Revolutionizing Zn-Air batteries with chainmail catalysts: Ultrathin carbon-encapsulated FeNi alloys on N-doped graphene for enhanced oxygen electrocatalysis

doi:10.1016/S1872-2067(23)64603-0

Abstract

Abstract:

The sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) pose significant challenges for the viability of rechargeable Zn-air batteries. Developing efficient, cost-effective, stable, and dual-purpose oxygen electrocatalysts remains a formidable hurdle. In this study, we successfully synthesized a highly promising chainmail catalyst named FeNi@NC, comprising ultrathin carbon shells encapsulating FeNi alloy nanoparticles on N-doped graphene-like nanosheets. The strong synergistic effects between FeNi alloys and N-doped carbon shells result in outstanding bifunctional catalytic activity, particularly in alkaline media. Consequently, Zn-air batteries incorporating FeNi@NC as the catalyst demonstrate exceptional performance, operating reliably at high power density with extended lifespan. Furthermore, computational analyses provided further confirmation of the catalytic activity and revealed that the electron transfer from FeNi alloy nanoparticles to the carbon shells activates the carbon surface, leading to enhanced catalytic performance. This research not only sheds light on the rational design and synthesis of heteroatom-doped carbon materials supporting the growth-constrained transition metal alloys but also offers a practical solution for advancing the application of Zn-air batteries.

Key words: Zn-air batteries, Chainmail catalyst, Bifunctional electrocatalyst, FeNi alloy, Carbon shell

Yibo Guo, Yuanyuan Xue, Zhen Zhou. Revolutionizing Zn-Air batteries with chainmail catalysts: Ultrathin carbon-encapsulated FeNi alloys on N-doped graphene for enhanced oxygen electrocatalysis[J]. Chinese Journal of Catalysis, 2024, 58: 206-215.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64603-0

https://www.cjcatal.com/EN/Y2024/V58/I3/206

Figures/Tables 6

Fig. 1. Schematic illustration of the preparation of FeNi@NC.

Fig. 2. SEM (a), TEM (b), HRTEM (c), elemental mapping (d) of Fe, Ni, C, N and O. (e) EDS of FeNi@NC.

Fig. 3. XPS survey (a), and fine spectra of C 1s (b), N 1s (c), O 1s (d), Fe 2p (e) and Ni 2p (f) of FeNi@NC. The positive shift of binding energy of Fe (g) and Ni (h) in FeNi@NC compared to the metal Fe and Ni. (i) Schematic diagram of electron transfer from FeNi alloys to carbon shell for FeNi@NC chainmail catalyst.

Fig. 4. (a) CV curves of FeNi@NC under different atmospheres. (b) LSV curves of different samples for ORR at 0.1 mol L?1 KOH. (c) Tafel slope. (d) LSV curves of FeNi@NC at different rotational speeds. (e) Electron transfer numbers according to the K-L equation. (f) Electron transfer number and hydrogen peroxide yield from the RRDE test curves (inset). (g) LSV curves of different samples for OER at 0.1 mol L?1 KOH. (h) Tafel slope. (i) LSV curves for OER at 1 mol L?1 KOH.

Fig. 5. (a) Free energy profile for the OER process at 0 V vs. RHE. (b) Free energy profile for the ORR process at 0 V vs. RHE. (c) Calculated differential charge density of FeNi@NC, where the isosurface value is set to be 0.004 e ??1. Cyan and yellow represent charge depletion and charge accumulation, respectively. (d) Calculated electrostatic potential profile averaged on the plane perpendicular to the c-axis. The fermi level is aligned at 0 eV. (e) Calculated total DOS with the fermi level aligned at 0 eV. (f) Calculated total DOS and projected DOS of FeNi@NC with the fermi level aligned at 0 eV.

Fig. 6. (a) Zn-air batteries assembled with FeNi@NC catalysts lighting up the LED screen. (b) Charge-discharge curves of batteries assembled with different catalysts. (c) Discharge curves and power density curves of batteries assembled with different catalysts. (d) Cycle tests of batteries assembled with FeNi@NC catalysts at 10 mA cm-2. (e) Long cycle tests of batteries assembled with different catalysts at 5 mA cm-2.

