Integration of atomic Co-N5 sites with defective N-doped carbon for efficient zinc-air batteries

doi:10.1016/S1872-2067(23)64471-7

Abstract

Abstract:

Transition metal single-atom catalysts have attracted considerable attention for their applicability in electrocatalytic oxygen reduction reactions (ORR), but it is still very challenging to regulate the interaction between the active sites and oxygen-containing intermediates. In this study, atomically dispersed Co-N₅ sites integrated with defective N-doped carbon (Co-N₅/DHC) were developed using a facile templating approach, followed by NH₃ treatment. NH₃ can simultaneously etch inactive amorphous substrates on the surfaces of metal sites and construct intrinsic carbon defects, thereby increasing the number of both metal and metal-free active sites. By bridging the intrinsic carbon defects and metal sites, the optimized Co-N₅/DHC catalyst exhibited significantly improved electrocatalytic ORR performance compared to the pristine Co-N_x/HC sample (cobalt-nitrogen sites anchored on heteroatom-doped carbon). Density functional calculations revealed that the strong interaction between the Co-N₅ sites and carbon defects modified the electronic localization, thus optimizing the binding energy with oxygen-containing intermediates and resulting in significantly improved ORR catalytic activity with a half-wave potential of 0.877 V. In addition, a zinc-air battery assembled with the Co-N₅/DHC as the cathode achieves a maximum power density of 160.7 mW cm^-2 and affords a specific capacity of 766.2 mA h g_Zn⁻¹.

Key words: Single-atom catalyst, Co-N₅ sites, Defective N-doped carbon, Oxygen reduction reaction, Zinc-air batteries

Lei Zhao, Zhen Zhang, Zhaozhao Zhu, Pingbo Li, Jinxia Jiang, Tingting Yang, Pei Xiong, Xuguang An, Xiaobin Niu, Xueqiang Qi, Jun Song Chen, Rui Wu. Integration of atomic Co-N₅ sites with defective N-doped carbon for efficient zinc-air batteries[J]. Chinese Journal of Catalysis, 2023, 51: 216-224.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64471-7

https://www.cjcatal.com/EN/Y2023/V51/I8/216

Figures/Tables 5

Fig. 1. (a) Schematic of the synthesis procedure of Co-N5/DHC. SEM (b,c), TEM (d), AC-STEM (e), HAADF-STEM (f) images, and corresponding EDS elemental mappings (g) of Co-N5/DHC.

Fig. 2. (a) XRD patterns of Co-N5/DHC, Co-Nx/HC, and DHC. (b) EPR spectra of Co-N5/DHC and Co-Nx/HC. (c) N 1s high-resolution spectra of Co-N5/DHC. Co K-edge XANES spectra (d) and Co K-edge FT-EXAFS spectra (e) of Co-N5/DHC and references. (f) Co K-edge EXAFS fitting result of Co-N5/DHC. (g) Co K-edge WT-EXAFS contour plots of Co-N5/DHC, CoPc, Co foil, and CoO.

Fig. 3. (a) CV curves and (b) LSV curves for DHC, Co-Nx/HC, Co-N5/DHC, and commercial Pt/C catalysts. (c) LSV curves at different rotating rates and (d) corresponding K-L plots at different potentials for Co-N5/DHC. (e) Methanol tolerance tests. (f) LSV curves before and after 10000 potential cycles for Co-N5/DHC.

Fig. 4. DFT calculations of ORR on CoN4, CoN5, and Co-N5/DHC. Free energy diagrams at U = 0 V (a) and U = 1.23 V (b). (c) Differential charge densities. The yellow and blue regions represent charge accumulation and depletion, respectively. (d) Co 3d PDOS.

Fig. 5. (a) Schematic of ZAB configuration. Open-circuit plots (b), discharge polarization and power density curves (c), discharge profiles (d) at different current densities, specific capacities (e) at 10 mA cm-2 for ZABs using Co-N5/DHC and Pt/C catalysts as the cathode. (f) Photograph of a LED panel powered by the Co-N5/DHC catalyst-based ZAB.

