中高温质子交换膜燃料电池催化剂研究进展

doi:10.3866/PKU.WHXB202009087

Abstract

Abstract:

High-temperature polymer exchange membrane fuel cells (HT-PEMFCs), promising and sustainable energy conversion devices, have received considerable attention ascribed to their high energy conversion efficiency and zero emission. Different from the traditional Nafion PEMFCs, the working temperature ranks from 120 to 250 ℃ for HT-PEMFCs; as a result, HT-PEFMCs show impressive merits, such as theoretically higher kinetics, simple water/heat management and better tolerance toward impurities in hydrogen fuel; especially the elimination of flooding issue in fuel cells. Moreover, the working temperature matches well with the temperature for hydrogen generation from methanol reforming revealing that the generated heat from HT-PEMFCs can be utilized for methanol reforming to generate hydrogen; in this case, hydrogen tank can be replaced by methanol reforming system for HT-PEMFCs leading to a higher safety. Similar to traditional Nafion PEMFCs, polymer electrolyte membrane (PEM) associated with two electrodes representing for anode and cathode compose the membrane electrode assembly (MEA). Electrocatalyst as heart of HT-PEMFCs significantly affects the output of fuel cells, especially the cathodic electrocatalyst since the oxygen reduction reaction (ORR) kinetics is substantially sluggish than hydrogen oxidation reaction (HOR). Phosphoric acid doped polybenzimidazole (PA-PBI) is the state-of-the-art PEM for HT-PEMFCs; while, due to the low interaction between PA and PBI, PA leaching to the catalyst layer is normally observed during the long-term operation resulting in blocking of active sites to reduce three-phase boundary (TPB); besides, oxygen dissolution/diffusion in PA is much lower compared to Nafion, thereby, lower fuel cell performance is customarily recorded than Nafion PEMFCs. Thus, construction of high-performance ORR electrocatalyst with exceptional tolerance toward phosphate and increasing of oxygen concentration at TPB are highly desirable to realize the commercialization of HT-PEMFCs. Additionally, the stability of electrocatalyst should be significantly considered because the coalescence of platinum (Pt) nanoparticles as well as carbon corrosion is accelerated at high working temperature. In this review, we have summarized the recently reported Pt, non-Pt and meta-free electrocatalysts in HT-PEMFCs application. Surficial modification, alloying effect as well as substrate effect have been invited to construct high-performance Pt electrocatalyst in phosphoric acid electrolyte since the adsorption of phosphate on Pt is alleviated by surface coating and modulation of electronic configuration of Pt. Due to the comparably lower interaction with phosphate than Pt and considerable catalytic activity toward ORR, non-Pt and metal-free electrocatalyst have also been systematically investigated as HT-PEMFCs cathodic electrocatalyst. Finally, the perspectives and challenges in HT-PEMFCs have been discussed.

Key words: High-temperature polymer exchange membrane fuel cell, Phosphoric acid poisoning, O₂ dissolution, Pt electrocatalyst, Non-Pt electrocatalyst, Metal-free electrocatalyst

Fang Luo, Shuyuan Pan, Zehui Yang. Recent Progress on Electrocatalyst for High-Temperature Polymer Exchange Membrane Fuel Cells[J]. Acta Phys. -Chim. Sin. 2021, 37(9), 2009087. doi: 10.3866/PKU.WHXB202009087

