Mesoporous bowl-like carbon support for boosting oxygen transport of fuel cell cathode

doi:10.1016/S1872-2067(24)60285-8

Abstract

Abstract:

The development of advanced support is conducive to promoting the practical application of fuel cells but remains an enormous challenge in terms of stabilizing catalyst particles and enabling improved accessibility to O₂. Beyond solid carbon black and conventional porous carbon, we demonstrate a new type of mesoporous bowl-like carbon support with a high specific surface area of over 1200 m² g^-1 and ~ 4 nm pore. Both rotating disk electrode and membrane electrode assembly (MEA) tests show that BC-supported Pt₃Co (Pt₃Co/BC) catalyst greatly outperforms hollow porous carbon spheres and solid carbon spheres supported Pt₃Co catalysts. The Pt₃Co/BC catalysts exhibited remarkable performance as cathode catalyst in MEA, achieving a comparable open-circuit voltage of approximately 0.95 V under H₂-air condition and a current density of 1.3 A cm^-2 at 0.6 V with a loading of only 0.2 mg_Pt cm^-2. Diffusion simulations and physical characterizations demonstrate that the high porosity and highly accessible pore structure of BC support facilitate the uniform distribution of catalyst particles and enhance the mass transport of O₂, thereby resulting in a significant improvement in catalytic activity and durability. This work provides new insights into the influence of support shape on mass transport of reactants and electrochemical performances of the catalyst in MEA.

Key words: Fuel cell, Oxygen reduction reaction, Mass transport, Support, Bowl-like carbon

Mingjia Lu, Jinhui Liang, Binwen Zeng, Wei Li, Yunqi Li, Qinqxin Wang, Yuhuai Li, Hong Chen, Jianzheng Li, Yangyang Chen, Lecheng Liang, Li Du, Yan Xiang, Shijun Liao, Zhiming Cui. Mesoporous bowl-like carbon support for boosting oxygen transport of fuel cell cathode[J]. Chinese Journal of Catalysis, 2025, 72: 254-265.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60285-8

https://www.cjcatal.com/EN/Y2025/V72/I5/254

Figures/Tables 6

Scheme 1. Schematic illustrating the synthesis of BC, HPCS and CS support.

Fig. 1. SEM image (a-c), nitrogen adsorption-desorption isotherms (d), and conductivity diagram (e) of BC, HPCS, and CS. (f) XRD patterns of Pt3Co/BC, Pt3Co/HPCS, Pt3Co/CS, and Pt/C.

Fig. 2. (a,b) TEM image of Pt3Co/BC. (c,d) TEM image of Pt3Co/HPCS. (e,f) TEM images of Pt3Co/CS, and particle size distribution map in the inset. (g) Atomic resolution HAADF-STEM image of Pt3Co NP. (h) Crop of the superlattice feature in (g). (i) Line scans of a single Pt3Co nanoparticle. Blue-colored atom is Pt, yellow colored is Co.

Fig. 3. (a) CVs of different electrocatalysts in 0.1 mol L?1 HClO4 solution. (b) ORR polarization curves in O2-saturated 0.1 mol L?1 HClO4. Rotation rate:1600 r min?1; sweep rate:10 mV s?1. (c) Histogram of mass and specific activities of different electrocatalysts. (d?f) ORR polarization curves before and after ADT for Pt3Co/BC, Pt3Co/HPCS, and Pt3Co/CS, the inset shows enlarged views of the area near 0.8?0.94 V. TEM images and the histograms of particle size distribution maps for Pt3Co/BC (g), Pt3Co/HPCS (h), and Pt3Co (i) after ADT.

Fig. 4. Electrochemical performance test on MEA. (a) H2-air fuel polarization plots and power density plots. (b) Nyquist plots of Pt3Co/BC measured at 800 mA cm-2 under 100%RH. (c) Catalytic layer porosity of Pt3Co/BC, Pt3Co/HPCS, Pt3Co/CS and Pt/C. The SEM of MEA with the Pt3Co/BC (d), Pt3Co/HPCS (e), and Pt3Co/CS (f) catalyst as cathodes.

