Self-Catalyzed Growth of Co₄N and N-Doped Carbon Nanotubes toward Bifunctional Cathode for Highly Safe and Flexible Li-Air Batteries

The practical application of high-energy density lithium-oxygen (Li-O₂) batteries is severely impeded by the notorious cycling stability and safety, which mainly comes from slow kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at cathodes, causing inferior redox overpotentials and reactive lithium metal in flammable liquid electrolyte. Herein, a bifunctional electrode, a safe gel polymer electrolyte (GPE), and a robust lithium anode are proposed to alleviate above problems. The bifunctional electrode is composed of N-doped carbon nanotubes (N-CNTs) and Co₄N by in situ chemical vapor deposition self-catalyzed growth on carbon cloth (N-CNTs@Co₄N@CC). The self-supporting, binder-free N-CNTs@Co₄N@CC electrode has a strong and stable three-dimensional (3D) interconnected conductive structure, which provides interconnectivity between the active sites and the electrode to promote the transfer of electrons. Furthermore, the N-CNT-intertwined Co₄N ensures efficient catalytic activity. Hence, the electrode demonstrates improved electrochemical properties even under a large current density (2000 mA g^-1) and long cycling operation (250 cycles). Moreover, a highly safe and flexible rechargeable cell using the 3D N-CNTs@Co₄N@CC electrode, GPE, and robust lithium anode design has been explored. The open circuit voltage is stable at ∼3.0 V even after 9800 cycles, which proves the mechanical durability of the integrated GPE cell. The stable cable-type Li-air battery was demonstrated to stably drive the light-emitting diodes (LEDs), highlighting the reliability for practical use.