References

[1]	Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Norskov, T. F. Jaramillo, Science, 2017, 355, eaad4998.
[2]	Y. Xue, Y. Guo, H. Cui, Z. Zhou, Small Methods, 2021, 5, 2100736.
[3]	H. Cui, Y. Guo, Z. Zhou, Small, 2021, 17, 2005255.
[4]	H. Cui, Y. Guo, W. Ma, Z. Zhou, ChemSusChem, 2020, 13, 1155-1171.
[5]	Y. Guo, Y.-N. Chen, H. Cui, Z. Zhou, Chin. J. Catal., 2019, 40, 1298-1310.
[6]	Y. Jiang, Y. P. Deng, R. Liang, J. Fu, D. Luo, G. Liu, J. Li, Z. Zhang, Y. Hu, Z. Chen, Adv. Energy Mater., 2019, 9, 1900911.
[7]	C. Zhu, Z. Yin, W. Lai, Y. Sun, L. Liu, X. Zhang, Y. Chen, S.-L. Chou, Adv. Energy Mater., 2018, 8, 1802327.
[8]	Y. Guo, S. Yao, L. Gao, A. Chen, M. Jiao, H. Cui, Z. Zhou, J. Mater. Chem. A, 2020, 8, 4386-4395.
[9]	M. Liu, Z. Zhao, X. Duan, Y. Huang, Adv. Mater., 2019, 31, 1802234.
[10]	H. Cui, M. Jiao, Y.-N. Chen, Y. Guo, L. Yang, Z. Xie, Z. Zhou, S. Guo, Small Methods, 2018, 2, 1800144.
[11]	Y.-N. Chen, Y. Guo, H. Cui, Z. Xie, X. Zhang, J. Wei, Z. Zhou, J. Mater. Chem. A, 2018, 6, 9716-9722.
[12]	Y. Xue, Y. Guo, Q. Zhang, Z. Xie, J. Wei, Z. Zhou, Nano-Micro Lett., 2022, 14, 162.
[13]	H. L. Meng, S. Y. Lin, J. J. Feng, L. Zhang, A. J. Wang, J. Colloid Interface Sci., 2022, 610, 573-582.
[14]	W. Wan, X. Liu, H. Li, X. Peng, D. Xi, J. Luo, Appl. Catal. B, 2019, 240, 193-200.
[15]	Y. Tong, J. Liu, L. Wang, B. J. Su, K. H. Wu, J. Y. Juang, F. Hou, L. Yin, S. X. Dou, J. Liu, J. Liang, Adv. Funct. Mater., 2022, 32, 2205654.
[16]	L. Wu, R. Zhao, G. Du, H. Wang, M. Hou, W. Zhang, P. Sun, T. Chen, Green Energy Environ., 2023, 8, 1693-1702.
[17]	B. Wang, J. Tang, X. Zhang, M. Hong, H. Yang, X. Guo, S. Xue, C. Du, Z. Liu, J. Chen, Chem. Eng. J., 2022, 437, 135295.
[18]	K. Liu, J. Fu, Y. Lin, T. Luo, G. Ni, H. Li, Z. Lin, M. Liu, Nat. Commun., 2022, 13, 2075.
[19]	Z. Wang, J. Ang, J. Liu, X. Y. D. Ma, J. Kong, Y. Zhang, T. Yan, X. Lu, Appl. Catal. B, 2020, 263, 118344.
[20]	Y. Guo, S. Yao, Y. Xue, X. Hu, H. Cui, Z. Zhou, Appl. Catal. B, 2022, 304, 120997.
[21]	H. Cui, Y. Guo, L. Guo, L. Wang, Z. Zhou, Z. Peng, J. Mater. Chem. A, 2018, 6, 18782-18793.
[22]	Y. Pan, K. Sun, S. Liu, X. Cao, K. Wu, W. C. Cheong, Z. Chen, Y. Wang, Y. Li, Y. Liu, D. Wang, Q. Peng, C. Chen, Y. Li,, J. Am. Chem. Soc., 2018, 140, 2610-2618.
