Atomically Dispersed Fe–N4 Sites and NiFe-LDH Sub-Nanoclusters as an Excellent Air Cathode for Rechargeable Zinc–Air Batteries

The sluggish four-electron processes of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) limit the development of rechargeable Zn-air batteries (RZABs). Highly efficient ORR/OER bifunctional electrocatalysts are therefore highly desired for the commercialization of RZABs in large scale. Herein, the Fe-N4-C (ORR active sites) and NiFe-LDH clusters (OER active sites) are successfully integrated within a NiFe-LDH/Fe,N-CB electrocatalyst. The NiFe-LDH/Fe,N-CB electrocatalyst is first prepared by the introduction of Fe-N4 into carbon black (CB), followed by the growth of NiFe-LDH clusters. The cluster nature of NiFe-LDH effectively avoids the blocking of Fe-N4-C ORR active centers and affords excellent OER activity. The NiFe-LDH/Fe,N-CB electrocatalyst thus exhibits an excellent bifunctional ORR and OER performance, with a potential gap of only 0.71 V. The NiFe-LDH/Fe,N-CB-based RZAB exhibits an open-circuit voltage of 1.565 V and a specific capacity of 731 mAh gZn-1, which is much better than the RZAB composed of Pt/C and IrO2. Particularly, the NiFe-LDH/Fe,N-CB-based RZAB displays excellent long-term charging/discharging cyclic stability and rechargeability. Even at a large charging/discharging current density (20 mA cm-2), the charging/discharging voltage gap is only ∼1.33 V and exhibits an increase smaller than 5% after 140 cycles. This work provides a new low-cost bifunctional ORR/OER electrocatalyst with high activity and superior long-term stability and will be helpful to the commercialization of RZAB in large scale.