Fig. 5. (a) COMSOL Multiphysics Modeling of O2 diffusion into cathode catalytic layer consisting of three catalysts, respectively. Enlarged O2 diffusion images of Pt3Co/BC (b), Pt3Co/HPCS (c), and Pt3Co/CS (d). (e) Distribution of O2 diffusion concentration for Pt3Co/BC, Pt3Co/HPCS, and Pt3Co/CS at identical point.

References

[1]	K. Jiao, J. Xuan, Q. Du, Z. Bao, B. Xie, B. Wang, Y. Zhao, L. Fan, H. Wang, Z. Hou, S. Huo, N. P. Brandon, Y. Yin, M. D. Guiver, Nature, 2021, 595, 361-369.
[2]	I. Staffell, D. Scamman, A. Velazquez Abad, P. Balcombe, P. E. Dodds, P. Ekins, N. Shah, K. R. Ward, Energy Environ. Sci., 2019, 12, 463-491.
[3]	M. K. Debe, Nature, 2012, 486, 43-51.
[4]	K. Kodama, T. Nagai, A. Kuwaki, R. Jinnouchi, Y. Morimoto, Nat. Nanotechnol., 2021, 16, 140-147.
[5]	Y. Zeng, J. Liang, C. Li, Z. Qiao, B. Li, S. Hwang, N. N. Kariuki, C.-W. Chang, M. Wang, M. Lyons, S. Lee, Z. Feng, G. Wang, J. Xie, D. A. Cullen, D. J. Myers, G. Wu, J. Am. Chem. Soc., 2023, 145, 17643-17655.
[6]	M. Tang, S. Zhang, S. Chen, Chem. Soc. Rev., 2022, 51, 1529-1546.
[7]	Y. C. Park, H. Tokiwa, K. Kakinuma, M. Watanabe, M. Uchida, J. Power Sources, 2016, 315, 179-191.
[8]	P. Wang, Q. Shao, X. Huang, Joule, 2018, 2, 2514-2516.
[9]	M. Sabharwal, M. Secanell, Electrochim. Acta, 2022, 419, 140410.
[10]	S. Ott, A. Orfanidi, H. Schmies, B. Anke, H. N. Nong, J. Hubner, U. Gernert, M. Gliech, M. Lerch, P. Strasser, Nat. Mater., 2020, 19, 77-85.
[11]	J. Fan, M. Chen, Z. Zhao, Z. Zhang, S. Ye, S. Xu, H. Wang, H. Li, Nat. Energy, 2021, 6, 475-486.
[12]	C. Jackson, X. Lin, P. B. J. Levecque, A. R. J. Kucernak, ACS Catal., 2021, 12, 200-211.
[13]	C. Y. Ahn, J. E. Park, S. Kim, O. H. Kim, W. Hwang, M. Her, S. Y. Kang, S. Park, O. J. Kwon, H. S. Park, Y. H. Cho, Y. E. Sung, Chem. Rev., 2021, 121, 15075-15140.
[14]	T. Lazaridis, B. M,. Stühmeier , H. A. Gasteiger, H. A. EI-Sayed, Nat. Catal., 2022, 5, 363-373.
[15]	Z. Qiao, S. Hwang, X. Li, C. Wang, W. Samarakoon, S. Karakalos, D. Li, M. Chen, Y. He, M. Wang, Z. Liu, G. Wang, H. Zhou, Z. Feng, D. Su, J. S. Spendelow, G. Wu, Energy Environ. Sci., 2019, 12, 2830-2841.
[16]	Z. Li, J. Zou, X. Xi, P. Fan, Y. Zhang, Y. Peng, D. Banham, D. Yang, A. Dong, Adv. Matter., 2022, 34, 2202743.
[17]	W. Zhao, Y. Ye, W. Jiang, J. Li, H. Tang, J. Hu, L. Du, Z. Cui, S. Liao, J. Mater. Chem. A, 2020, 8, 15822-15828.
