Mechanistic Insights of Bipolar Redox Cathodes for Organic Rechargeable Batteries: LUMO Anti‒Bonding Contributions

Abstract

Abstract The search for sustainable organic cathode materials has been constrained by intrinsically low redox potentials and limited understanding of p ‒type redox chemistry. In this study, we establish a rational design framework for bipolar cathodes by combining p ‒type functionalities (‒NH 2 , ‒OH, ‒SH) with carbonyl backbones and elucidating their structure‒property relationships using the first‐principles calculations. We find that redox potentials and resultant discharging behaviors are governed by the interplay between backbone electron deficiency, p ‒type pendant group identity, and solvation stability, in conjunction with charging energy and the lowest unoccupied molecular orbital (LUMO) anti‐bonding contributions as principal electronic descriptors. While PF 6 anion‐induced decomposition occurs through backbone fluorination and/or locally HF‐coordinated bipolar compound generation depending on p ‒type functionality, its onset beyond the electrochemical voltage window allows full utilization of both n ‒type and p ‒type mechanisms. This design strategy enables theoretical charge capacities and energy densities that surpass those of state‐of‐the‐art inorganic and organic cathodes. These insights highlight the underexplored role of p ‒type functionalities and provide molecular‒level guidelines for engineering next‒generation, high‒performance organic cathodes.