3D hierarchically macro-/mesoporous graphene frameworks enriched with pyridinic-nitrogen-cobalt active sites as efficient reversible oxygen electrocatalysts for rechargeable zinc-air batteries

doi:10.1016/S1872-2067(20)63642-7

Abstract

Abstract:

Efficient and affordable electrocatalysts for reversible oxygen reduction and oxygen evolution reactions (ORR and OER, respectively) are highly sought-after for use in rechargeable metal-air batteries. However, the construction of high-performance electrocatalysts that possess both largely accessible active sites and superior ORR/OER intrinsic activities is challenging. Herein, we report the design and successful preparation of a 3D hierarchically porous graphene framework with interconnected interlayer macropores and in-plane mesopores, enriched with pyridinic-nitrogen-cobalt (pyri-N-Co) active sites, namely, CoFe/3D-NLG. The pyri-N-Co bonding significantly accelerates sluggish oxygen electrocatalysis kinetics, in turn substantially improving the intrinsic ORR/OER activities per active site, while copious interlayer macropores and in-plane mesopores enable ultra-efficient mass transfer throughout the graphene architecture, thus ensuring sufficient exposure of accessible pyri-N-Co active sites to the reagents. Such a robust catalyst structure endows CoFe/3D-NLG with a remarkably enhanced reversible oxygen electrocatalysis performance, with the ORR half-wave potential identical to that of the benchmark Pt/C catalyst, and OER activity far surpassing that of the noble-metal-based RuO₂ catalyst. Moreover, when employed as an air electrode for a rechargeable Zn-air battery, CoFe/3D-NLG manifests an exceedingly high open-circuit voltage (1.56 V), high peak power density (213 mW cm^-2), ultra-low charge/discharge voltage (0.63 V), and excellent charge/discharge cycling stability, outperforming state-of-the-art noble-metal electrocatalysts.

Key words: Hierarchical pores, Composite catalyst, Oxygen electrocatalysis, Spinel oxide, Rechargeable zinc-air battery

Sheng Zhou, Jiayi Qin, Xueru Zhao, Jing Yang. 3D hierarchically macro-/mesoporous graphene frameworks enriched with pyridinic-nitrogen-cobalt active sites as efficient reversible oxygen electrocatalysts for rechargeable zinc-air batteries[J]. Chinese Journal of Catalysis, 2021, 42(4): 571-582.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63642-7

https://www.cjcatal.com/EN/Y2021/V42/I4/571

Figures/Tables 5

Fig. 1. (a) Synthetic scheme for the CoFe/3D-NLG catalyst. (b) SEM image of 3D-NLG. (c) TEM image of CoFe/3D-NLG. The inset shows the corresponding SAED pattern. (d) HR-TEM image of the NPs and (e) TEM image of the in-plane mesopores on the graphene sheet of CoFe/3D-NLG, as indicated by the yellow circles in c. (f) Pore size distribution, (g) N2 adsorption-desorption isotherm curves, and (h) Raman spectra of CoFe/NG, CoFe/NLG, CoFe/3D-NG, and CoFe/3D-NLG.

Fig. 2. (a) N K-edge EELS profiles of CoFe/NG and CoFe/3D-NLG. (b) N 1s XPS profiles of CoFe/3D-NLG, CoFe/NG, and 3D-NLG. (c) Co 2p XPS profiles, (d) Co L-edge EELS profiles, and (e) Raman spectra of CoFe, CoFe/NG, and CoFe/3D-NLG. (f) Raman spectra of NG, 3D-NLG, and CoFe/3D-NLG.

Fig. 3. (a) OER LSV curves, (b) Tafel plots, and (c) Nyquist plots of CoFe/NG, CoFe/NLG, CoFe/3D-NG, CoFe/3D-NLG, and RuO2. The inset in (c) shows the equivalent circuit used to calculate charge transfer resistance of the catalysts, where Rs is the electrolyte resistance, Rct is the charge transfer resistance, and Cdl represents the double-layer capacitance. (d) Charging current density plots with varying scan rates for the samples. (e) Comparison of the ECSA and OER specific activity of different samples. (f) Chronoamperometric response (i-t) curves of CoFe/3D-NLG and RuO2.

Fig. 4. (a) ORR LSV curves measured in O2-saturated 0.1 M KOH solution (rotation rate: 1600 rpm). (b) Corresponding bar plots of onset potential (Eonset) and half-wave potential (E1/2). (c) Tafel plots. (d) Comparison of the ORR mass activity at 0.7 V vs. RHE. (e) i-t curve before and after the addition of 1.0 M methanol. (f) Chronoamperometric response of CoFe/3D-NLG and Pt/C at 0.7 V vs. RHE. The inset shows the ORR LSV curves before and after 10 h of continuous polarization.