[18]	P. Xu, J. Zhang, G. Jiang, F. Hassan, J.-Y. Choi, X. Fu, P. Zamani, L. Yang, D. Banham, S. Ye, Z. Chen, Nano Energy, 2018, 51, 745-753.
[19]	Y. L. Wu, X. Li, Y. S. Wei, Z. Fu, W. Wei, X. T. Wu, Q. L. Zhu, Q. Xu, Adv. Mater., 2021, 33, 2006965.
[20]	G. S. Harzer, A. Orfanidi, H. El-Sayed, P. Madkikar, H. A. Gasteiger, J. Electrochem. Soc., 2018, 165, F770-F779.
[21]	Q. Zhang, S. Dong, P. Shao, Y. Zhu, Z. Mu, D. Sheng, T. Zhang, X. Jiang, R. Shao, Z. Ren, J. Xie, X. Feng, B. Wang, Science, 2022, 378, 181-186.
[22]	V. Yarlagadda, M. K. Carpenter, T. E. Moylan, R. S. Kukreja, R. Koestner, W. Gu, L. Thompson, A. Kongkanand, ACS Energy Lett., 2018, 3, 618-621.
[23]	Z. Zhao, L. Duan, Y. Zhao, L. Wang, J. Zhang, F. Bu, Z. Sun, T. Zhang, M. Liu, H. Chen, Y. Yang, K. Lan, Z. Lv, L. Zu, P. Zhang, R. Che, Y. Tang, D. Chao, W. Li, D. Zhao, J. Am. Chem. Soc., 2022, 144, 11767-11777.
[24]	C. Li, Q. Li, Y. V. Kaneti, D. Hou, Y. Yamauchi, Y. Mai, Chem. Soc. Rev., 2020, 49, 4681-4736.
[25]	S. H. Lee, J. Kim, D. Y. Chung, J. M. Yoo, H. S. Lee, M. J. Kim, B. S. Mun, S. G. Kwon, Y. E. Sung, T. Hyeon, J. Am. Chem. Soc., 2019, 141, 2035-2045.
[26]	A. Orfanidi, P. Madkikar, H. A. El-Sayed, G. S. Harzer, T. Kratky, H. A. Gasteiger, J. Electrochem. Soc., 2017, 164, F418-F426.
[27]	Y. He, S. Liu, C. Priest, Q. Shi, G. Wu, Chem. Soc. Rev., 2020, 49, 3484-3524.
[28]	J. Hou, M. Yang, C. Ke, G. Wei, C. Priest, Z. Qiao, G. Wu, J. Zhang, Energy Chem, 2020, 2, 100023.
[29]	F. Chen, S. Chen, A. Wang, M. Wang, L. Guo, Z. Wei, Nat. Catal., 2023, 6, 392-401.
[30]	M. N. Islam, A. B. M. Basha, V. O. Kollath, A. P. Soleymani, J. Jankovic, K. Karan, Nat. Commun., 2022, 13, 6157.
[31]	V. Yarlagadda, N. Ramaswamy, R. S. Kukreja, S. Kumaraguru, J. Power Sources, 2022, 532, 231349.
[32]	W. Zhang, X. Feng, Z. X. Mao, J. Li, Z. Wei, Adv. Funct. Mater., 2022, 32, 2204110.
[33]	L. Zeng,. X. Lu, C. Yuan, W. Yuan, K. Chen, J. Guo, X. Zhang, J. Wang, Q. Liao, Z. Wei, Adv. Mater., 2024, 36, 2305711.
[34]	E. P. Ambrosio, C. Francia, C. Gerbaldi, N. Penazzi, P. Spinelli, M. Manzoli, G. Ghiotti, J. Am. Chem. Soc., 2023, 145, 27262-27272.
[35]	P. Cui. L. Zhao, Y. Long, L. Dai, C. Hu, Angew. Chem. Int. Ed., 2023, 62, e202218269.
[36]	F. Pei, T. An, J. Zang, X. Zhao, X. Fang, M. Zheng, Q. Dong, N. Zheng, Adv. Energy Mater., 2016, 6, 1502539.
[37]	G. Kresse, J. Hafner, Phys. Rev. B, 1993, 47, 558-561.
[38]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[39]	J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, C. Fiolhais, Phys. Rev. B, 1992, 46, 6671-6687.
