Ultrasonic Plasma Engineering Toward Facile Synthesis of Single-Atom M-N4/N-Doped Carbon(M=Fe,Co) as Superior Oxygen Electrocatalyst in Rechargeable Zinc-Air Batteries

As bifunctional oxygen evolution/reduction electrocatalysts,transition-metal-based single-atom-doped nitrogen-carbon(NC)matrices are promising successors of the corresponding noblemetal-based catalysts,offering the advantages of ultrahigh atom utilization effciency and surface active energy.However,the fabrication of such matrices(e.g.,well-dispersed single-atom-doped M-N4/NCs)often requires numerous steps and tedious processes.Herein,ultrasonic plasma engineering allows direct carbonization in a precursor solution containing metal phthalocyanine and aniline.When combining with the dispersion effect of ultrasonic waves,we successfully fabricated uniform single-atom M-N4(M=Fe,Co)carbon catalysts with a production rate as high as 10 mg min-1.The Co-N4/NC presented a bifunctional potential drop ofΔE=0.79 V,outperforming the benchmark Pt/C-Ru/C catalyst(ΔE=0.88 V)at the same catalyst loading.Theoretical calculations revealed that Co-N4 was the major active site with superior O2 adsorption-desorption mechanisms.In a practical Zn-air battery test,the air electrode coated with Co-N4/NC exhibited a specific capacity(762.8 mAh g(-1))and power density(101.62 mW cm^(-2)),exceeding those of Pt/C-Ru/C(700.8 mAh g^(-1) and 89.16 mW cm^(-2),respectively)at the same catalyst loading.Moreover,for Co-N4/NC,the potential difference increased from 1.16 to 1.47 V after 100 charge-discharge cycles.The proposed innovative and scalable strategy was concluded to be well suited for the fabrication of single-atom-doped carbons as promising bifunctional oxygen evolution/reduction electrocatalysts for metal-air batteries.