Framework Structures for Mg Battery Cathodes

Abstract

Rechargeable Mg batteries have received intensive attention as affordable rechargeable batteries with high electromotive force, high energy density, and high safety. Mg possesses two valence electrons and has the lowest standard electrode potential (ca. -2.36 V vs. SHE) among the air-stable metals. There is another advantage that Mg metal can be used as an active material because Mg metal hardly forms dendrites. However, the slow diffusion of Mg ions in solid crystals prevents the realization of active materials for Mg rechargeable batteries at room temperature. Although some complex oxides have been reported to work as active materials at higher temperatures, Chevrel compounds are still the gold standards, which work at room temperature. However, the working voltage of the Mg battery using a Chevrel compound for the cathode is only ca. 1.2 V, which is far below that of Li-ion batteries (3-5 V). Nevertheless, Chevrel compounds have the significant advantage that a relatively large space exists in the crystal structure, which allows for fast Mg ion diffusion. In the present study, we investigated some materials with framework structures as cathodes for Mg batteries, which can alleviate the electrostatic constraint between Mg ions and cathode constituents. Specifically, we investigated the redox behavior of the thin films of Prussian blue and Prussian blue analogues in electrolytes containing an Mg salt using electrochemical quartz crystal microbalance and X-ray absorption spectroscopy. In addition, we discuss the electrochemical insertion/extraction behavior of Mg ions and their solvation structures.