Design and Study on Pore Structure of Cathode Double Catalytic Layer in High-temperature Proton Exchange Membrane Fuel Cell★

doi:10.6023/A23040184

Abstract

High-temperature proton exchange membrane fuel cell (HT-PEMFCs) has the advantages of simple hydro-thermal management, strong resistance to CO, direct feeding of reforming gas and high efficiency of cogeneration. It is one of the ideal power sources for the development of clean energy. As the core component of HT-PEMFCs, membrane electrode assembly (MEA) is mainly composed of cathode and anode gas diffusion electrode and proton exchange membrane, which determines the performance and cost of HT-PEMFCs. Therefore, optimizing the structure of gas diffusion electrode (GDE) is an important means to improve the performance and reduce the cost of HT-PEMFC. In this work, from the point of view of catalytic layer, pore-forming agent was introduced into catalytic layer to construct double catalytic layer with different pore structure. Among them, MEA 2 uses 46.7% (w) PtCo/C in the inner catalyst layer without adding pore-forming agent, and the outer catalyst layer uses 40% (w) Pt/C and adds 20% (w) pore-forming agent. It has relatively small ohmic polarization, minimum mass transfer polarization and activation polarization, and has the largest electrochemical active area, and the electrochemical performance is the best. At 160 ℃ and atmospheric pressure, hydrogen and air as fuel, the maximum power density of the single cell composed of the membrane electrode is 439 mW•cm^-2, which is 69 mW•cm^-2 higher than that of the single cell without pore-forming agent. Whether the pore-forming agent is added into the inner catalytic layer (CL) or the outer CL, the pore structure is adjusted to optimize the phosphoric acid (PA) distribution and reduce the oxygen mass transfer resistance to improve the electrochemical performance. The former catalyst layer has a greater hydrophobicity change and the electrochemical performance is more affected by the PA content, while the latter catalyst layer hydrophobicity changes less and the electrochemical performance is more affected by the oxygen mass transfer resistance. Excessive addition of pore-forming agent inside or outside CL will produce larger ohmic polarization resistance (R_Ω), and the acid drowning caused by insufficient hydrophobicity of CL will further reduce the electrochemical performance of the battery.

Key words: high-temperature proton exchange-membrane fuel cell, double catalytic layer, pore-forming agent, electrochemical performance

Cite this article

Shikun Liu, Chengwei Deng, Feng Ji, Yulin Min, Hexing Li. Design and Study on Pore Structure of Cathode Double Catalytic Layer in High-temperature Proton Exchange Membrane Fuel Cell^★[J]. Acta Chimica Sinica, 2023, 81(9): 1135-1141.

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Fig. & Tab. 11

	内CL		外CL
	Pt载量/ (mg•cm^-2)	造孔剂质量∶总固体质量/%	Pt载量/ (mg•cm^-2)	Pt载量/ (mg•cm^-2)
MEA 0	0.250	0	0.253	0.250
MEA 1	0.252	0	0.248	0.252
MEA 2	0.251	0	0.248	0.251
MEA 3	0.250	0	0.251	0.250
MEA 4	0.249	10	0.253	0.249
MEA 5	0.252	10	0.251	0.252
MEA 6	0.250	10	0.252	0.250

Table 1. Basic information of cathodic double catalytic layer

Figure 1. SEM topography. Cross-section view catalytic layer of MEA 0 (a); plane topography of cathodic catalytic layer of MEA 0 (b, c); cross-section view catalytic layer of MEA 2 (d); plane topography of cathodic catalytic layer of MEA 2 (e, f)

Figure 2. The pore distribution of Pt/C after adding different proportion of pore-forming agent

Figure 3. Hydrophilic and hydrophobic test pattern. The contact angle test results of CL within MEA 0 (a), CL within MEA 4 (b), CL outside MEA 0 (c), CL outside MEA 1 (d), CL outside MEA 2 (e) and CL outside MEA 3 (f)

