竹岡 裕子

Despite being safe for use in secondary Mg batteries, solid electrolytes exhibit lower ionic conductivities than those of traditional liquid electrolytes. Organic ionic plastic crystals-soft crystals with excellent thermal and electrochemical stabilities and ionic conductivities-are promising solid electrolytes. Herein, we investigated the effects of various anion species and Mg salt concentrations on the properties of pyrrolidinium-based organic ionic plastic crystals (N,N-diethylpyrrolidinium bis(fluorosulfonyl)amide [[C2epyr][FSA]] and N,N-diethylpyrrolidinium bis(trifluoromethylsulfonyl)amide [[C2epyr][TFSA]]) upon Mg(TFSA)2 addition. The Mg-ion transference number (tMg2+) was measured using the Vincent-Bruce method; ionic conductivity via impedance measurements; and phase transition via differential scanning calorimetry. The phase transition behavior, dissociation state of the Mg salt, and electrochemical properties varied with the organic ionic plastic crystal anionic structure. The FSA system became liquid when the Mg salt concentration exceeded 15 mol%. The ionic conductivity of the pyrrolidinium-based organic ionic plastic crystals increased substantially with the Mg salt concentration. In the solid state, [C2epyr][FSA]/Mg(TFSA)2 (5 mol%) (FT5) showed the highest ionic conductivity (2.9 × 10−4 S cm−1 at 25 °C). The tMg2+ of FT5 at 60 °C was 0.29. Mg exhibited redox behavior in FT5 but not in [C2epyr][TFSA]/Mg(TFSA)2 (5 mol%). The FSA− structure is suitable for Mg electrochemistry and will aid in developing high-performance secondary Mg batteries.