固態電解質(Solid Polymer Electrolyte, SPE)最大挑戰在於提升固態電解質室溫下的離子導電度。本研究成功的使用原位聚合(In situ polymerization)法來製備一具有相互貫穿網狀結構(interpenetrating network; IPN)的固態電解質薄膜，並進而利用交聯劑六甲烯基四氨（HMTA）來交聯網狀之酚醛樹酯 (Phenolic resin)，使其能穩定酚醛所產生之網狀結構，有效地增加電解質的機械性能與提昇其尺寸安定性。其室溫下展現 10-4~10-5 S/cm以上的導電度，較未使用原位聚合(in situ polymerization)酚醛的PEO與鹽類複合的高分子電解質，提昇了兩個order，展現良好作為固態電解質的應用的潛力。 由DSC、TGA、XRD、SEM、FT-IR、NMR、AC-impedance等量測，來對原位聚合固態電解質進行交聯前後其結晶度、物質相容性、熱穩定性、表面型態、分子運動能力與狀態、分子結構以及離子傳導等材料特性的分析與研究。 此外，藉由AC-impedance與DSC的實驗也發現由原位聚合方法所形成的Phenolic網狀區塊(domain)，能有效限制高分子的結晶行為，所形成的非結晶的複合膜，也是導致導電度提昇的重要因素之一。從Solid state NMR光譜可知原位聚合所製備酚醛的結構多為交錯狀而非線性的結構，造成在特性上的差異。而原位聚合製備的電解質其Tm較摻合的來的低，可能是由於聚合成的酚醛分子量較低，能以較短但較多的酚醛分子鏈段，平均分散PEO高分子的結晶區塊，使結晶顆粒變小。 The major challenge of Solid Polymer Electrolytes (SPE) is to achieve fair ionic conductivities at ambient temperature, while maintaining film-forming property. Present study disclosed a unique network structured polymer electrolyte by in-situ polymerize phenolic in PEO solution which is subsequently cross-linked by HMTA to form a mechanical stable freestanding and homogenous film.The structure and PEO crystalline before and after cross-linking、thermal stability、surface morphology、molecular motion ability and state、structure and ion transport are characterized. by DSC、TGA、XRD、SEM、FT-IR、NMR、AC-impedance experiments, respectively. These results show the present in situ composite Solid Polymer electrolytes (in situ CSPE) establish a fair interpenetrating network (IPN) structure with good mechanical properties suitable for general electrolyte applications. The CSPE exhibits lower Tm and Tc than that obtained from blending, which implies the PEO crystallite is well-dispersed and large crystallite is hindered in the confined polymer matrix which results in lowering crystalline of polymer. Due to the unique microstructure, re-crystallization of PEO polymer is not occurring after cross-linking phenolic.
