Spin state modulation on dual Fe center by adjacent Ni sites enabling the boosted activities and ultra-long stability in Zn-air batteries

Canhui Zhang; Xingkun Wang; Zhentao Ma; Hanxu Yao; Hengjun Liu; Cheng Li; Jian Zhou; Ren Xu; Xusheng Zheng; Huanlei Wang; Qiang Li; Meng Gu; Heqing Jiang; Minghua Huang

doi:10.1016/j.scib.2023.07.049

Spin state modulation on dual Fe center by adjacent Ni sites enabling the boosted activities and ultra-long stability in Zn-air batteries

Sci Bull (Beijing). 2023 Sep 30;68(18):2042-2053. doi: 10.1016/j.scib.2023.07.049. Epub 2023 Jul 31.

Authors

Canhui Zhang¹, Xingkun Wang², Zhentao Ma³, Hanxu Yao², Hengjun Liu⁴, Cheng Li⁵, Jian Zhou¹, Ren Xu¹, Xusheng Zheng³, Huanlei Wang¹, Qiang Li⁴, Meng Gu⁶, Heqing Jiang⁷, Minghua Huang⁸

Affiliations

¹ School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China.
² School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China; Qingdao Key Laboratory of Functional Membrane Material and Membrane Technology, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China.
³ National Synchrotron Radiation Laboratory (NSRL), University of Science and Technology of China, Hefei 230029, China.
⁴ College of Physics, University-Industry Joint Center for Ocean Observation and Broadband Communication, State Key Laboratory of Bio-Fibers and Eco-Textiles, Weihai Innovation Research Institute, Qingdao University, Qingdao 266071, China.
⁵ Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China.
⁶ Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China. Electronic address: [email protected].
⁷ Qingdao Key Laboratory of Functional Membrane Material and Membrane Technology, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China. Electronic address: [email protected].
⁸ School of Materials Science and Engineering, Ocean University of China, Qingdao 266100, China. Electronic address: [email protected].

PMID: 37574374
DOI: 10.1016/j.scib.2023.07.049

Abstract

Breakthrough in developing cost-effective Fe-based catalysts with superior oxygen reduction reaction (ORR) activities and ultra-long-term stability for application in Zn-air batteries (ZABs) remain a priority but still full of challenges. Herein, the neighboring NiN₄ single-metal-atom and Fe₂N₅ dual-metal-atoms on the N-doped hollow carbon sphere (Fe/Ni-NHCS) were deliberately constructed as the efficient and robust ORR catalyst for ZABs. Both theory calculations and magnetic measurements demonstrate that the introduction of NiN₄ provides a significant role on optimizing the electron spin state of Fe₂N₅ sites and reducing the energy barrier for the adsorption and conversion of the oxygen-containing intermediates, enabling the Fe/Ni-NHCS with excellent ORR performance and ultralow byproduct HO₂^- yield (0.5%). Impressively, the ZABs driven by Fe/Ni-NHCS exhibit unprecedented long-term rechargeable stability over 1200 h. This work paves a new venue to manipulate the spin state of active sites for simultaneously achieving superior catalytic activities and ultra-long-term stability in energy conversion technologies.

Keywords: Dual-metal-atom; Electron spin state; Oxygen reduction reaction; Rechargeable stability.