π-Conjugated Hexaazatrinaphthylene-Based Azo Polymer Cathode Material Synthesized by a Reductive Homocoupling Reaction for Organic Lithium-Ion Batteries.

A novel hexaazatrinaphthylene-based (HATN) azo polymer (PAH) was synthesized from a newly designed tri-nitro compound trinitrodiquinoxalino[2,3-a:2',3'-]phenazine (HATNTN) through a Zn-induced reductive homocoupling reaction and used as a cathode material for lithium-ion batteries (LIBs). The integration of redox-active HATN units and azo linkages can improve the specific capacity, rate performance, and cycling stability of the PAH cathode. The control LIBs were assembled from HATNTN, in which HATNTN can be electrochemically reduced to an HATN-based azo polymer. Compared with the HATNTN cathode, the PAH cathode delivers higher specific capacities with much-improved cycling stability (97 mA h g capacity retention after 1500 cycles at 500 mA g, which is around 28 times that of the HATNTN cathode) and considerably better rate performance (118 mA h g at 2000 mA g, which is around 90 times that of the HATNTN cathode), simultaneously. This work provides a chemical polymerization strategy to construct extended π-conjugated azo polymers with multiple redox centers from nitro compounds for developing high-performance LIBs.