Tuning the Electrochemical Properties of Organic Battery Cathode Materials: Insights from Evolutionary Algorithm DFT Calculations

Several forms of organic materials have arisen as promising candidates for future active electrode materials for Li‐ion and post‐Li‐ion batteries, owing to a series of key features that encompasses sustainability, accessibility, and tunable electrochemical properties by molecular modifications. In this context, a series of organic electrode materials (OEMs) are investigated to further understand their thermodynamic and electronic properties. Through an evolutionary algorithm approach combined with first‐principles calculations, the crystal structure of lithiated and delithiated phases of these OEMs and their respective NO(2)‐substituted analogues are predicted. This framework allows a first assessment of their electrochemical and electronic properties and further understanding on the effects of the nitro group in the substituted compounds. NO(2) is found to strongly affect structural and thermodynamic aspects during the electrochemical reaction with the reducing equivalents (Li(+)+e(−)), changing the OEM's character from a low‐potential anode to a high‐potential cathode by creating a localization of the additional electrons, thus resulting in a better‐defined redox‐active center and leading to a shift in the potential from 0.92 V to 2.66 V vs. Li/Li(+).