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Research Article

Enhancing zinc–air battery performance by constructing three-dimensional N-doped carbon coating multiple valence Co and MnO heterostructures

Qi Liu1, Panzhe Qiao3, Miaomiao Tong2, Ying Xie2, Xinxin Zhang2, Kuo Lin1, Zhijian Liang2, Lei Wang2( ), Honggang Fu1,2( )
Key Laboratory of Superlight Materials and Surface Technology of the Ministry of Education of the People’s Republic of China, Harbin Engineering University, Harbin 150080, China
Key Laboratory of Functional Inorganic Material Chemistry Ministry of Education of the People’s Republic of China, Heilongjiang University, Harbin 150080, China
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China
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Graphical Abstract

Three-dimensional (3D) structures composed of N-doped carbon coating multiple valence Co and MnO heterostructures supported on carbon cloth substrate (Co-MnO@NC/CC) has been synthesized by combining electrochemical deposition with pyrolytic strategy. The synergy between multiple valence cobalt and MnO significantly improves the oxygen evolution reaction (OER)/oxygen reduction reaction (ORR) activity, and the MnO acts as the main OER active site could significantly optimize the energy barrier of O* → OOH*, thus the assembled Zn–air battery shows high peak power density of 175 mW·cm−2 and a small charging-discharging voltage gap of 0.75 V at 10 mA·cm−2.

Abstract

Developing highly-efficient bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) electrocatalysts is crucial for the widespread application of rechargeable Zn–air batteries (ZABs). Herein, an efficiency electrodeposition and pyrolytic strategy to synthesize the three-dimensional (3D) N-doped carbon coating multiple valence Co and MnO heterostructures supported on carbon cloth substrate (Co-MnO@NC/CC). It contains Co–Co, Co–N, and Co–O bonds, which synergistically enhance the oxygen reaction activity with MnO. It exhibits a working potential of 1.473 V at 10 mA·cm−2 for OER and onset potential of 0.97 V for ORR. Theory calculations demonstrate that the synergy between cobalt and manganese species could optimize the d-band center and reduce the energy barrier of Co-MnO@NC/CC for both OER and ORR processes. Besides, the MnO acts as the main OER active site could significantly optimize the energy barrier of O* → OOH*, thus further promoting the OER activity. It can be directly used as the air-cathode for both liquid-state and solid-state ZABs, which could afford a small voltage gap of 0.75 V at 10 mA·cm−2, a high power density of 172.5 mW·cm−2 and a long-term durability for 400 h, surpassing those of the Pt/C + RuO2-based ZAB. Importantly, the assembled batteries show potential applications in portable devices.

Keywords

heterostructuresynergyvalence cobaltmanganese oxideZn–air battery

Electronic Supplementary Material

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Nano Research
Volume 17 Issue 6,
June 2024
Pages 5104-5113
DOI: 10.1007/s12274-023-6404-5
Cite this article:
Liu Q, Qiao P, Tong M, et al. Enhancing zinc–air battery performance by constructing three-dimensional N-doped carbon coating multiple valence Co and MnO heterostructures. Nano Research, 2024, 17(6): 5104-5113. https://doi.org/10.1007/s12274-023-6404-5
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Received: 16 November 2023
Revised: 06 November 2023
Accepted: 08 December 2023
Published: 13 January 2024
© Tsinghua University Press 2023
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