Duraisamy Senthil Raja, Pandiyarajan Anand, Yu‐Chieh Ting, Shih‐Yuan Lu
Abstract Cost‐effective highly efficient and robust bifunctional oxygen electrocatalysts are essential for commercialization of rechargeable zinc air batteries (ZABs). Doping is a simple and effective defect engineering approach for enhancement of electrocatalytic activities. Herein, Fe‐doped, carbon‐coated CoNi alloy nanoparticle catalysts, Fe‐CoNi@C, derived from CoNi bimetallic metal‐organic frameworks, are developed as outstanding bifunctional oxygen electrocatalysts for rechargeable ZABs. Fe‐CoNi@C achieves an ultrasmall voltage gaps at 10 mA cm −2 (Δ E 10 ) of 0.668 V, significantly smaller than 0.767 V of (Pt/C + IrO 2 ). The Fe‐CoNi@C based ZAB delivers a high peak power density of 307.7 mW cm −2 at a high current density of 521 mA cm −2 , largely surpassing the (Pt/C + IrO 2 ) based one (199.7 mW cm −2 at 310 mA cm −2 ), and exhibits excellent cycling stability with a stable operation of up to 1800 cycles (600 h), much longer than 940 cycles (313 h) achieved by the (Pt/C + IrO 2 ) based one.