Azatriangulenetrione as the Anode Material for Sodium-Ion Batteries: Reversible Redox Chemistry Mediated by Lone Pair Electrons.

Redox-active organic molecules have potential as electrode materials, but their cycling stability is often limited by the irreversible formation of σ-bonds from the radical intermediates. Herein, we present an effective approach to achieve high reversibility by using lone pair electrons to mediate intramolecular radical-radical coupling. Azatriangulenetrione ( 1 ) was examined as the anode in sodium-ion batteries, which displayed a reversible four-step, one-electron redox chemistry. In situ electron spin resonance, ex situ Fourier transform infrared/X-ray photoelectron spectroscopy, and density functional theory calculation revealed that the unstable radical anions can couple with each other through the lone pair electrons of the central nitrogen atom, leading to stabilized radical species. Furthermore, scan-rate-dependent cyclic voltammetry measurements and galvanostatic intermittent titration techniques demonstrated that the redox reaction kinetics for radical formation were much faster than the radical paring process. This study offers deep insights into the design of highly reversible organic electrodes.