Figures/Tables 8

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

Fig 7

Fig 8

References 69

1	Li Q. ; Jensen J. O. ; Savinell R. F. ; Bjerrum N. J. Prog. Polym. Sci. 2009, 34, 449. doi: 10.1016/j.progpolymsci.2008.12.003
2	Asensio J. A. ; Sánchez E. M. ; Gómez-Romero P. Chem. Soc. Rev. 2010, 39, 3210. doi: 10.1039/B922650H
3	Aili D. ; Zhang J. ; Dalsgaard Jakobsen M. T. ; Zhu H. ; Yang T. ; Liu J. ; Forsyth M. ; Pan C. ; Jensen J. O. ; Cleemann L. N. ; et al J. Mater. Chem. A 2016, 4, 4019. doi: 10.1039/C6TA01562J
4	Liu S. ; Rasinski M. ; Rahim Y. ; Zhang S. ; Wippermann K. ; Reimer U. ; Lehnert W. J. Power Sources 2019, 439, 227090. doi: 10.1016/j.jpowsour.2019.227090
5	Li Q. ; He R. ; Jensen J. O. ; Bjerrum N. J. Fuel Cells 2004, 4, 147. doi: 10.1002/fuce.200400020
6	Araya S. S. ; Zhou F. ; Liso V. ; Sahlin S. L. ; Vang J. R. ; Thomas S. ; Gao X. ; Jeppesen C. ; Kær S. K. Int. J. Hydrogen Energy 2016, 41, 21310. doi: 10.1016/j.ijhydene.2016.09.024
7	Singdeo D. ; Dey T. ; Gaikwad S. ; Andreasen S. J. ; Ghosh P. C. Appl. Energy 2017, 195, 13. doi: 10.1016/j.apenergy.2017.03.022
8	Bai H. ; Peng H. ; Xiang Y. ; Zhang J. ; Wang H. ; Lu S. ; Zhuang L. J. Power Sources 2019, 443, 227219. doi: 10.1016/j.jpowsour.2019.227219
9	Yu S. ; Benicewicz B. C. Macromolecules 2009, 42, 8640. doi: 10.1021/ma9015664
10	Holst-Olesen K. ; Reda M. ; Hansen H. A. ; Vegge T. ; Arenz M. ACS Catal. 2018, 8, 7104. doi: 10.1021/acscatal.8b01584
11	Cheng Y. ; He S. ; Lu S. ; Veder J. P. ; Johannessen B. ; Thomsen L. ; Saunders M. ; Becker T. ; De Marco R. ; Li Q. ; et al Adv. Sci. 2019, 6, 1802066. doi: 10.1002/advs.201802066
12	Strickland K. ; Pavlicek R. ; Miner E. ; Jia Q. ; Zoller I. ; Ghoshal S. ; Liang W. ; Mukerjee S. ACS Catal. 2018, 8, 3833. doi: 10.1021/acscatal.8b00390
13	Kodama K. ; Motobayashi K. ; Shinohara A. ; Hasegawa N. ; Kudo K. ; Jinnouchi R. ; Osawa M. ; Morimoto Y. ACS Catal. 2018, 8, 694. doi: 10.1021/acscatal.7b03571
14	Bahlakeh G. ; Hasani-Sadrabadi M. M. ; Emami S. H. ; Eslami S. N. S. ; Dashtimoghadam E. ; Shokrgozar M. A. ; Jacob K. I. J. Membr. Sci. 2017, 535, 221. doi: 10.1016/j.memsci.2017.04.045
15	Hu Y. ; Jiang Y. ; Jensen J. O. ; Cleemann L. N. ; Li Q. J. Power Sources 2018, 375, 77. doi: 10.1016/j.jpowsour.2017.11.054
16	Kaserer S. ; Caldwell K. M. ; Ramaker D. E. ; Roth C. J. Phys. Chem. C 2013, 117, 6210. doi: 10.1021/jp311924q