Figure 4. The polarization curve (a) and power density curve (b) of the inner catalytic layer does not contain pore-forming agents and the outer catalytic layer contains cathodic catalytic layers with different proportions of pore-forming agents. The polarization curve (c) and power density curve (d) of the inner catalytic layer contains 10% (w) pore-forming agents and the outer catalytic layer contains cathodic catalytic layers with different proportions of pore-forming agents

	电压/V					最大功率密度/ (mW•cm^-2)
	0.2 A•cm^-2	0.5 A•cm^-2		1.2 A•cm^-2		最大功率密度/ (mW•cm^-2)
MEA 0	0.618		0.507		0.306	370
MEA 1	0.615		0.518		0.352	425
MEA 2	0.632		0.531		0.366	439
MEA 3	0.605		0.500		0.301	363
MEA 4	0.619		0.514		0.316	379
MEA 5	0.606		0.523		0.359	432
MEA 6	0.620		0.521		0.342	410

Table 2. Voltage at 0.2, 0.5, 1.2 A?cm-2 current density and peak power density of each membrane electrode

Figure 5. The CV curve (a) and EIS curve (b) of the inner catalytic layer does not contain pore-forming agents and the outer catalytic layer contains cathodic catalytic layers with different proportions of pore-forming agents. The CV curve (c) and EIS curve (d) of the inner catalytic layer contains 10% (w) pore-forming agents and the outer catalytic layer contains cathodic catalytic layers with different proportions of pore-forming agents

	R_Ω/(m_Ω•cm²)	R_p/(m_Ω•cm²)	(R_ct+R_mt)/(m_Ω•cm²)
MEA 0	0.091	0.038	0.388
MEA 1	0.094	0.018	0.24
MEA 2	0.099	0.021	0.204
MEA 3	0.112	0.043	0.303
MEA 4	0.108	0.049	0.264
MEA 5	0.112	0.025	0.214
MEA 6	0.118	0.046	0.221

