Metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrids as efficient bifunctional oxygen electrodes for Zn−air batteries

doi:10.1007/s11705-022-2153-3

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (9) : 1367-1376 https://doi.org/10.1007/s11705-022-2153-3

RESEARCH ARTICLE

Metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrids as efficient bifunctional oxygen electrodes for Zn−air batteries

Cai-Yue Wang, Meng-Qi Gao, Cheng-Cai Zhao, Li-Min Zhao, Hui Zhao(

)

School of Materials Science and Engineering, Liaocheng University, Liaocheng 252000, China

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Abstract

The exploration of efficient bifunctional electrocatalysts for oxygen reduction reaction and oxygen evolution reaction is pivotal for the development of rechargeable metal–air batteries. Transition metal phosphides are emerging as promising catalyst candidates because of their superb activity and low cost. Herein, a novel metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrid was developed by a carbothermal reduction of cobalt/nickel phosphonate hybrids with different Co/Ni molar ratios. The metal phosphonate derivation method achieved an intimately coupled interaction between metal phosphides and a heteroatom-doped carbon substrate. The resultant Co₂P/Ni₃P@NC-0.2 enables an impressive electrocatalytic oxygen reduction reaction activity, comparable with those of state-of-the-art Pt/C catalysts in terms of onset potential (0.88 V), 4e^‒ selectivity, methanol tolerance, and long-term durability. Moreover, remarkable oxygen evolution reaction activity was also observed in alkaline conditions. The high activity is ascribed to the N-doping, abundant accessible catalytic active sites, and the synergistic effect among the components. This work not only describes a high-efficiency electrocatalyst for both oxygen reduction reaction and oxygen evolution reaction, but also highlights the application of metal phosphonate hybrids in fabricating metal phosphides with tunable structures, which is of great significance in the energy conversion field.

Keywords metal phosphonate cobalt/nickel phosphide N-doped carbon oxygen electrochemistry Zn−air battery

Corresponding Author(s): Hui Zhao

About author:

Tongcan Cui and Yizhe Hou contributed equally to this work.

Online First Date: 29 April 2022 Issue Date: 20 September 2022

Cite this article:

Cai-Yue Wang,Meng-Qi Gao,Cheng-Cai Zhao, et al. Metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrids as efficient bifunctional oxygen electrodes for Zn−air batteries[J]. Front. Chem. Sci. Eng., 2022, 16(9): 1367-1376.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2153-3
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I9/1367

Scheme1 Illustration of the fabrication of Co/Ni phosphides@N-doped carbon hybrids.

Fig.1 (a) XRD patterns of the as-synthesized Co₂P@NC and Co₂P/Ni₃P@NC samples; (b) FESEM image and (c–e) TEM images of Co₂P/Ni₃P@NC-0.2; (f) Raman spectra of the as-synthesized Co₂P@NC and Co₂P/Ni₃P@NC samples.

Fig.2 (a) N₂ adsorption–desorption isotherm curves of the as-synthesized samples; high-resolution XPS spectra of (b) Co, (c) Ni, (d) C, (e) P, and (f) N of Co₂P/Ni₃P@NC-0.2.

Fig.3 (a) CV and (b) LSV curves of synthesized samples and Pt/C for ORR in O₂-saturated 0.1 mol·L^–1 KOH; (c) electron transfer number (n) and H₂O₂ yield of the as-synthesized samples and Pt/C for ORR in O₂-saturated 0.1 mol·L^–1 KOH; (d) ORR Tafel plots; (e) the i?t relationship of resistance to methanol poison for Co₂P/Ni₃P@NC-0.2 and Pt/C through the addition of 5 mL of 3 mol·L^–1 methanol into the solution; (f) chronoamperometric response of Co₂P/Ni₃P@NC-0.2 and Pt/C over 20000 s.

Fig.4 (a) LSV curves of fabricated catalysts measured for both the potential ORR and OER; (b) optical photograph of the open-circuit voltage of the Co₂P/Ni₃P@NC-0.2 assembled ZAB; (c) the curves of the galvanodynamic charge/discharge polarization of the assembled ZABs; (d) the discharge polarization curves and the corresponding power densities of the assembled ZABs; (e) discharge?charge cycling curves of the assembled ZABs; (f) digital photograph of LED light lit by the Co₂P/Ni₃P@NC-0.2-assembled ZABs (three) in series.

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[1]	Rui-Qi Zhang, Ang Ma, Xiang Liang, Li-Min Zhao, Hui Zhao, Zhong-Yong Yuan. Cobalt nanoparticle decorated N-doped carbons derived from a cobalt covalent organic framework for oxygen electrochemistry[J]. Front. Chem. Sci. Eng., 2021, 15(6): 1550-1560.
[2]	Wanyue Liu, Xiaoqin Liu, Jinming Chang, Feng Jiang, Shishi Pang, Hejun Gao, Yunwen Liao, Sheng Yu. Efficient removal of Cr(VI) and Pb(II) from aqueous solution by magnetic nitrogen-doped carbon[J]. Front. Chem. Sci. Eng., 2021, 15(5): 1185-1196.
[3]	Miaomiao Tong, Lei Wang, Peng Yu, Xu Liu, Honggang Fu. 3D Network nanostructured NiCoP nanosheets supported on N-doped carbon coated Ni foam as a highly active bifunctional electrocatalyst for hydrogen and oxygen evolution reactions[J]. Front. Chem. Sci. Eng., 2018, 12(3): 417-424.

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