References

[1]	T. Zhou, N. Zhang, C. Wu, Y. Xie, Energy Environ. Sci., 2020, 13, 1132-1153.
[2]	Z. Zhang, X. Zhao, S. Xi, L. Zhang, Z. Chen, Z. Zeng, M. Huang, H. Yang, B. Liu, S. J. Pennycook, P. Chen, Adv. Energy Mater., 2020, 10, 2100497.
[3]	X. Shu, M. Yang, M. Liu, W. Pan, J. Zhang, J. Energy Chem., 2022, 68, 213-221.
[4]	X. Xu, S. Wang, S. Guo, K. San Hui, J. Ma, D. A. Dinh, K. N. Hui, H. Wang, L. Zhang, G. Zhou, Adv. Powder Mater., 2022, 1, 100027.
[5]	Q. Liu, R. Liu, C. He, C. Xia, W. Guo, Z.-L. Xu, B. Y. Xia, eScience, 2022, 2, 453-466.
[6]	W. Zhang, J. Chang, Y. Yang, SusMat, 2023, 3, 2-20.
[7]	Y. Niu, S. Gong, X. Liu, C. Xu, M. Xu, S.-G. Sun, Z. Chen, eScience, 2022, 2, 546-556.
[8]	Y. Guo, Y.-N. Chen, H. Cui, Z. Zhou, Chin. J. Catal., 2019, 40, 1298-1310.
[9]	J. Wang, C.-X. Zhao, J.-N. Liu, D. Ren, B.-Q. Li, J.-Q. Huang, Q. Zhang, Nano Mater. Sci., 2021, 3, 313-318.
[10]	L. Zhao, R. Wu, J. Wang, Z. Li, X. Wei, J. S. Chen, Y. Chen, J. Energy Chem., 2021, 60, 61-74.
[11]	H. Niu, C. Xia, L. Huang, S. Zaman, T. Maiyalagan, W. Guo, B. You, B. Y. Xia, Chin. J. Catal., 2022, 43, 1459-1472.
[12]	Z. Yu, C. Liu, J. Chen, Z. Yuan, Y. Chen, L. Wei, Nano Mater. Sci., 2021, 3, 420-428.
[13]	M. Zhang, H. Li, J. Chen, F. X. Ma, L. Zhen, Z. Wen, C. Y. Xu, Adv. Funct. Mater., 2022, 33, 2209726.
[14]	P. Rao, D. Wu, T.-J. Wang, J. Li, P. Deng, Q. Chen, Y. Shen, Y. Chen, X. Tian, eScience, 2022, 2, 399-404.
[15]	Z. Li, L. Leng, S. Ji, M. Zhang, H. Liu, J. Gao, J. Zhang, J. H. Horton, Q. Xu, J. Zhu, J. Energy Chem., 2022, 73, 469-477.
[16]	Y. Chen, R. Gao, S. Ji, H. Li, K. Tang, P. Jiang, H. Hu, Z. Zhang, H. Hao, Q. Qu, X. Liang, W. Chen, J. Dong, D. Wang, Y. Li, Angew. Chem. Int. Ed., 2021, 60, 3212-3221.
[17]	M. Zhang, K. Zhang, X. Ai, X. Liang, Q. Zhang, H. Chen, X. Zou, Chin. J. Catal., 2022, 43, 2987-3018.
[18]	C. Tang, L. Chen, H. Li, L. Li, Y. Jiao, Y. Zheng, H. Xu, K. Davey, S. Z. Qiao, J. Am. Chem. Soc., 2021, 143, 7819-7827.
[19]	K. M. Zhao, S. Liu, Y. Y. Li, X. Wei, G. Ye, W. Zhu, Y. Su, J. Wang, H. Liu, Z. He, Z. Y. Zhou, S. G. Sun, Adv. Energy Mater., 2022, 12, 2103588.
[20]	J. Wang, H. Li, S. Liu, Y. Hu, J. Zhang, M. Xia, Y. Hou, J. Tse, J. Zhang, Y. Zhao, Angew. Chem. Int. Ed., 2021, 60, 181-185.
[21]	J. Zou, C. Chen, Y. Chen, Y. Zhu, Q. Cheng, L. Zou, Z. Zou, H. Yang, ACS Catal., 2022, 12, 4517-4525.
[22]	X. Hai, S. Xi, S. Mitchell, K. Harrath, H. Xu, D. F. Akl, D. Kong, J. Li, Z. Li, T. Sun, H. Yang, Y. Cui, C. Su, X. Zhao, J. Li, J. Perez-Ramirez, J. Lu, Nat. Nanotechnol., 2022, 17, 174-181.
[23]	H. Lv, W. Guo, M. Chen, H. Zhou, Y. Wu, Chin. J. Catal., 2022, 43, 71-91.
[24]	W. Xia, J. Tang, J. Li, S. Zhang, K. C. Wu, J. He, Y. Yamauchi, Angew. Chem. Int. Ed., 2019, 58, 13354-13359.
[25]	C. Hu, R. Paul, Q. Dai, L. Dai, Chem. Soc. Rev., 2021, 50, 11785-11843.
[26]	H.-J. Zhang, J. Geng, C. Cai, Z.-F. Ma, Z. Ma, W. Yao, J. Yang, Chin. Chem. Lett., 2021, 32, 745-749.
[27]	L. Yang, J. Shui, L. Du, Y. Shao, J. Liu, L. Dai, Z. Hu, Adv. Mater., 2019, 31, e1804799.