Fig. 5. (a) The overall polarization curves of CoFe/3D-NLG, CoFe/NG, and Pt/C + RuO2, measured in O2-saturated 1.0 M KOH solution. The inset shows the potential difference between ORR and OER (ΔE) for the catalysts. (b) Open-circuit plots, (c) galvanodynamic charge/discharge profiles and power density curves, (d) discharge curves at a constant current density of 10 mA cm-2, and (e) charge/discharge cycling curves at a current density of 5 mA cm-2 of Zinc-air batteries assembled with CoFe/3D-NLG and Pt/C + RuO2 (duration: 1200 s per cycle).

References

[1]	M. Armand, J. M. Tarascon, Nature, 2008,451, 652-657.
[2]	L. Trotochaud, S. W. Boettcher, Scr. Mater., 2014,74, 25-32.
[3]	G. Fu, X. Yan, Y. Chen, L. Xu, D. Sun, J. M. Lee, Y. Tang, , Adv. Mater., 2018,30, 1704609/1-1704609/11.
[4]	A. Morozan, B. Jousselme, S. Palacin, Energy Environ. Sci., 2011,4, 1238-1254.
[5]	Y. Fang, Y. Guo, Chin. J. Catal., 2018,39, 566-582.
[6]	Q. Liu, L. Du, G. Fu, Z. Cui, Y. Li, D. Dang, X. Gao, Q. Zheng, J. B. Goodenough, Adv. Energy Mater., 2019,9, 1803040/1- 1803040/7.
[7]	G. Ma, R. Jia, J. Zhao, Z. Wang, C. Song, S. Jia, Z. Zhu, J. Phys. Chem. C, 2011,115, 25148-25154.
[8]	J. Jin, J. Yin, H. Liu, P. Xi, Chin. J. Catal., 2019,40, 43-51.
[9]	X. Wen, X. Yang, M. Li, L. Bai, J. Guan, Electrochim. Acta, 2019,296, 830-841.
[10]	W. Yan, X. Cao, J. Tian, C. Jin, K. Ke, R. Yang, Carbon, 2016,99, 195-202.
[11]	C. Zhang, J. Liu, Y. Ye, Z. Aslam, R. Brydson, C. Liang, ACS Appl. Mater. Interfaces, 2018,10, 2423-2429.
[12]	S. Sun, G. Shen, J. Jiang, W. Mi, X. Liu, L. Pan, X. Zhang, J. J. Zou, Adv. Energy Mater., 2019,9, 1901505/1-1901505/8.
[13]	Z. S. Wu, S. Yang, Y. Sun, K. Parvez, X. Feng, K. Mullen, J. Am. Chem. Soc. 2012,134, 9082-9085.
[14]	X. R. Wang, J. Y. Liu, Z. W. Liu, W. C. Wang, J. Luo, X. P. Han, X. W. Du, S. Z. Qiao, J. Yang, Adv. Mater., 2018,30, 1800005.
[15]	H. Miao, S. Li, Z. Wang, S. Sun, M. Kuang, Z. Liu, J. Yuan, Int. J. Hydrog. Energy, 2017,42, 28298-28308.
[16]	Y. Li, J. Yang, J. Huang, Y. Zhou, K. Xu, N. Zhao, X. Cheng, Carbon, 2017,122, 237-246.
[17]	D. A. Dikin, S. Stankovich, E. J. Zimney, R. D. Piner, G. H. B. Dommett, G. Evmenenko, S. T. Nguyen, R. S. Ruoff, Nature, 2007,448, 457-460.
[18]	J. He, M. Wang, W. Wang, R. Miao, W. Zhong, S.-Y. Chen, S. Poges, T. Jafari, W. Song, J. Liu, S. L. Suib, ACS Appl. Mater. Interfaces, 2017,9, 42676-42687.
[19]	F. Shi, X. Zhu, W. Yang, Chin. J. Catal., 2020,41, 390-403.
[20]	Y. Li, T. Gao, Y. Yao, Z. Liu, Y. Kuang, C. Chen, J. Song, S. Xu, E. M. Hitz, B. Liu, R. J. Jacob, M. R. Zachariah, G. Wang, L. Hu, Adv. Energy Mater., 2018, 8, 1801289/1-1801289/8.
[21]	L. Xiao, Q. Yang, M. J. Wang, Z. X. Mao, J. Li, Z. Wei, J. Mater. Sci., 2018,53, 15246-15256.
[22]	X. Li, Y. Zhao, Y. Yang, S. Gao, Nano Energy, 2019,62, 628-637.
[23]	Z. Li, Q. Gao, X. Liang, H. Zhang, H. Xiao, P. Xu, Z. Liu, Carbon, 2019,150, 93-100.
