矽氧烷改質有機無機複合式高分子電解質之結構鑑定與動力學研究

Structural characterization and dynamic properties of organic-inorganic hybrid electrolytes based on alkoxysilane modification

陳育修(Yu-hsiu Chen)

指導教授 ： 高憲明

國立中央大學/理學院/化學系/碩士(2007年)

摘要

本研究著重於製備與鑑定有機/無機複合式高分子電解質根據poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (ED600、ED900、ED2000) 和過氯酸鋰共混合經由 TEOS 和 3-(Triethoxysilyl)propyl isocyanate 共水解。乾燥的有機/無機複合式高分子電解質經過以重量比 1:1 的 EC/PC 電解液混合液，然後獲得塑化。離子導電度經由塑化後上升2個級數，達到室溫最高導電度 2.11×10-3 S/cm。由 DSC、TGA、FT-IR、SEM、XRD、AC-Impedance 和 Solid State NMR光譜用來鑑定複合式高分子電解質結構和動力學特性和離子遷移率。根據熱差式掃描卡計儀結果，玻璃轉化溫度隨著鋰鹽的增加而上升。用 2D 1H-13C WISE (WIdeline SEparation) NMR 技術，複合式高分子電解質系統的動力學能夠被定量的確定由測量在 F1 dimension 上的 1H 的譜寬和在 F2 dimension 上結構相關連的碳譜，而且，乾式複合式高分子電解質的 7Li 擴散係數由 Pulse Gradient Spin- Echo 和離子導電度相關。

關鍵字

玻璃轉換溫度 ； 擴散係數 ； 離子導電度 ； 有機/無機複合式高分子電解質

並列摘要

This research focus on the preparation and characterization of organic–inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (ED600、ED900、ED2000) complexed with LiClO4 via the co-condensation of tetraethoxysilane (TEOS) and 3-(triethoxysilyl)propyl isocyanate. The dry organic–inorganic hybrid electrolytes thus obtained were also plasticized by a solution of ethylene carbonate (EC)/propylene carbonate (PC) mixture (1:1 by volume). The ionic conductivity of the dry hybrid electrolyte films was enhanced by two orders of magnitude via plasticization, reaching a maximum conductivity value of 2.11×10-3 S/cm of the polymer molecule weight 2000 at 30℃. A variety of techniques such as DSC、TGA、FT-IR、SEM、XRD、AC Impedance and solid state NMR spectroscopy are performed to elucidate the realtionship between the structural and dynamic properties of the hybrid electrolyte and the ion mobility. According to DSC results, the glass transition temperature (Tg) raised with increasing the lithium salt content. By means of 2D 1H-13C WISE (WIdeline SEparation) NMR, the dynamic information within such a hybrid system can be qualitatively assessed by examining the proton line shapes in the F1 dimension that are directly related to structural elements resolved in the 13C CP/MAS NMR spectrum in the F2 dimension. Furthermore, the 7Li diffusion coefficients of the dry hybrid electrolytes were determined by pulsed gradient spin-echo (PGSE) experiment to correlate with the behavior of the ion conductivity.

並列關鍵字

Organic-inorganic hybrid electrolytes ； ion conductivity ； glass transition temperature ； self-diffusion coefficients

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