Facile Synthesis of Diazaanthraquinone Dimers as High-Capacity Organic Cathode Materials for Rechargeable Lithium...

Organic cathode materials (OCMs) have tremendous potential to construct sustainable and highly efficient batteries beyond conventional Li-ion batteries. Thereinto, quinone/pyrazine hybrids show significant advantages in material availability, energy density, and cycling stability. Herein, we propose a facile method to synthesize quinone/pyrazine hybrids, i.e., the condensation reaction between ortho-diamine and bromoacetyl groups. Based on it, we have successfully synthesized three 1,4-diazaanthraquinone (DAAQ) dimers, including 2,2'-bi(1,4-diazaanthraquinone) (BDAAQ) with an exceptional theoretical capacity of 512 mAh g^-1 based on the eight-electron reaction. It can be fully utilized in Li batteries in a wide voltage range of 0.8-3.8 V, at the cost of inferior cycling stability. In an optimal voltage range of 1.4-3.8 V, BDAAQ exhibits one of the best comprehensive electrochemical performances for small-molecule OCMs, including a high specific capacity of 366 mAh g^-1, an average discharge voltage of 2.26 V, as well as a respectable capacity retention of 59% after 500 cycles. Moreover, the in-depth investigations reveal the redox reaction mechanisms based on C═O and C═N groups as well as the capacity fading mechanisms based on dissolution-redeposition behaviors. In brief, this work provides an instructive synthesis method and mechanism understanding of high-performance OCMs based on a quinone/pyrazine hybrid structure.