Study on Fundamental Properties of Solvate Electrolytes and Their Application in Batteries

• Published in: Denki kagaku oyobi kōgyō butsuri kagaku Vol. 90; no. 10; p. 101003
• Main Author: DOKKO, Kaoru
• Format: Journal Article
• Language: English
• Published: The Electrochemical Society of Japan 05.10.2022
• Subjects: Electrolytes; Ionic Conductivity; Ionic Liquids; Lithium Batteries
• ISSN: 1344-3542; 2186-2451
• DOI: 10.5796/electrochemistry.22-00072

Li salts and polar solvents form solvates, and certain solvates have low melting temperatures and remain in a liquid state at room temperature. Liquid-state solvates exhibit ionic conductivity and can be used as electrolytes in lithium batteries. The author and co-workers have systematically studied the interactions of Li+ ions with solvents and anions, Li+-coordination structures, thermal properties, transport properties, and electrochemical properties in molten-solvate electrolytes. In molten solvates, almost all solvent molecules are coordinated to Li+ ions, and uncoordinated (free) solvents are rare. Additionally, anions are involved in the coordination of the Li+ ions. The molten solvate electrolytes show non-flammability and negligible vapor pressure at room temperature because of the extremely low concentration (activity) of the free solvent, which can improve the thermal stability of Li batteries. The low activity of the free solvent results in a wide electrochemical window of the molten-solvate electrolytes, thereby suppressing undesired side reactions in Li batteries. The activity of the free solvent in the electrolytes significantly affects the electrochemical reaction processes, such as the reduction reaction of sulfur (S8) in a Li–S battery and the oxygen reduction reaction (ORR) in a Li–air battery. The solubility of the reaction intermediates of the S8 cathode and the ORR decreases with the decrease in solvent activity, which enables the highly efficient charge–discharge of Li–S and Li–air batteries. In molten solvates, Li+ ions diffuse and migrate by exchanging ligands (solvents and anions). Certain molten-solvate electrolytes show high Li+ ion transference numbers over 0.5, and these high transference numbers are useful in mitigating the concentration overpotential during the charging and discharging of Li batteries at high current densities.