LAUSR

In efforts to design organic cathode materials for rechargeable batteries, a fundamental understanding of the redox properties of diverse non-carbon-based functionalities incorporated into 9,10-anthraquinone is lacking despite their potential impact. Herein, a preliminary investigation of the potential of anthraquinones with halogenated nitrogen-based functionalities reveals that the Li-triggered structural collapse observed in the early stage of discharging can be ascribed to the preference toward the strong Lewis acid-base interaction of N-Li-X (X = F or Cl) over the repulsive interaction of the electron-rich N-X bond. A further study of three solutions (i.e., substitution of NX2 with (i) BX2, (ii) NH2, and (iii) BH2) to the structural decomposition issue highlights four conclusive remarks. First, the replacement of N and/or X with electron-deficient atom(s), such as B and/or H, relieves the repulsive force on the N-X bond without the assistance of Li, and thus, no structural decomposition occurs. Second, the incorporation of BH2 is verified to be the most beneficial for improving the theoretical performance. Third, all the redox properties are better correlated with electron affinity and solvation energy than the electronegativity of functionality, implying that these key parameters cooperatively contribute to the electrochemical redox potential; additionally, solvation energy plays a crucial role in determining cathodic deactivation. Fourth, the improvement to the Li storage capability of anthraquinone using the third solution can primarily be ascribed to solvation energy remaining at a negative value even after the binding of more Li atoms than the other derivatives.