Ultrasonic Plasma Engineering Toward Facile Synthesis of Single-Atom M-N(4)/N-Doped Carbon (M = Fe, Co) as Superior Oxygen Electrocatalyst in Rechargeable Zinc-Air Batteries

超声等离子体工程在简易合成单原子MN(4)/N掺杂碳(M = Fe, Co)作为可充电锌空气电池中优异氧电催化剂方面的应用

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Abstract

As bifunctional oxygen evolution/reduction electrocatalysts, transition-metal-based single-atom-doped nitrogen-carbon (NC) matrices are promising successors of the corresponding noble-metal-based catalysts, offering the advantages of ultrahigh atom utilization efficiency and surface active energy. However, the fabrication of such matrices (e.g., well-dispersed single-atom-doped M-N(4)/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-N(4) (M = Fe, Co) carbon catalysts with a production rate as high as 10 mg min(-1). The Co-N(4)/NC presented a bifunctional potential drop of ΔE = 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-N(4) was the major active site with superior O(2) adsorption-desorption mechanisms. In a practical Zn-air battery test, the air electrode coated with Co-N(4)/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-N(4)/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.

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