[23]	X. H. Li, S. Kurasch, U. Kaiser, M. Antonietti, Angew. Chem. Int. Ed., 2012, 51, 9689-9692.
[24]	T. Jiang, H. Hu, F. Lei, J. Hu, M. Wu, D. Ho, ACS Appl. Mater. Interfaces, 2020, 12, 38031-38044.
[25]	J. Zhu, M. Xiao, Y. Zhang, Z. Jin, Z. Peng, C. Liu, S. Chen, J. Ge, W. Xing, ACS Catal., 2016, 6, 6335-6342.
[26]	X. Wei, S. Song, N. Wu, X. Luo, L. Zheng, L. Jiao, H. Wang, Q. Fang, L. Hu, W. Gu, W. Song, C. Zhu, Nano Energy, 2021, 84, 105840.
[27]	M.-Q. Wang, C. Ye, M. Wang, T.-H. Li, Y.-N. Yu, S.-J. Bao, Energy Storage Mater., 2018, 11, 112-117.
[28]	Z. Wang, J. Ang, B. Zhang, Y. Zhang, X. Y. D. Ma, T. Yan, J. Liu, B. Che, Y. Huang, X. Lu, Appl. Catal. B, 2019, 254, 26-36.
[29]	X. Zhu, T. Jin, C. Tian, C. Lu, X. Liu, M. Zeng, X. Zhuang, S. Yang, L. He, H. Liu, S. Dai, Adv. Mater., 2017, 29, 1704091.
[30]	C. Yang, Y. Gao, T. Ma, M. Bai, C. He, X. Ren, X. Luo, C. Wu, S. Li, C. Cheng, Adv. Mater., 2023, 35, 2301836.
[31]	L. Tang, X. Meng, D. Deng, X. Bao, Adv. Mater., 2019, 31, 1901996.
[32]	L. Gao, X. Cui, C.D. Sewell, J. Li, Z. Lin, Chem. Soc. Rev., 2021, 50, 8428-8469.
[33]	Y. Yan, S. Liang, X. Wang, M. Zhang, S. M. Hao, X. Cui, Z. Li, Z. Lin, Proc. Natl. Acad. Sci. U. S. A., 2021, 118, e2110036118.
[34]	L. Gao, X. Cui, Z. Wang, C.D. Sewell, Z. Li, S. Liang, M. Zhang, J. Li, Y. Hu, Z. Lin, Proc. Natl. Acad. Sci. U. S. A., 2021, 118, e2023421118.
[35]	Y. Tu, J. Deng, C. Ma, L. Yu, X. Bao, D. Deng, Nano Energy, 2020, 72, 104700.
[36]	X. Chen, J. Xiao, J. Wang, D. Deng, Y. Hu, J. Zhou, L. Yu, T. Heine, X. Pan, X. Bao, Chem. Sci., 2015, 6, 3262-3267.
[37]	L. Yu, D. Deng, X. Bao, Angew. Chem. Int. Ed., 2020, 59, 15294-15297.
[38]	J. Deng, P. Ren, D. Deng, X. Bao, Angew. Chem. Int. Ed., 2015, 54, 2100-2104.
[39]	D. Chen, J. Zhu, X. Mu, R. Cheng, W. Li, S. Liu, Z. Pu, C. Lin, S. Mu, Appl. Catal. B, 2020, 268, 118729.
[40]	L. Tao, Y. Wang, Y. Zou, N. Zhang, Y. Zhang, Y. Wu, Y. Wang, R. Chen, S. Wang, Adv. Energy Mater., 2020, 10, 1901227.
[41]	J. Meng, C. Niu, L. Xu, J. Li, X. Liu, X. Wang, Y. Wu, X. Xu, W. Chen, Q. Li, Z. Zhu, D. Zhao, L. Mai, J. Am. Chem. Soc., 2017, 139, 8212-8221.
[42]	H. W. Liang, X. Zhuang, S. Bruller, X. Feng, K. Mullen, Nat. Commun., 2014, 5, 4973.