Table 3. The equivalent circuit fitting results of each membrane electrode

Figure 6. Oxygen gain curves of different MEA

Figure 7. Durability test of MEA 2 at 0.2 A?cm-2

Figure 8. Equivalent circuit model

References 43

[1]	Xiao, F.; Wang, Y.; Wu, Z.; Chen, G.; Yang, F.; Zhu, S.; Shao, M. Adv. Mater. 2021, 33, 2006292. doi: 10.1002/adma.v33.50
[2]	Tang, M. H.; Zhang, S. M.; Chen, S. L. Chem. Soc. Rev. 2022, 51, 1529. doi: 10.1039/D1CS00981H
[3]	Chen, J. N.; Bailey, J. J.; Britnell, L.; Maria, P. P.; Zhang, Z.; Strudwick, A.; Hack, J.; Guo, Z. M.; Martin, P.; Dan, J. L.; Stuart, M. H. Nano Energy 2022, 93, 106829. doi: 10.1016/j.nanoen.2021.106829
[4]	Hong, L. H.; Wang, B. L.; Zhao, C. G. Appl. Surf. Sci. 2019, 31, 785.
[5]	Mazúr, P.; Soukup, J.; Paidar, M.; Bouzek, K. J. Appl. Electrochem. 2011, 41, 1013. doi: 10.1007/s10800-011-0325-9
[6]	Yurko, Y.; Elbaz, L. Electrochim. Acta 2021, 389, 138676. doi: 10.1016/j.electacta.2021.138676
[7]	Tian, X. L.; Xu, Y. Y.; Zhang, W. Y.; Wu, T.; Xia, B. Y.; Wang, X. ACS Energy Lett. 2017, 2, 2035. doi: 10.1021/acsenergylett.7b00593
[8]	Wannek, C.; Lehnert, W.; Mergel, J. J. Power Sources 2009, 192, 258. doi: 10.1016/j.jpowsour.2009.03.051
[9]	Yin, Y.; Liu, J.; Chang, Y. F.; Zhu, Y. Z.; Xie, X.; Qin, Y. Z.; Zhang, J. F.; Jiao, K.; Guiver, M. D. Electrochim. Acta 2018, 296, 450. doi: 10.1016/j.electacta.2018.11.048
[10]	Ji, Z. Q.; Chen, J. N.; Guo, Z. M.; Zhao, Z. Y.; Cai, R. S.; Rigby, T. P.; Sarah, J.; Shen, Y. T.; Holmes, S. M. J. Energy Chem. 2022, 75, 399. doi: 10.1016/j.jechem.2022.08.004
[11]	Li, W. W.; Shang, Y. M.; Wang, S. B.; Xie, X. F.; Lu, Y. F. Chem. Eng. J. 2011, 62, 131. (in Chinese)
	(李微微, 尚玉明, 王树博, 谢晓峰, 吕亚非, 化工学报, 2011, 62, 131.)
[12]	Lee, E.; Kim, D. H.; Pak, C. H. Appl. Surf. Sci. 2020, 510, 145461. doi: 10.1016/j.apsusc.2020.145461
[13]	Kazeminasab, B.; Rowshanzamir, S.; Ghadamian, H. Korean J. Chem. Eng. 2017, 34, 2978. doi: 10.1007/s11814-017-0202-2
[14]	Barron, O.; Su, H. N.; Linkov, V.; Pollet, B. G.; Pasupathi, S. K. J. Power Sources 2015, 278, 718. doi: 10.1016/j.jpowsour.2014.12.139
[15]	Gao, C. M.; Hu, M. S.; Wang, L.; Wang, L. Polymers 2020, 12, 515. doi: 10.3390/polym12030515
[16]	Sun, M.; Huang, J. C.; Xia, Z. G.; Wang, S. L.; Sun, G. G. AIChE J. 2022, 68, 8.
[17]	Kim, S.; Yuk, S.; Kim, H. G.; Choi, C. Y.; Kim, R. Y.; Lee, J. Y.; Hong, Y. T.; Kim, H. T. J. Mater. 2017, 5, 33.
[18]	Seland, F.; Berning, T.; Børresen, B.; Tunold, R. J. Power Sources 2006, 160, 1. doi: 10.1016/j.jpowsour.2005.12.081
[19]	Kim, G. H.; Eom, S.; Kim, M. J.; Yoo, S. J.; Jang, J. H.; Kim, H.; Cho, E. ACS Appl. Mater. Interfaces 2015, 7, 27581. doi: 10.1021/acsami.5b07346
[20]	Su, H. N.; Liang, H. G.; Bladergroen, J.; Linkov, V.; Pollet, B. G.; Pasupathi, S. J. Electrochem. 2014, 161, 4.
[21]	Liu, S.; Klaus, W.; Werner, L. Int. J. Hydrog. 2021, 46, 27.
[22]	Zhang, J. J.; Wang, H. N.; Li, W.; Zhang, J.; Lu, D.; Yan, W.; Xiang, Y.; Lu, S. F. J. Power Sources 2021, 505, 230059. doi: 10.1016/j.jpowsour.2021.230059
