Engineering Antiperovskite Ni4N/VN Heterostructure with Improved Intrinsic Interfacial Charge Transfer as a Bifunctional Catalyst for Rechargeable Zinc–Air Batteries

Development of an oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional electrocatalyst based on a low-cost and earth-abundant raw material is pivotal for large-scale application of rechargeable zinc–air batteries (ZABs). Herein, an antiperovskite Ni 4 N/VN heterostructure anchored on nitrogen-doped graphene (Ni 4 N/VN–NG) was designed and synthesized. Both experimental and theoretical results suggest that the electronic coupling between Ni 4 N and VN can regulate the electronic structure of the catalyst for promoted catalytic kinetics. Remarkably, the Ni 4 N/VN–NG exhibited excellent bifunctional catalytic activity and stability with an overvoltage difference of 0.75 V. The ZABs with Ni 4 N/VN–NG as the air cathode can achieve a high-power density of 140 mW cm –2 and a long-term operational stability for 180 h, superior to the battery with commercial Pt/C and RuO 2 catalysts. This work proposes the construction of pretransition metal and post-transition metal nitride heterojunctions to promote ORR/OER activity and provides a new strategy for the rational design and synthesis of efficient oxygen bifunctional electrocatalysts for ZABs.