3D TM-N-C Electrocatalysts with Dense Active Sites for the Membraneless Direct Methanol Fuel Cell and Zn-Air Batteries

Xiaoting Cao; Ruili Song; Xiaoshuang Zhou; Xi Wang; Xu Dong; Ningyi Yuan; Jianning Ding

doi:10.1021/acs.langmuir.2c00347

3D TM-N-C Electrocatalysts with Dense Active Sites for the Membraneless Direct Methanol Fuel Cell and Zn-Air Batteries

Langmuir. 2022 Apr 26;38(16):4948-4957. doi: 10.1021/acs.langmuir.2c00347. Epub 2022 Apr 13.

Authors

Xiaoting Cao¹, Ruili Song¹, Xiaoshuang Zhou¹, Xi Wang¹, Xu Dong¹, Ningyi Yuan¹, Jianning Ding^{1

2}

Affiliations

¹ Jiangsu Collaborative Innovation Center for Photovoltaic Science and Engineering, Jiangsu Province Cultivation base for State Key Laboratory of Photovoltaic Science and Technology, School of Materials Science and Engineering, Changzhou University, Changzhou, Jiangsu 213164, P. R. China.
² Yangzhou University, Yangzhou, Jiangsu 225009, P. R. China.

PMID: 35414176
DOI: 10.1021/acs.langmuir.2c00347

Abstract

Electrocatalysts with high cost-effectiveness for the oxygen reduction reaction (ORR) are essential for fuel cells (FC) and Zn-Air batteries (ZAB), which need highly active sites and suitable carbon substrates to accelerate the charge transfer kinetics. Herein, a simple and extensible method using ball milling and space-confinement pyrolysis is reported to prepare a series of transition metals and N-C catalysts (M-NLPC), which possess three-dimensional porous carbon substrates and dense active sites for efficient ORR. M-NLPC catalysts (especially Fe-NLPC) exhibit outstanding ORR activity with a half-wave potential (E_1/2, 0.88 V) in an alkaline medium, high stability, and strong methanol resistance. The M-N₄ sites are proven to be the active centers in M-NLPC by theoretical calculation, and methanol molecules are more likely to desorb than react on the Fe-N₄ sites, which is the origin of the inactivity for the methanol oxidation reaction (MOR). Furthermore, Fe-NLPC was applied to membraneless alkaline direct methanol FC (DMFC) in practice, exhibiting outstanding performance. Meanwhile, the Fe-NLPC-based ZAB also shows excellent electrochemical performance.