Electrochemical Film Formation on Magnesium Metal in an Ionic Liquid That Dissolves Metal Triflate and Its Application to an Active Material with Anion Charge Carrier.

Abstract

Irregular metallic growth at the anode during recharging of batteries can seriously influence the safety of batteries. To address this problem, we have attempted to design active anode materials with anion charge carriers and recently observed the formation and dissolution of an electrochemical film by triflate anions (CF3SO3-) at the surface of magnesium in an ionic liquid (IL) electrolyte of Mg(CF3SO3)2, which represents a rare anode material. The effect of heterogeneous cations on film formation was examined in this work. In an IL that dissolves NaCF3SO3, sodium ions with a lower reduction potential than Mg2+/Mg would not be expected to assist film formation. However, to our surprise, we discovered that some sodium ions are involved in film formation. The sodium ions are believed to act as a cross-linking point for the formation of a film network, which resulted in fairly good reversibility for film formation. In a Ce(CF3SO3)3-IL electrolyte, an electrochemically formed film free of Ce3+ was obtained. The trivalent cerium cations were deactivated and transformed to an oxide on Mg metal. However, the reversibility of film formation in the Ce(CF3SO3)3 system did not meet the expected level. By coupling the film formation and dissolution behavior with a V2O5 cathode, a rechargeable battery was fabricated with dual ion transport species of Na+ or Ce3+ for the cathode and CF3SO3- for the anode. The unique battery with NaCF3SO3 is demonstrated to exhibit good discharge/charge performance with long-term cyclability.