[24]	S. Chen, S. Z. Qiao, ACS Nano, 2013,7, 10190-10196.
[25]	Z. Zuo, T. Y. Kim, I. Kholmanov, H. Li, H. Chou, Y. Li, Small, 2015,11, 4922-4930.
[26]	Y. Chai, Z. Li, J. Wang, Z. Mo, S. Yang, J. Alloys Compd., 2019,775, 1206-1212.
[27]	M. Mi, X. Liu, W. Kong, Y. Ge, W. Dang, J. Hu, Desalination, 2019,464, 18-24.
[28]	W. S. Hummers, R. E. Offeman, J. Am. Chem. Soc., 1958,80, 1339-1339.
[29]	W. Lv, C. Zhang, Z. Li, Q. H. Yang, J. Phys. Chem Lett., 2015,6, 658-668.
[30]	J. Du, Y. Pan, T. Zhang, X. Han, F. Cheng, J. Chen, J. Mater. Chem. A, 2012,22, 15812-15818.
[31]	Y. Liang, H. Wang, J. Zhou, Y. Li, J. Wang, T. Regier, H. Dai, J. Am. Chem. Soc., 2012,134, 3517-3523.
[32]	G. Wang, L.-T. Jia, B. Hou, D.-B. Li, J.-G. Wang, Y.-H. Sun, New Carbon Mater., 2015,30, 30-40.
[33]	M. Li, Y. Xiong, X. Liu, X. Bo, Y. Zhang, C. Han, L. Guo, Nanoscale, 2015,7, 8920-8930.
[34]	D. Kong, W. Yuan, C. Li, J. Song, A. Xie, Y. Shen, Appl. Surf. Sci., 2017,393, 144-150.
[35]	G. Lin, R. Ma, Y. Zhou, Q. Liu, X. Dong, J. Wang, Electrochim. Acta, 2018,261, 49-57.
[36]	Z. Huang, Z. Liao, W. Yang, H. Zhou, C. Fu, Y. Gong, L. Chen, Y. Kuang, Electrochim. Acta, 2017,245, 957-966.
[37]	X. Cui, S. Yang, X. Yan, J. Leng, S. Shuang, P. M. Ajayan, Z. Zhang, Adv. Funct. Mater. 2016,26, 5708-5717.
[38]	M. Zeng, Y. Liu, F. Zhao, K. Nie, N. Han, X. Wang, W. Huang, X. Song, J. Zhong, Y. Li, Adv. Funct. Mater., 2016,26, 4397-4404.
[39]	X. Fu, Y. Liu, X. Cao, J. Jin, Q. Liu, J. Zhang, Appl. Catal. B, 2013, 130-131, 143-151.
[40]	W. I. Choi, S.-H. Jhi, K. Kim, Y.-H. Kim, Phys. Rev. B, 2010,81, 085441/1-085441/5.
[41]	J. M. Ziegelbauer, T. S. Olson, S. Pylypenko, F. Alamgir, C. Jaye, P. Atanassov, S. Mukerjee, J. Phys. Chem. C, 2008,112, 8839-8849.
[42]	Y. Li, Y. Li, Y. Yin, D. Xia, H. Ding, C. Ding, J. Wu, Y. Yan, Y. Liu, N. Chen, P. K. Wong, A. Lu, Appl. Catal. B, 2018,226, 324-336.
[43]	Y. Kumar, A. Sharma, P. M. Shirage, J. Alloys Compd., 2019,778, 398-409.
[44]	L. Wei, H. E. Karahan, S. Zhai, H. Liu, X. Chen, Z. Zhou, Y. Lei, Z. Liu, Y. Chen, Adv. Mater., 2017,29, 1701410/1-1701410/11.
[45]	X. T. Wang, T. Ouyang, L. Wang, J. H. Zhong, T. Ma, Z. Q. Liu, Angew. Chem. Int. Ed., 2019,58, 13291-13296.
[46]	X. Liu, M. Park, M. G. Kim, S. Gupta, G. Wu, J. Cho, Angew. Chem. Int. Ed., 2015,54, 9654-9658.
[47]	Y. Meng, W. Song, H. Huang, Z. Ren, S. Y. Chen, S. L. Suib, J. Am. Chem. Soc., 2014,136, 11452-11464.
[48]	J. Zhang, L. Dai, ACS Catal., 2015,5, 7244-7253.
[49]	X. Tong, S. Chen, C. Guo, X. Xia, X. Y. Guo, ACS Appl. Mater. Interfaces, 2016,8, 28274-28282.
[50]	Y. Liang, H. Wang, J. Zhou, Y. Li, J. Wang, T. Regier, H. Dai, J. Am. Chem. Soc., 2012,134, 3517-3523.
[51]	Y. Shao, M. F. El-Kady, C. W. Lin, G. Zhu, K. L. Marsh, J. Y. Hwang, Q. Zhang, Y. Li, H. Wang, R. B. Kaner, Adv. Mater., 2016,28, 6719-6726.
[52]	M. Wu, G. Zhang, J. Qiao, N. Chen, W. Chen, S. Sun, Nano Energy, 2019,61, 86-95.