17	Mamtani K. ; Jain D. ; Zemlyanov D. ; Celik G. ; Luthman J. ; Renkes G. ; Co A. C. ; Ozkan U. S. ACS Catal. 2016, 6, 7249. doi: 10.1021/acscatal.6b01786
18	Li Y. ; Jiang L. ; Wang S. ; Sun G. Chin. J. Catal. 2016, 37, 1134. doi: 10.1016/S1872-2067(16)62472-5
19	Stamenkovic V. R. ; Fowler B. ; Mun B. S. ; Wang G. ; Ross P. N. ; Lucas C. A. ; Marković N. M. Science 2007, 315, 493. doi: 10.1126/science.1135941
20	Greeley J. ; Stephens I. E. L. ; Bondarenko A. S. ; Johansson T. P. ; Hansen H. A. ; Jaramillo T. F. ; Rossmeisl J. ; Chorkendorff I. ; Nørskov J. K. Nat. Chem. 2009, 1, 552. doi: 10.1038/nchem.367
21	Srivastava R. ; Mani P. ; Hahn N. ; Strasser P. Angew. Chem. Int. Ed. 2007, 46, 8988. doi: 10.1002/anie.200703331
22	Yang T. Y. ; Cui C. ; Rong H. P. ; Zhang J. T. ; Wang D. S. Acta Phys. -Chim. Sin. 2020, 36, 2003047.
	杨天怡; 崔铖; 戎宏盼; 张加涛; 王定胜. 物理化学学报, 2020, 36, 2003047. doi: 10.3866/PKU.WHXB202003047
23	He Q. ; Yang X. ; Chen W. ; Mukerjee S. ; Koel B. ; Chen S. Phy. Chem. Chem. Phy. 2010, 12, 12544. doi: 10.1039/C0CP00433B
24	Li D. ; Wang C. ; Tripkovic D. ; Sun S. ; Markovic N. M. ; Stamenkovic V. R. ACS Catal. 2012, 2, 1358. doi: 10.1021/cs300219j
25	Wang C. ; Daimon H. ; Lee Y. ; Kim J. ; Sun S. J. Am. Chem. Soc. 2007, 129, 6974. doi: 10.1021/ja070440r
26	Peng Z. ; You H. ; Yang H. ACS Nano 2010, 4, 1501. doi: 10.1021/nn9016795
27	Zhang J. ; Fang J. J. Am. Chem. Soc. 2009, 131, 18543. doi: 10.1021/ja908245r
28	Chung Y. H. ; Chung D. Y. ; Jung N. ; Sung Y. E. J. Phy. Chem. Lett. 2013, 4, 1304. doi: 10.1021/jz400574f
29	Chung Y. H. ; Kim S. J. ; Chung D. Y. ; Park H. Y. ; Sung Y. E. ; Yoo S. J. ; Jang J. H. Chem. Commun. 2015, 51, 2968. doi: 10.1039/C4CC09019E
30	Luo F. ; Zhang Q. ; Yang Z. ; Guo L. ; Yu X. ; Qu K. ; Ling Y. ; Yang J. ; Cai W. ChemCatChem 2018, 10, 5314. doi: 10.1002/cctc.201801256
31	Zhang Q. ; Ling Y. ; Cai W. ; Yu X. ; Yang Z. Int. J. Hydrogen Energy 2017, 42, 16714. doi: 10.1016/j.ijhydene.2017.05.070
32	Strmcnik D. ; Escudero-Escribano M. ; Kodama K. ; Stamenkovic V. R. ; Cuesta A. ; Marković N. M. Nat. Chem. 2010, 2, 880. doi: 10.1038/nchem.771
33	Jeong D. C. ; Mun B. ; Lee H. ; Hwang S. J. ; Yoo S. J. ; Cho E. ; Lee Y. ; Song C. RSC Adv. 2016, 6, 60749. doi: 10.1039/C6RA13123A
34	Delikaya Ö. ; Zeyat M. ; Lentz D. ; Roth C. ChemElectroChem 2019, 6, 3892. doi: 10.1002/celc.201900251
