Toward coupling of electrochemical redox properties with electrostatic potential surfaces tailored by dopant architectures for pyrenetetrone

Abstract Despite the promise of pyrenetetrone derivatives as insoluble organic cathode compounds for lithium-ion batteries, there is limited information on their electrochemical characteristics. Herein, a highly reliable computational protocol is employed to systematically explore the redox properties and theoretical performances of pyrenetetrone derivatives. This comprehensive analysis reveals that the electrochemical redox properties of pyrenetetrone derivatives at fully charged states are determined by complementary contributions from key factors, such as dopant electronegativity, electrostatic potential of the central backbone, and interatomic electronic flow. In contrast, dopant electronegativity becomes a dominant factor for tuning the redox behaviors of these organic compounds during the Li-involved discharging process, indicating the potential of boron-doped compounds for high-performance cathodes. Further investigation highlights that the entire discharging process can be summarized as Li-induced continuous reduction in electron affinity terminated by a sudden increase in solvation energy (depending on dopant electronegativity), which emphasizes the importance of solvation energy in determining cathodic deactivation.