[23]	Bender, G.; Zawodzinski, T.; Saab, A. P. J. Power Sources 2003, 124, 114. doi: 10.1016/S0378-7753(03)00735-3
[24]	Chung, Y. H.; Kim, S. J.; Chung, D. Y.; Park, H. Y.; Sung, Y. E.; Yoo, S.; Jang, J. ChemComm. 2015, 51, 2968.
[25]	Chao, G.; Tang, H. Y.; Ju, Q.; Li, N. W.; Geng, K. J. Power Sources 2023, 556, 232473. doi: 10.1016/j.jpowsour.2022.232473
[26]	Yoon, Y. G.; Yang, T. H.; Park, G. G.; Lee, W. Y.; Kim, C. S. J. Power Sources 2003, 118, 189. doi: 10.1016/S0378-7753(03)00092-2
[27]	Su, H. N.; Jao, T. C.; Pasupathi, S.; Bladergroen, B. J.; Linkov, V.; Pollet, B. G. J. Power Sources 2014, 246, 63. doi: 10.1016/j.jpowsour.2013.07.062
[28]	Garsany, Y.; Atkinson, R. W.; Gould, R. D.; Martin, R.; Dubau, L.; Chatenet, M.; Swider, K. M. J. Power Sources 2021, 514, 230514.
[29]	Zlotorowicz, A.; Jayasayee, K.; Dahl, P. I.; Thomassen, M. S.; Kjelstrup, S. J. Power Sources 2015, 287, 472. doi: 10.1016/j.jpowsour.2015.04.079
[30]	Zhao, J.; He, X.; Wang, L.; Tian, J.; Wan, C.; Jiang, C. Int. J. Hydrog. 2007, 32, 380. doi: 10.1016/j.ijhydene.2006.06.057
[31]	Tian, J. H.; Liu, B. W.; Liu, X.; Zhu, K.; Chen, Y. X. PST. 2005, 03, 154. (in Chinese)
	(田建华, 刘邦卫, 刘翔, 朱科, 陈延禧, 化学电源, 2005, 03, 154.)
[32]	Gloaguen, F.; Convert, P.; Gamburzev, S.; Velev, O. A.; Srinivasan, S. Electrochim. Acta 1998, 43, 3767. doi: 10.1016/S0013-4686(98)00136-4
[33]	Cui, L. R.; Zhang, J.; Sun, Y. Y.; Lu, S. F.; Xiang, Y. Acta Chim. Sinica 2019, 77, 47. (in Chinese) doi: 10.6023/A18080344
	(崔丽瑞, 张劲, 孙一焱, 卢善富, 相艳, 化学学报, 2019, 77, 47.) doi: 10.6023/A18080344
[34]	Wang, M.; Chen, M.; Yang, Z. Y.; Liu, G. C.; Lee, J. K.; Yang, W.; Wang, X. D. Energy Convers. Manag. 2019, 191, 132. doi: 10.1016/j.enconman.2019.04.014
[35]	Ji, F.; Zheng, B. W.; Luo, R. Y.; Du, W.; Deng, C. W.; Yang, S.; Liu, Z. Q. Chem. Ind. Eng. Prog. 2022, 41, 5325. (in Chinese)
	(姬峰, 郑博文, 罗若尹, 杜玮, 邓呈维, 杨声, 刘志强, 化工进展, 2022, 41, 5325.) doi: 10.16085/j.issn.1000-6613.2021-2558
[36]	Bevilacqua, N.; Schmid, M.; Zeis, R. Power Sources. 2020, 471, 228469. doi: 10.1016/j.jpowsour.2020.228469
[37]	Zhang, W. Q.; Yao, D. G.; Tian, L. L.; Xie, Z.; Ma, Q.; Xu, Q.; Pasupathi, S.; Xing, L.; Su, H. N. J. Taiwan Inst. Chem. Eng. 2021, 125, 258.
[38]	Wang, H. S.; Chih, P. H.; Shiuan, W. S.; Tseng, Y. J.; Gang, F. J. Am. Chem. Soc. 2012, 243, 529.
[39]	Zhang, S. M. Ph.D. Dissertation, Zhejiang University, Hangzhou, 2023. (in Chinese)
	(张硕猛, 博士论文, 浙江大学, 杭州, 2023.)
[40]	Duan, K. J.; Roswitha, Z.; Sui, B. J. J. Chongqing Univ. 2022, 45, 34. (in Chinese)
	(段康俊, Roswitha, Z., 隋邦傑, 重庆大学学报, 2022, 45, 34.)
[41]	Bjorn, W. J.; Douglas, R. M. Energy Environ. Sci. 2011, 4, 2790. doi: 10.1039/c0ee00652a
[42]	Li, T. Y.; Wang, K. J.; Wang, J. H.; Liu, Y. Q.; Han, Y. F.; Song, J. H.; Hu, H. W.; Lin, G. G.; Liu, Y. Mater. Sci. 2020, 55, 4558. doi: 10.1007/s10853-019-04323-9
[43]	Eunae, L.; Do-Hyung, K.; Chanho, P. Appl. Surf. Sci. 2020, 510, 13242.

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