2.0×10-5, and 1.8×10-5 S cm-1 at 30°C, and from LiBF4–acetonitrile solution, 7.6×10-7, 1.6×10-6, and 2.8×10-5 S cm-1 at 30°C, respectively. DSC and dynamic mechanical spectroscopy of the polymer electrolytes suggested that the network structures in the electrolytes were influenced by the polar solvent.

収録刊行物

  • Polymer Journal

    Polymer Journal 33 (12), 927-933, 2001

    The Society of Polymer Science, Japan

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