Inhibiting Demetalation of Fe─N─C via Mn Sites for Efficient Oxygen Reduction Reaction in Zinc-Air Batteries.

Hu, Chuan; Xing, Gengyu; Han, Wentao; Hao, Yixin; Zhang, Chenchen; Zhang, Ying; Kuo, Chun-Han; Chen, Han-Yi et al. · Adv Mater · 2024

basic_science · Level V

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Abstract

Demetalation caused by the electrochemical dissolution of metallic Fe atoms is a major challenge for the practical application of Fe─N─C catalysts. Herein, an efficient single metallic Mn active site is constructed to improve the strength of the Fe─N bond, inhibiting the demetalation effect of Fe─N─C. Mn acts as an electron donor inducing more delocalized electrons to reduce the oxidation state of Fe by increasing the electron density, thereby enhancing the Fe─N bond and inhibiting the electrochemical dissolution of Fe. The oxygen reduction reaction pathway for the dissociation of Fe─Mn dual sites can overcome the high energy barriers to direct O─O bond dissociation and modulate the electronic states of Fe─N<sub>4</sub> sites. The resulting FeMn─N─C exhibits excellent ORR activity with a high half-wave potential of 0.92 V in alkaline electrolytes. FeMn─N─C as a cathode catalyst for Zn-air batteries has a cycle stability of 700 h at 25 °C and a long cycle stability of more than 210 h under extremely cold conditions at -40 °C. These findings contribute to the development of efficient and stable metal-nitrogen-carbon catalysts for various energy devices.