Hypercrosslinked polymer-mediated fabrication of binary metal phosphide decorated spherical carbon as an efficient and durable bifunctional electrocatalyst for rechargeable Zn–air batteries

Bifunctional oxygen catalysts with excellent catalytic activity and durability towards both oxygen reduction and oxygen evolution reactions (ORR/OER) are pivotal for long-term rechargeable Zn-air batteries. Herein, we report a spherical carbon decorated with FeP and CoP nanoparticles (denoted as FeCoP/NPC) as an ORR/OER bifunctional electrocatalyst for rechargeable Zn-air batteries. HCTCz@Fe/Co-PA is first produced by the modification of phytic acid (PA) onto (into) a porous cross-linked polymeric sphere of poly(bis(N-carbazolyl)-1,2,4,5-tetrazine) (HCTCz), followed by chelating with metal ions (i.e., Fe3+ and Co2+). The subsequent pyrolysis yields FeCoP/NPC, which shows prominent activity and reliability for the ORR and OER due primarily to the synergistic effect of FeP and CoP active sites and N/P co-doped carbon. The aqueous Zn-air battery assembled with FeCoP/NPC provides high specific capacity and peak power density. Notably, the constructed Zn-air battery can be repetitively charged and discharged for 1200 h at 5 mA cm-2. In addition, a flexible solid-state Zn-air battery made from FeCoP/NPC exhibits a power density of 74 mW cm-2 and repeatedly works for 90 h at 2 mA cm-2. This work opens up an avenue for the preparation of highly efficient bifunctional electrocatalysts for Zn-air batteries considering the extensive N-rich polymer precursors and various metal phosphide nanoparticles.