Interfacial Stabilization of LiO-Based Cathodes by Malonic-Acid-Functionalized Fullerenes as a Superoxo-Radical Scavenger for Suppressing Parasitic Reactions.

The utilization of an anionic redox reaction as an innovative strategy for overcoming the limitations of cathode capacity in lithium-ion batteries has recently been the focus of intensive research. LiO-based materials using the anionic (oxygen) redox reaction have the potential to deliver a much higher capacity than commercial cathodes using cationic redox reactions based on transition-metal ions. However, parasitic reactions attributed to the superoxo species (such as LiO), derived from the LiO active material of the cathode, deteriorate the stability of the interface between the cathode and electrolyte, which has limited the commercialization of LiO-based cathodes. To address this issue, malonic-acid-functionalized fullerenes (MC) were applied in the electrolyte as an additive for scavenging the superoxo radicals (O in LiO) that trigger parasitic reactions. MC can efficiently capture superoxo radicals using the π-conjugated surface and the malonate functionality on the surface. As a result, MC considerably enhanced the available capacity and cycling performance of the LiO-based cathodes, decreased the interfacial layer formed on the cathode surface, and hindered the generation of byproducts, such as LiCO, CO, and C-F, derived from parasitic reactions. In addition, the loss of LiO from the cathode surface during cycling was also suppressed, validating the ability of MC to capture superoxo radicals. This result confirms that the introduction of MC can effectively alleviate the parasitic reactions at the cathode/electrolyte interface and improve the electrochemical performance of LiO-based cathodes by scavenging the superoxo species.