Effect of Salt Concentration on the Glass Transition Temperature and Ionic Conductivity of Poly(ethylene glycol)-Polyurethane/LiClO<sub>4</sub> Complexes

Pil-Ho Huh; Myung-Geun Choi; Nam Ju Jo; Jin-Kook Lee; Jang-Oo Lee; Wongkang Yang

Macromolecular Research, Vol.12, No.4, 422-426, August, 2004

Effect of Salt Concentration on the Glass Transition Temperature and Ionic Conductivity of Poly(ethylene glycol)-Polyurethane/LiClO₄ Complexes

Pil-Ho Huh, Myung-Geun Choi, Nam Ju Jo, Jin-Kook Lee, Jang-Oo Lee^†, and Wongkang Yang¹

Department of Polymer Science and Engineering, Pusan National University, Busan 609-735, Korea
¹Department of Chemistry, College of Natural Science, Dongguk University, Korea

E-mail:

Solid polymer electrolytes based on poly(ethylene glycol)-polyurethane (PEG-PU) complexed with LiClO4 salt have been prepared by the solvent casting method. A PEG-PU material (PEG:4,4'-diphenylmethane diisocyanate:1,4-butanediol = 1:2:1) was synthesized through a typical two-step condensation reaction. We investigated the effects of the salt concentration on the ionic conductivity ( σ) and the glass transition temperature (T_g) of the complex electrolytes by using alternating current impedance spectroscopy, differential scanning calorimetry, and dynamic mechanical thermal analysis. The measured values of both σ and T_g exhibited similar tendencies in that they had maxima within the range studied, probably because of two opposite effects, i.e., the increased number of carrier ions and the decreased chain mobility (or increased T_g) caused by the increase in the salt concentration. The highest conductivity, on the order of 2.43×10⁶ Scm^-1, was obtained at an [O]/[Li⁺] ratio of ca. 16 (0.92 mol salt per kg of matrix polymer).

Keywords:thermal T_g;dynamic T_g;chain mobility;ionic conductivity

[References]

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[1] Fenton DE, Parker JM, Wright PV, Polymer, 14, 589 (1973)

[2] Wright PV, Br. Polym. J., 7, 319 (1975)

[3] MacCallum JR, Vincent CA, Polymer Electrolyte Reviews, Elsevier Appled Science Edition, London, UK, 1987, Vol. 1, Chapters 1 and 8.

[4] Eisenberg A, Ovans K, Yoon HN, The Viscosity Enhancement of Polyethers by Salts. In Ions in Polymers, A. Eisenberg, Ed., Advances in Chemistry Series187, ACS, Washington, DC, 267 (1980)

[5] Armand MB, Chabagano JM, Duclot MJ, Polyethers as Solid Electrolytes. In Fast Ion Transport in Solids:Electrodes Electrolytes, Proc. Int. Conf., P. Vashishta, J. N. Mundy, and G.K., Shenoy, Eds., North Holland, New York, 131 (1979)

[6] Chemical and Engineering News, Nov. 25, 28 (1985)

[7] Chao S, Wrighton MS, J. Am. Chem. Soc., 109, 2197 (1987)

[8] Tsuchida E, J. Mac. Sci. Chem., A25, 687 (1988)

[9] Burroughes JH, Jones CA, Friend RH, Nature, 335, 137 (1988)

[10] Robila G, Ivanoin M, Buruiana EC, J. Appl. Polym. Sci., 49, 2025 (1993)

[11] Okamoto V, Yeh TF, Lee HS, Skotheimic TA, J. Polym. Sci. A: Polym. Chem., 31, 2573 (1993)

[12] Wen TC, Luo SS, Yang CH, Polymer, 41, 6755 (2000)

[13] Donoso JP, Bonagamba TJ, Frare PL, Panepucci H, Electrochim. Acta, 40, 2361 (1995)

[14] Acosta JL, Morales E, Solid State Ion., 85, 85 (1996)

[15] Strauss E, Golodnitsky D, Ardel G, Peled E, Electrochim. Acta, 43(10-11), 1315 (1998)

[16] Kim JY, Hong SU, Won J, Kang YS, Macromolecules, 33, 3165 (2000)

[17] Kim JH, Min BR, Won J, Kang YS, J. Phys. Chem. B, 107, 5901 (2003)

[18] Huh PH, Thesis MS, Pusan National University, Kr (2002)

[19] Cole KS, Cole S, J. Chem. Phys., 9, 341 (1941)

[20] Sperling LH, in Sound and Vibration Damping with Polymers, R. D. Corsaro and L. H. Sperling, Eds., ACS Books Symp. Ser. 424, American Chemical Society, Washington, DC (1990)

[21] Catsiff E, Tobolsky AV, J. Polym. Sci., 19, 111 (1956)