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In this dissertation, two categories of novel materials for polymer electrolytes based on polysiloxane hybrid were prepared, and their microstructures associated with ion conduction behavior were investigated. This monograph is divided into four parts as follows:
1. A new hybrid polymer electrolyte system containing polysiloxane and polyether segments is designed and prepared via epoxide-crosslinking. The thermal behavior, structure, and ionic conductivity of the hybrid materials are investigated and characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), 13C solid-state NMR, and alternating current (AC) impedance measurements. Two glass transition temperatures have been observed, showing their dependence on the composition and LiClO4/PC content. The miscibility of the polymer components in the hybrid has been studied by examining the 1H spin-relaxation times in the laboratory frame (T1(H)) and in the rotating frame (T1r(H)) with various compositions. Multi-relaxation T1r(H) behavior has been observed, indicative of the presence of structural heterogeneity at the time scale of T1r(H). These results are correlated and used to interpret the phenomena of conductivity of lithium ion in the matrix of hybrid networks.
2. Solid polymer electrolytes based on epoxide-crosslinked polysiloxane/polyether hybrid (SE55) were characterized by DSC, impedance measurements and 7Li MAS NMR spectra. The DSC results indicate that initially a cation complexation dominated by the crosslink site of SE55 is present, and subsequently the formation of transient cross-links between Li+ ions and the ether oxygens of polyether segment results in an increase in Tg of the polyether segment (Tg1). However, the Tg1 remains almost invariant at the highest salt concentration of O/Li+ = 4. A VTF-like temperature dependence of ionic conductivity is observed, implying that the diffusion of charge carrier is coupled with the segmental motions of the polymer chains, and furthermore, a maximum conductivity value is observed at O/Li+ = 20 in the analyzed temperature range. Significantly, the 7Li MAS NMR spectra provide high spectral resolution to demonstrate the presence of at least two distinct Li+ local environments in SE55-based electrolytes. Detailed analyses of DSC and 7Li MAS NMR spectra results are achieved and discussed in terms of ion-polymer and ion-ion interactions, and further correlated with ion transport behavior.
3. Hybrid organic-inorganic materials derived from 3-glycidoxypropyltrimethoxyl- silane (GPTMS) were prepared via two different synthetic routes: (1) HCl-catalyzed sol-gel approach of silane followed by lithium perchlorate (LiClO4)/HCl catalyzed opening of epoxide; (2) simultaneous gelation of tin/LiClO4 catalyzed silane/epoxide groups. LiClO4 catalyzes the epoxide polymerization, and its effects on the structure of these hybrid materials were studied by solid-state 13C and 29Si CP/MAS NMR. The different synthetic routes have been found to significantly affect the polymerization behaviors of organic and inorganic sides in the presence of LiClO4. Larger amount of LiClO4 promotes the opening of epoxide and leads to the formation of longer PEO chains via HCl-catalyzed sol-gel approach, whereas in the case of tin-catalyzed, the faster polymerization of inorganic side hinders the growth of the organic network. The addition of LiClO4 was proved to be without crystalline salt present in the hybrid networks by wide-angle X-ray powder diffraction.
4. A new class of hybrid ionic conductors with covalent bonds between the organic poly(ethylene oxide) chains and the siloxane phase were prepared based on poly(ethylene glycol) diglycidyl ether (PEGDE) and 3-glycidoxypropyltrisilane (GPTMS) in the presence of lithium perchlorate (LiClO4) which acted as both ionic source and the epoxide ring-opening catalyst. The effect of salt-doped level on the microstructure and ionic conductivity of these composite electrolytes were investigated by means of Fourier transform infra-red (FT-IR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), a. c. impedance and multinuclear solid-state nuclear magnetic resonance (NMR) measurements. Specially, DSC results indicate the formation of transient cross-links between Li+ ions and the ether oxygens on complexation with LiClO4 results in an increase in polyether segment Tg. However, the polyether segment Tg decreases at the highest salt concentration (5.0 mmol LiClO4 /g PEGDE). This is ascribed to the plasticizing effect, and can be further confirmed by 13C, 1H and 7Li MAS NMR spectra. Moreover, the behavior of ion transport is coupled with the segmental motions of polymer chains and also correlated with the interactions between ions and polymer host.

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