Density Functional Theory Modeling-Assisted Investigation of Thermodynamics and Redox Properties of Boron-Doped Corannulenes for Cathodes in Lithium-Ion Batteries

Understanding thermodynamics and reduction potentials of boron-doped corannulenes (BDCs) can provide meaningful insight to establish strategies for designing doping processes of organic materials applicable to cathodes in lithium-ion batteries (LIBs). In this study, a comprehensive set of BDC models is prepared to investigate the effect of the number and geometric position of doped boron atoms on the thermodynamic stability and redox properties of the corannulene. Our investigation enables us to evaluate their potential as organic cathode materials in LIBs. In this study, it is found that the first and second boron atoms can be exclusively doped in thermodynamically stable positions. Corannulene derivatives doped by the boron atom show enhanced reduction potentials ranged from 2.41 to 5.05 V vs Li/Li+ as compared with the pristine corannulene (0.9 V vs Li/Li+). A higher level of structural heterogeneity created by another boron atom does not guarantee a higher reduction potential (3.03 and 2.51 V vs Li/Li+ for probability-averaged reduction potentials of 1- and 2-boron-doped corannulenes, respectively). Reduction potential is strongly correlated with the spin state as well as the structural and electronic properties. The doped boron atoms play a critical role in improving the stability of the Li-binding thermodynamics, showing their positive impact on the enhancement of the charge capacity.