Fujita Masahiro

Ionic plastic crystals (IPCs), which are soft crystals with plasticity and ionic conductivity, are expected to be applied as solid electrolytes in battery applications. Further improvement of ionic conductivity is necessary for practical use as an electrolyte for energy storage devices. Materials Informatics (MI) is a method of incorporating information science in materials development. In this research, MI is being used to develop IPCs with high ionic conductivity. By using informatics science in addition to chemical knowledge, this research can be carried out efficiently and innovatively. The synthesis of eight new compounds resulted in six of them being solid at room temperature, while two of them were in a liquid state, namely ionic liquids. We evaluated the phase transition temperatures and ionic conductivity for each compound. Notably, N-ethyl-N-methylpyrrolidinium trifluoromethyltrifluoroborate ([C2mpyr][CF3BF3]) exhibited a high ionic conductivity of 1.75×10-4 S cm-1 at 25 oC, which is one of the highest values reported among IPCs to date. The combination of an experimental and MI based approach revealed an improved understanding of the relationship between ion size and ionic conductivity for a series of pyrrolidinium-based IPCs, and it is expected that further improvements to this approach will yield greater understanding of structure-property relationships.

Cellulose is attracting attention for the development of environmentally friendly, carbon-neutral, sustainable materials. Cellulose derivatives with cationic groups have the potential for applications in various fields, e.g., electrolytes. However, the current situation is marked by a low degree of cationic group incorporation and a need for more efficient synthesis methods. In this study, cationic cellulose was synthesized using an epoxy derivative, 2,3-epoxypropyltrimethylammonium chloride (EPTMAC), in an aqueous pyrrolidinium hydroxide solution. Since an aqueous pyrrolidinium hydroxide solution is a strong alkaline solution, the solution not only exhibits a high cellulose solubility at room temperature but also facilitates the reaction between cellulose and the epoxy derivative. We investigated the influence of reaction time, temperature, cellulose concentration, cationic reagent concentration, and the selection of a precipitation solvent for purification on the degree of substitution (DS) value of cationic cellulose. The structure of the obtained cationic cellulose was examined using 1H NMR, 1H-1H TOCSY, 1H-13C HSQC measurements, and Fourier-transform infrared spectroscopy (FT-IR). As a result of increasing cellulose and EPTMAC concentrations, the DS value increased, reaching a maximum value of 1.9. Solubility tests indicated that the cationic cellulose with chloride counter-anions exhibited notable solubility even in ethanol when the DS values were over 1.2. Cationic cellulose with bis(trifluoromethylsulfonyl)amide (TFSA) anion synthesized with a view to battery applications was insoluble in water and exhibited a film-forming property. Thus, the solubility of cationic cellulose could be controlled by varying the anionic species.

Cellulose is one of the main components of plant cell walls, abundant on earth, and is a non-edible material that can be acquired at a low cost. Furthermore, there has been increasing interest in its use in environmentally friendly, carbon-neutral, sustainable materials. It is expected that the applications of cellulose will expand with the development of a simple processing method. Previously, it was demonstrated that cellulose can be dissolved in a non-heated, short-duration process using an aqueous pyrrolidinium hydroxide solution. In this study, we dissolved cellulose in aqueous N-butyl-N-methylpyrrolidinium hydroxide solution ([C4mpyr][OH]/H2O) and investigated the cellulose regeneration process based on changes in solubility upon application of CO2 gas. We investigated the effect of transformation of the anion chemical structure on cellulose solubility by flowing CO2 gas into [C4mpyr][OH]/H2O and conducted pH, FT-IR, and 13C NMR measurements. We observed that the changes in anion structure allowed for the modulation of cellulose solubility in [C4mpyr][OH]/H2O, thus establishing a simple and safe cellulose regeneration process. This regeneration process was also applied to enable the production of cellulose hydrogels. The hydrogel formed using this approach was revealed to be of a higher mechanical strength than that of an analogous hydrogel produced using the same dissolution solvent with addition of a cross-linker. The ability to produce cellulose-based hydrogels of different mechanical properties is expected to expand the possible applications.