[40]	J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jónsson, J. Phys. Chem. B, 2004, 108, 17886-17892.
[41]	G. A. Vliegenthart, G. Gompper, New J. Phys., 2011, 13, 045020
[42]	M. B. Sassin, Y. Garsany, R. W. Atkinson, R. M. E. Hjelm, K. E. Swider-Lyons, Int. J. Hydrogen Energy, 2019, 44, 16944-16955.
[43]	W. Qiu, H. Xiao, Y. Li, X. Lu, Y. Tong, Small, 2019, 15, 1901285.
[44]	K. Kim, G. Kim, T. Jeong, W. Lee, Y. Yang, B. H. Kim, B. Kim, B. Lee, J. Kang, M. Kim, J. Am. Chem. Soc., 2024, 146, 34033-34042.
[45]	J. Li, M. Chen, D. A. Cullen, S. Hwang, M. Wang, B. Li, K. Liu, S. Karakalos, M. Lucero, H. Zhang, C. Lei, H. Xu, G. E. Sterbinsky, Z. Feng, D. Su, K. L. More, G. Wang, Z. Wang, G. Wu, Nat. Catal., 2018, 1, 935-945.
[46]	Q. Gong, H. Zhang, H. Yu, S. Jeon, Y. Ren, Z. Yang, C.-J. Sun, E. A. Stach, A. C. Foucher, Y. Yu, M. Smart, G. M. Filippelli, D. A. Cullen, P. Liu, J. Xie, Matter, 2023, 6, 963-982.
[47]	C.-L. Yang, L.-N. Wang, P. Yin, J. Liu, M.-X. Chen, Q.-Q. Yan, Z.-S. Wang, S.-L. Xu, S.-Q. Chu, C. Cui, H. Ju, J. Zhu, Y. Lin, J. Shui, H.-W. Liang, Science, 2021, 374, 459-464.
[48]	J. Zhang, L. Zhang, J. Liu, C. Zhong, Y. Tu, P. Li, L. Du, S. Chen, Z. Cui, Nat. Commun., 2022, 13, 5497.
[49]	W. Zhao, B. Chi, L. Liang, P. Yang, W. Zhang, X. Ge, L. Wang, Z. Cui, S. Liao, ACS Catal., 2022, 12, 7571-7578.
[50]	C. Galeano, J. C. Meier, V. Peinecke, H. Bongard, I. Katsounaros, A. A. Topalov, A. Lu, K. J. Mayrhofer, F. Schuth, J. Am. Chem. Soc., 2012, 134, 20457-20465.
[51]	Z. Wang, X. Yao, Y. Kang, L. Miao, D. Xia, L. Gan, Adv. Funct. Mater., 2019, 29, 1902987.
[52]	X. Zhao, H. Cheng, X. Chen, Q. Zhang, C. Li, J. Xie, N. Marinkovic, L. Ma, J.-C. Zheng, K. Sasaki, J. Am. Chem. Soc., 2024, 146, 3010-3022.
[53]	L. Castanheira, L. Dubau, M. Mermoux, G,. Berthomé N,. Caqué, E. Rossinot, M. Chatenet, F. Maillard, ACS Catal., 2014, 4, 2258-2267.
[54]	T. A. M. Suter, K. Smith, J. Hack, L. Rasha, Z. Rana, G. M. A. Angel, P. R. Shearing, T. S. Miller, D. J. L. Brett, Adv. Energy Mater., 2021, 11, 2101025.
[55]	X. Fu, G. Jiang, G. Wen, R. Gao, S. Li, M. Li, J. Zhu, Y. Zheng, Z. Li, Y. Hu, L. Yang, Z. Bai, A. Yu, Z. Chen, Appl. Catal. B, 2021, 293, 120176.
[56]	X. Lu, H. Xu, P. Yang, L. X., Y. Li, J. Ma, R. Li, L. Liu, A. Liu, V. Kondratiev, O. Levin, J. Zhang, M. An, Appl. Catal. B, 2022, 313, 121454.