35	Liu G. ; Zhang H. ; Zhai Y. ; Zhang Y. ; Xu D. ; Shao Z. G. Electrochem. Commun. 2007, 9, 135. doi: 10.1016/j.elecom.2006.08.056
36	Hong S. G. ; Kwon K. ; Lee M. J. ; Yoo D. Y. Electrochem. Commun. 2009, 11, 1124. doi: 10.1016/j.elecom.2009.03.028
37	Jung N. ; Shin H. ; Kim M. ; Jang I. ; Kim H. J. ; Jang J. ; Kim H. ; Yoo S. Nano Energy 2015, 17, 152. doi: 10.1016/j.nanoen.2015.08.012
38	Jeong G. ; Kim M. ; Han J. ; Kim H. J. ; Shul Y. G. ; Cho E. J. Power Sources 2016, 323, 142. doi: 10.1016/j.jpowsour.2016.05.042
39	Mack F. ; Morawietz T. ; Hiesgen R. ; Kramer D. ; Gogel V. ; Zeis R. Int. J. Hydrogen Energy 2016, 41, 7475. doi: 10.1016/j.ijhydene.2016.02.156
40	Liu J. ; Tang J. ; Gooding J. J. J. Mater. Chem. 2012, 22, 12435. doi: 10.1039/C2JM31218B
41	Berber M. R. ; Fujigaya T. ; Sasaki K. ; Nakashima N. Sci. Rep. 2013, 3, 1764. doi: 10.1038/srep01764
42	Yang Z. ; Moriguchi I. ; Nakashima N. ACS Appl. Mater. Interfaces 2015, 7, 9800. doi: 10.1021/acsami.5b01724
43	Stamatin S. N. ; Speder J. ; Dhiman R. ; Arenz M. ; Skou E. M. ACS Appl. Mater. Interfaces 2015, 7, 6153. doi: 10.1021/am508982d
44	Yin S. ; Mu S. ; Lv H. ; Cheng N. ; Pan M. ; Fu Z. Appl. Catal. B 2010, 93, 233. doi: 10.1016/j.apcatb.2009.09.034
45	Lobato J. ; Zamora H. ; Plaza J. ; Cañizares P. ; Rodrigo M. A. Appl. Catal. B 2016, 198, 516. doi: 10.1016/j.apcatb.2016.06.011
46	Zamora H. ; Plaza J. ; Velhac P. ; Cañizares P. ; Rodrigo M. A. ; Lobato J. Appl. Catal. B 2017, 207, 244. doi: 10.1016/j.apcatb.2017.02.019
47	Kim D. K. ; Kim H. ; Park H. ; Oh S. ; Ahn S. H. ; Kim H. J. ; Kim S. K. J. Power Sources 2019, 438, 227022. doi: 10.1016/j.jpowsour.2019.227022
48	Yang Z. ; Nakashima N. J. Mater. Chem. A 2015, 3, 23316. doi: 10.1039/C5TA06735A
49	Yang Z. ; Berber M. R. ; Nakashima N. Electrochim. Acta 2015, 170, 1. doi: 10.1016/j.electacta.2015.04.122
50	Park H. Y. ; Lim D. H. ; Yoo S. J. ; Kim H. J. ; Henkensmeier D. ; Kim J. Y. ; Ham H. C. ; Jang J. H. Sci. Rep. 2017, 7, 7186. doi: 10.1038/s41598-017-06812-w
51	Millán M. ; Zamora H. ; Rodrigo M. A. ; Lobato J. ACS Appl. Mater. Interfaces 2017, 9, 5927. doi: 10.1021/acsami.6b13071
52	Lim J. E. ; Lee U. J. ; Ahn S. H. ; Cho E. ; Kim H. J. ; Jang J. H. ; Son H. ; Kim S. K. Appl. Catal. B 2015, 165, 495. doi: 10.1016/j.apcatb.2014.10.042
