Multinuclear solid-state NMR, self-diffusion coefficients, differential scanning calorimetry, and ionic conductivity of solid organic - inorganic hybrid electrolytes based on PPG - PEG - PPG diamine, siloxane, and lithium perchlorate

Hsien Ming Kao, Shih Wei Chao, Pai Ching Chang

研究成果: 雜誌貢獻期刊論文同行評審

49 引文 斯高帕斯(Scopus)

摘要

Organic - inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)block-poly(propylene glycol) bis(2-aminopropyl ether) (D2000) complexed with LiClO4 via the co-condensation of an epoxy trialkoxysilane and tetraethoxysilane have been prepared and characterized. The hybrid electrolytes thus obtained were rubbery thin films with good mechanical strength and a good degree of elasticity. Characterization was made by a variety of techniques including alternating current impedance, Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), multinuclear solid-state NMR spectroscopy, and pulse-gradient spin - echo (PGSE) NMR measurements. A VTF (Vogel - Tamman - Fulcher)-like temperature dependence of ionic conductivity was observed for all the compositions studied, implying that the diffusion of charge carriers was assisted by the segmental motions of the polymer chains. A maximum ionic conductivity value of 6.23 × 10-5 S/cm was obtained at 30°C. 13C cross-polarization/magic angle spinning NMR results from variable contact time measurements along with 2D wide-line separation NMR indicated that a significant decrease in the mobility of the polymer chains as the salt content was increased, consistent with the increase in Tg as observed by DSC. Solid-state 7Li NMR characterization was performed to study ionic mobility by measuring spectral line widths, T1 relaxation times, and diffusion coefficients. The results of the lithium diffusion coefficient measurements indicated that the ionic conductivity in the present electrolytes was mainly dominated by the mobility of the lithium cations.

原文???core.languages.en_GB???
頁(從 - 到)1029-1040
頁數12
期刊Macromolecules
39
發行號3
DOIs
出版狀態已出版 - 7 2月 2006

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