Polymer-Based Ion Gels as a Versatile Platform of Solid Electrolytes

University of Minnesota Ph.D. dissertation. July 2018. Major: Material Science and Engineering. Advisors: Carl Frisbie, Timothy Lodge. 1 computer file (PDF); xii, 163 pages.Ion gels are a versatile class of functional materials. Combining the excellent electrical properties such as high ionic conductivity and capacitance of the ionic liquid (IL) and the mechanical integrity of the polymer, the composite materials have led to a variety of applications such as electrolyte-gated transistors (EGTs), electroluminescent, and electrochromic soft materials. This thesis is built up from previous research on the electrical and mechanical properties of the ABA triblock polymer-based ion gels and continues to improve properties of the materials for electrochemical device applications. In the first part of the thesis work, the objective is to improve the existing ABA triblock polymer systems with poly(ethylene oxide) (PEO) or poly(methyl methacrylate) (PMMA) as the IL-solvating midblock by combining the merit of the low Tg from PEO and hydrophobicity from PMMA into one system. As a result, poly(styrene-b-ethyl acrylate-b-styrene) (SEAS) triblock polymer was developed. The ion gels made with SEAS demonstrate similarly high ionic conductivity as the PEO-based ion gels, which are significantly improved from those of the PMMA-based ion gels. By shortening the midblock size of the triblock polymer, a synergistic improvement of both the ionic conductivity and the modulus can be achieved. Additionally, the EGTs made by SEAS-based ion gels demonstrate superior stability under humidity compared with EGTs made by SOS-based ion gels. In the following two projects of the thesis work, the polymer platform changes from petroleum-based polymers with hydrocarbon backbones to renewable aliphatic polyesters with the potential aim of EGTs in biocompatible applications. To achieve the ion gels, both physical and chemical crosslinked-systems have been explored. The physically crosslinked ABA aliphatic polyester triblock ion gels demonstrate good mechanical integrity and can be successfully printed under similar conditions as the previous systems, and demonstrate improved ionic conductivity from the PMMA-based ion gels. In addition, the resulting ion gels also demonstrate efficient hydrolytic degradation under basic condition. In a different approach, chemically crosslinked poly(lactide) (PLA)-based ion gels can be synthesized from a facile one-pot method. Owing to a smaller volume fraction in ion-insulating domain, the ion gel demonstrates an excellent ionic conductivity at low polymer concentration. Meanwhile, the ion gel also possesses a high toughness owing to the chemical crosslinks. The thin chemically crosslinked PLA-ion gels can be laminated onto EGTs via a cut-and-stick method. On the other hand, the bulk ion gel demonstrates a good electromechanical response with high electromechanical sensitivity with the applied strain and a low hysteresis between stretching and unstretching