[28]	Y. Long, F. Ye, L. Shi, X. Lin, R. Paul, D. Liu, C. Hu, Carbon, 2021, 179, 365-376.
[29]	X. Yan, Y. Jia, X. Yao, Chem. Soc. Rev., 2018, 47, 7628-7658.
[30]	J. Zhang, J. Zhang, F. He, Y. Chen, J. Zhu, D. Wang, S. Mu, H. Y. Yang, Nano-Micro Lett., 2021, 13, 65.
[31]	C. Xie, D. Yan, W. Chen, Y. Zou, R. Chen, S. Zang, Y. Wang, X. Yao, S. Wang, Mater. Today, 2019, 31, 47-68.
[32]	W. Li, D. Wang, Y. Zhang, L. Tao, T. Wang, Y. Zou, Y. Wang, R. Chen, S. Wang, Adv. Mater., 2020, 32, 1907879.
[33]	X. Fu, N. Li, B. Ren, G. Jiang, Y. Liu, F. M. Hassan, D. Su, J. Zhu, L. Yang, Z. Bai, Z. P. Cano, A. Yu, Z. Chen, Adv. Energy Mater., 2019, 9, 1803737.
[34]	Z. Li, J. Jiang, X. Liu, Z. Zhu, J. Wang, Q. He, Q. Kong, X. Niu, J. S. Chen, J. Wang, R. Wu, Small, 2022, 18, 2203495.
[35]	W. Stöber, A. Fink, E. Bohn, J. Colloid Interface Sci., 1968, 26, 62-69.
[36]	G. Kresse, J. Furthmüller, Comput. Mater. Sci., 1996, 6, 15-50.
[37]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[38]	D. Yan, C. Xia, C. He, Q. Liu, G. Chen, W. Guo, B. Y. Xia, Small, 2022, 18, 2106606.
[39]	Y. Dong, Q. Zhang, Z. Tian, B. Li, W. Yan, S. Wang, K. Jiang, J. Su, C. W. Oloman, E. L. Gyenge, R. Ge, Z. Lu, X. Ji, L. Chen, Adv. Mater., 2020, 32, 2001300.
[40]	Y. Xue, Y. Guo, Q. Zhang, Z. Xie, J. Wei, Z. Zhou, Nano-Micro Lett., 2022, 14, 162.
[41]	W. Ni, Z. Liu, Y. Zhang, C. Ma, H. Deng, S. Zhang, S. Wang, Adv. Mater., 2021, 33, 2003238.
[42]	Y. Zhang, G. Li, J. Wang, D. Luo, Z. Sun, Y. Zhao, A. Yu, X. Wang, Z. Chen, Adv. Energy Mater., 2021, 11, 2100497.
[43]	C. Lv, Y. Qian, C. Yan, Y. Ding, Y. Liu, G. Chen, G. Yu, Angew. Chem. Int. Ed., 2018, 57, 10246-10250.
[44]	P. Zamani, D. C. Higgins, F. M. Hassan, X. Fu, J.-Y. Choi, M. A. Hoque, G. Jiang, Z. Chen, Nano Energy, 2016, 26, 267-275.
[45]	L. Yang, X. Zhang, L. Yu, J. Hou, Z. Zhou, R. Lv, Adv. Mater., 2022, 34, 2105410.
[46]	C. Fu, X. Qi, L. Zhao, T. Yang, Q. Xue, Z. Zhu, P. Xiong, J. Jiang, X. An, H. Chen, J. S. Chen, A. Cabot, R. Wu, Appl. Catal. B, 2023, 335, 122875.
[47]	M. Liu, J. Lee, T. C. Yang, F. Zheng, J. Zhao, C. M. Yang, L. Y. S. Lee, Small Methods, 2021, 5, 2001165.
[48]	Y. Ha, B. Fei, X. Yan, H. Xu, Z. Chen, L. Shi, M. Fu, W. Xu, R. Wu, Adv. Energy Mater., 2020, 10, 2002592.
[49]	K. Wang, Z. Lu, J. Lei, Z. Liu, Y. Li, Y. Cao, ACS Nano, 2022, 16, 11944-11956.
[50]	Z. Wang, X. Jin, C. Zhu, Y. Liu, H. Tan, R. Ku, Y. Zhang, L. Zhou, Z. Liu, S. J. Hwang, H. J. Fan, Adv. Mater., 2021, 33, 2104718.
[51]	T. Tang, Y. Wang, J. Han, Q. Zhang, X. Bai, X. Niu, Z. Wang, J. Guan, Chin. J. Catal., 2023, 46, 48-55.
[52]	Y. Tian, M. Li, Z. Wu, Q. Sun, D. Yuan, B. Johannessen, L. Xu, Y. Wang, Y. Dou, H. Zhao, S. Zhang, Angew. Chem. Int. Ed., 2022, 61, e202213296.
[53]	Y. Guo, S. Yao, Y. Xue, X. Hu, H. Cui, Z. Zhou, Appl. Catal. B, 2022, 304, 120997.

Integration of atomic Co-N₅ sites with defective N-doped carbon for efficient zinc-air batteries

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