Engineering cyano groups into hydrogen-bonded organic supramolecules with multi redox centers for high-performance Li-ion battery cathode

Bottom-up molecular engineering by rational design has emerged as a promising strategy for exploring advanced organic cathodes. However, directly programming organic moieties into high-performance electro-active materials remains a great challenge. Herein, we design and synthesize a hydrogen-bonded supramolecule (hexaazatrinaphthalene hexacarbonitrile, HATN-6CN) anchored with abundant cyano groups, which ensures structural stability, extended π-conjugated system, and multiple redox active centers. As a result, the HATN-6CN cathode delivers a high specific capacity (297.6 mAh g –1 at 0.5 A g –1 , 225.2 mAh g –1 at 5 A g –1 ) and outstanding long-term cycling performance (191.9 mAh g –1 over 1000 cycles at 5 A g –1 with a capacity retention of 85.2 %). Moreover, the charge storage mechanisms, structural evolution, and reversibility during the redox process of HATN-6CN were systematically investigated. This work offers a feasible and promising avenue for bottom-up molecular engineering of organic electrodes by rational design.