53	Neyerlin K. C. ; Singh A. ; Chu D. J. Power Sources 2008, 176, 112. doi: 10.1016/j.jpowsour.2007.10.030
54	Chung Y. H. ; Kim S. J. ; Chung D. Y. ; Lee M. J. ; Jang J. H. ; Sung Y. E. Phys. Chem. Chem. Phys. 2014, 16, 13726. doi: 10.1039/C4CP00187G
55	Lee K. S. ; Yoo S. J. ; Ahn D. ; Kim S. K. ; Hwang S. J. ; Sung Y. E. ; Kim H. J. ; Cho E. ; Henkensmeier D. ; Lim T. H. ; Jang J. H. Electrochim. Acta 2011, 56, 8802. doi: 10.1016/j.electacta.2011.07.084
56	Park H. ; Kim K. M. ; Kim H. ; Kim D. K. ; Won Y. S. ; Kim S. K. Korean J. Chem. Eng. 2018, 35, 1547. doi: 10.1007/s11814-018-0059-z
57	Park H. ; Kim D. K. ; Kim H. ; Oh S. ; Jung W. S. ; Kim S. K. Appl. Surf. Sci. 2020, 510, 145444. doi: 10.1016/j.apsusc.2020.145444
58	Zagudaeva N. M. ; Tarasevich M. R. Russ. J. Electrochem. 2010, 46, 530. doi: 10.1134/S102319351005006X
59	Mamlouk M. ; Scott K. J. Power Sources 2011, 196, 1084. doi: 10.1016/j.jpowsour.2010.08.021
60	Hu Y. ; Shen T. ; Zhao X. ; Zhang J. ; Lu Y. ; Shen J. ; Lu S. ; Tu Z. ; Xin H. L. ; Wang D. Appl. Catal. B 2020, 279, 11937. doi: 10.1016/j.apcatb.2020.119370
61	Ghoshal S. ; Jia Q. ; Bates M. K. ; Li J. ; Xu C. ; Gath K. ; Yang J. ; Waldecker J. ; Che H. ; Liang W. ; et al ACS Catal. 2017, 7, 4936. doi: 10.1021/acscatal.7b01061
62	Yang X. D. ; Chen C. ; Zhou Z. Y. ; Sun S. G. Acta Phys. -Chim. Sin. 2019, 35, 472.
	杨晓冬; 陈驰; 周志有; 孙世刚. 物理化学学报, 2019, 35, 472. doi: 10.3866/PKU.WHXB201806131
63	Wang Q. Q. ; Liu D. J. ; He X. Q. Acta Phys. -Chim. Sin. 2019, 35, 740.
	王倩倩; 刘大军; 何兴权. 物理化学学报, 2019, 35, 740. doi: 10.3866/PKU.WHXB201809003
64	Hu Y. ; Jensen J. O. ; Pan C. ; Cleemann L. N. ; Shypunov I. ; Li Q. Appl. Catal. B 2018, 234, 357. doi: 10.1016/j.apcatb.2018.03.056
65	Li Q. ; Wu G. ; Cullen D. A. ; More K. L. ; Mack N. H. ; Chung H. T. ; Zelenay P. ACS Catal. 2014, 4, 3193. doi: 10.1021/cs500807v
66	Jain D. ; Gustin V. ; Basu D. ; Gunduz S. ; Deka D. J. ; Co A. C. ; Ozkan U. S. J. Catal. 2020, 390, 150. doi: 10.1016/j.jcat.2020.07.012
67	Najam T. ; Shah S. S. A. ; Ding W. ; Wei Z. J. Phys. Chem. C 2019, 123, 16796. doi: 10.1021/acs.jpcc.9b03730
68	Fei H. L. ; Duan X. F. Acta Phys. -Chim. Sin. 2019, 35, 559.
	费慧龙; 段镶锋. 物理化学学报, 2019, 35, 559. doi: 10.3866/PKU.WHXB201809016
69	Najam T. ; Shah S. S. A. ; Ding W. ; Jiang J. ; Jia L. ; Yao W. ; Li L. ; Wei Z. Angew. Chem. Int. Ed. 2018, 57, 15101. doi: 10.1002/anie.201808383

