Abstract
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.
Similar content being viewed by others
Article PDF
References
M. A. Ratner and D. F. Shriver, Chem. Rev., 88, 109 (1988).
A. Nishino, J. Power Sources, 60, 137 (1996).
C. A. Vincent, Electrochim. Acta, 40, 2035 (1995).
M. C. Lonargan, D. F. Shriver, and M. A. Ratner, Electrochim. Acta, 40, 2041 (1995).
G. D. Hewitt and L. Ling, J. Polym. Sci., Part A: Polym. Chem., 33, 2033 (2000).
K. Nagaoka, H. Naruse, I. Shinohara, and M. Watanabe, J. Polym. Sci., Polym. Lett. Ed., 22, 659 (1984).
C. C. Lee and P. V. Wright, Polymer, 23, 681 (1982).
C. V. Nicholas, D. J. Wilson, C. Booth, and J. R. M. Files, Br. Polym. J., 20, 289 (1988).
C. Berthier, W. Gorecki, M. Minier, M. B. Armand, J. M. Chabagno, and P. Rigand, Solid State Ionics, 11, 91 (1983).
T.-C. Wen and W.-C. Chen, J. Appl. Polym. Sci., 77, 680 (2000).
M. Kono, K. Furuta, S. Mori, M. Watanabe, and N. Ogata, Polym. Adv. Technol., 4, 85 (1993).
L. Marchese, M. Andrei, A. Roggero, S. Passerini, P. Prosperi, and B. Scrosati, Electrochim. Acta, 37, 1559 (1992).
A. Nishimoto, K. Agehara, N. Furuya, T. Watanabe, and M. Watanabe, Macromolecules, 32, 1541 (1999).
D. R. Payne and P. V. Wright, Polymer, 23, 690 (1982).
P. Lobiz, H. Fullbier, A. Reiche, J. C. Illner, H. Reuter, and S. Horing, Solid State Ionics, 58, 41 (1992).
Y. Miwa, H. Tsutsumi, and T. Oishi, Polym. J., 33, 568 (2001).
M. Watanabe, S. Nagano, K. Sanui, and N. Ogata, Polym. J., 18, 809 (1986).
D. E. Fenton, J. M. Parker, and P. V. Wright, Polymer, 14, 589 (1973).
P. V. Wright, J. Polym. Sci., Polym. Phys. Ed., 14, 955 (1976).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Miwa, Y., Tsutsumi, H. & Oishi, T. New Type Polymer Electrolytes Based on Bis-Oxetane Monomer with Oligo(ethylene oxide) Units. Polym J 33, 927–933 (2001). https://doi.org/10.1295/polymj.33.927
Issue Date:
DOI: https://doi.org/10.1295/polymj.33.927