LAUSR

Abstract Despite the potential of organic materials for cathodes in lithium-ion batteries arising from their eco-friendly production processes and structural flexibility, their redox properties are not comprehensively unveiled. In this work, the redox properties and performances for chloranil derivatives with one to four cyano functional group(s) are studied to assess their potential as high-potential organic cathode materials. The well-designed computational protocol is employed to reliably predict the redox behaviors for the organic compounds. This investigation highlights synergistic effects of carbonyls and cyanides on improving the electrochemical properties, exhibiting the remarkably high open-circuit redox potential (4.50 ​V vs. Li/Li+) and theoretical performances (515 ​mA ​h/g and 1517 ​mWh/g) for the chloranil derivative with four cyano functionalities. Furthermore, this study emphasizes that the redox potential of a chloranil derivative strongly relies not only on its structural variation but also on the Li-involved discharging process, electronic properties, and, most importantly, “solvation energy”. A universal correlation of redox potential with electron affinity and solvation energy addresses that chloranils would experience two-stage transition behaviors during the discharging process, implying a critical role of solvation energy in their cathodic deactivation and thus suggesting a smart approach for the systematic design of high-performance organic cathodes. Electrostatic potential maps unambiguously describe the change in the reductive ability of a chloranil derivative during the Li-involved discharging process.