[1]	Liangliang Song, Haoyan Liang, Shunqing Li, Bao Qiu, Zhaoping Liu. Challenges and strategies on high-manganese Li-rich layered oxide cathodes for ultrahigh-energy-density batteries [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100085-.
[2]	Caiyun Jin, Zexuan Wu, Guopeng Li, Zhan Luo, Nian-Wu Li. Phosphazene-based flame-retardant artificial interphase layer for lithium metal batteries [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100094-.
[3]	Yu Peng, Jiawei Chen, Yue Yin, Yongjie Cao, Mochou Liao, Congxiao Wang, Xiaoli Dong, Yongyao Xia. Tailored cathode electrolyte interphase via ethylene carbonate-free electrolytes enabling stable and wide-temperature operation of high-voltage LiCoO₂ [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100087-.
[4]	Mingjie Lei, Wenting Hu, Kexin Lin, Xiujuan Sun, Haoshen Zhang, Ye Qian, Tongyue Kang, Xiulin Wu, Hailong Liao, Yuan Pan, Yuwei Zhang, Diye Wei, Ping Gao. Accelerating the reconstruction of NiSe₂ by Co/Mn/Mo doping for enhanced urea electrolysis [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100083-.
[5]	Mingxuan Qi, Lanyu Jin, Honghe Yao, Zipeng Xu, Teng Cheng, Qi Chen, Cheng Zhu, Yang Bai. Recent progress on electrical failure and stability of perovskite solar cells under reverse bias [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100088-.
[6]	Zeqiu Chen, Limiao Cai, Jie Guan, Zhanyang Li, Hao Wang, Yaoguang Guo, Xingtao Xu, Likun Pan. Advanced electrode materials in capacitive deionization for efficient lithium extraction [J]. Acta Phys. -Chim. Sin., 2025, 41(8): 100089-.
[7]	Chaoqiong Zhu, Ziming Cai, Peizhong Feng, Weichen Zhang, Kezhen Hui, Xiuhua Cao, Zhenxiao Fu, Xiaohui Wang. Reliability Mechanisms of the Ultrathin-Layered BaTiO₃-Based BME MLCC [J]. Acta Phys. -Chim. Sin., 2024, 40(1): 2304015-.
[8]	Xinxuan Duan, Marshet Getaye Sendeku, Daoming Zhang, Daojin Zhou, Lijun Xu, Xueqing Gao, Aibing Chen, Yun Kuang, Xiaoming Sun. Tungsten-Doped NiFe-Layered Double Hydroxides as Efficient Oxygen Evolution Catalysts [J]. Acta Phys. -Chim. Sin., 2024, 40(1): 2303055-.
[9]	Qian Wu, Qingping Gao, Bin Shan, Wenzheng Wang, Yuping Qi, Xishi Tai, Xia Wang, Dongdong Zheng, Hong Yan, Binwu Ying, Yongsong Luo, Shengjun Sun, Qian Liu, Mohamed S. Hamdy, Xuping Sun. Recent Advances in Self-Supported Transition-Metal-Based Electrocatalysts for Seawater Oxidation [J]. Acta Phys. -Chim. Sin., 2023, 39(12): 2303012-.
[10]	Luwei Peng, Yang Zhang, Ruinan He, Nengneng Xu, Jinli Qiao. Research Advances in Electrocatalysts, Electrolytes, Reactors and Membranes for the Electrocatalytic Carbon Dioxide Reduction Reaction [J]. Acta Phys. -Chim. Sin., 2023, 39(12): 2302037-.
[11]	Kuangyu Wang, Kai Liu, Hui Wu. Molten Alkali Metal Batteries Based on Solid Electrolytes [J]. Acta Phys. -Chim. Sin., 2023, 39(12): 2301009-.
[12]	Shuyi Zheng, Jia Wu, Ke Wang, Mengchen Hu, Huan Wen, Shibin Yin. Electronic Modulation of Ni-Mo-O Porous Nanorods by Co Doping for Selective Oxidation of 5-Hydroxymethylfurfural Coupled with Hydrogen Evolution [J]. Acta Phys. -Chim. Sin., 2023, 39(12): 2301032-.
[13]	Zheng-Min Wang, Qing-Ling Hong, Xiao-Hui Wang, Hao Huang, Yu Chen, Shu-Ni Li. RuP Nanoparticles Anchored on N-doped Graphene Aerogels for Hydrazine Oxidation-Boosted Hydrogen Production [J]. Acta Phys. -Chim. Sin., 2023, 39(12): 2303028-.
[14]	Jie Wang, Guigao Liu, Qinbai Yun, Xichen Zhou, Xiaozhi Liu, Ye Chen, Hongfei Cheng, Yiyao Ge, Jingtao Huang, Zhaoning Hu, Bo Chen, Zhanxi Fan, Lin Gu, Hua Zhang. Epitaxial Growth of Unconventional 4H-Pd Based Alloy Nanostructures on 4H-Au Nanoribbons towards Highly Efficient Electrocatalytic Methanol Oxidation [J]. Acta Phys. -Chim. Sin., 2023, 39(10): 2305034-.
[15]	Weifeng Xia, Chengyu Ji, Rui Wang, Shilun Qiu, Qianrong Fang. Metal-Free Tetrathiafulvalene Based Covalent Organic Framework for Efficient Oxygen Evolution Reaction [J]. Acta Phys. -Chim. Sin., 2023, 39(9): 2212057-0.

Recent Progress on Electrocatalyst for High-Temperature Polymer Exchange Membrane Fuel Cells

RichHTML

PDF

Like

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 69

Related Articles 15

Metrics

Recommended 0