氢气中杂质对车用燃料电池性能影响的研究进展

doi:10.16085/j.issn.1000-6613.2021-0458

摘要/Abstract

摘要：

车用质子交换膜燃料电池（proton exchange membrane fuel cells，PEMFCs）的耐久性是制约氢能在交通领域商业化应用的关键因素之一。阳极燃料气中含有的微量H₂S、CO和NH₃等杂质是影响PEMFCs耐久性的最主要因素之一。本文综述了PEMFCs阳极氢气中存在的三种关键杂质，即H₂S、CO和NH₃对PEMFCs阳极性能影响的研究进展，包括杂质毒化机制、动力学、燃料电池操作条件影响以及缓解策略，讨论了氢气杂质容限值规定的理论和实验基础。最后，指出了目前氢气杂质对车用PEMFCs影响研究存在的技术问题及未来发展方向，重点指出了根据我国PEMFCs技术发展水平精准推定满足我国车用燃料电池耐久性的氢气杂质容限值的必要性和紧迫性，从而为优化和完善我国车用燃料电池用氢质量标准提供基础数据，促进车用燃料电池寿命的提升。

关键词: 车用质子交换膜燃料电池, 耐久性, 氢气杂质, 容限值

Abstract:

The durability of proton exchange membrane fuel cells (PEMFCs) for vehicles is one of the key factors restricting the commercial application of hydrogen energy in the transportation field. The presence of trace amounts of CO, H₂S and NH₃contained in the fuel gas is regarded as one of the most important factors affecting the durability of PEMFCs. This article reviewed the effects of CO, H₂S, and NH₃in hydrogen on the anode performance of PEMFCs, including the poisoning mechanism, kinetics, the effect of operating conditions and the mitigation strategies, and also discussed the theoretical and experimental foundation for the determination of hydrogen impurity limits. Finally, it pointed out the technical problems and future development directions in the research on the effect of hydrogen impurities on vehicle fuel cells, and emphasized the necessity of determining the tolerance limits of hydrogen impurities that met the durability of vehicle fuel cells, according to the technical development level of PEMFCs technology in our country. It is valuable for the optimization and regulation of the China’s hydrogen quality standards for vehicle fuel cells by providing basic data, and thus prolonging vehicle fuel cell lifetime.

Key words: automotive fuel cell, durability, hydrogen impurity, tolerance limit

中图分类号:

TM911.4

何广利, 窦美玲. 氢气中杂质对车用燃料电池性能影响的研究进展[J]. 化工进展, 2021, 40(9): 4815-4822.

HE Guangli, DOU Meiling. Progress on effect of hydrogen impurities on the performance of automotive fuel cells[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 4815-4822.

图/表 3

参考文献 51

1	WU J F, YUAN X Z, MARTIN J J, et al. A review of PEM fuel cell durability: degradation mechanisms and mitigation strategies[J]. Journal of Power Sources, 2008, 184(1): 104-119.
2	CHEN H C, PEI P C, SONG M C. Lifetime prediction and the economic lifetime of proton exchange membrane fuel cells[J]. Applied Energy, 2015, 142: 154-163.
3	DU Z M, LIU C M, ZHAI J X, et al. A review of hydrogen purification technologies for fuel cell vehicles[J]. Catalysts, 2021, 11(3): 393.
4	LISZKA M, MALIK T, MANFRIDA G. Energy and exergy analysis of hydrogen-oriented coal gasification with CO₂ capture[J]. Energy, 2012, 45(1): 142-150.
5	MARTÍNEZ I, ROMANO M C, CHIESA P, et al. Hydrogen production through sorption enhanced steam reforming of natural gas: thermodynamic plant assessment[J]. International Journal of Hydrogen Energy, 2013, 38(35): 15180-15199.
6	CHUGH S, MEENAKSHI S, SONKAR K, et al. Performance evaluation of PEM fuel cell stack on hydrogen produced in the oil refinery[J]. International Journal of Hydrogen Energy, 2020, 45(8): 5491-5500.
7	CHENG X, SHI Z, GLASS N, et al. A review of PEM hydrogen fuel cell contamination: impacts, mechanisms, and mitigation[J]. Journal of Power Sources, 2007, 165(2): 739-756.
8	ZAMEL N, LI X G. Effect of contaminants on polymer electrolyte membrane fuel cells[J]. Progress in Energy and Combustion Science, 2011, 37(3): 292-329.
9	SHABANI B, HAFTTANANIAN M, KHAMANI S, et al. Poisoning of proton exchange membrane fuel cells by contaminants and impurities: review of mechanisms, effects, and mitigation strategies[J]. Journal of Power Sources, 2019, 427: 21-48.
10	DURST J, SIEBEL A, SIMON C, et al. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism[J]. Energy Environ. Sci., 2014, 7(7): 2255-2260.
11	ROSS P N, STONEHART P. Selective poisoning of H₂-D₂ equilibration on transition metals by carbon monoxide[J]. Journal of Catalysis, 1974, 35(3): 391-400.
12	IGARASHI H, FUJINO T, WATANABE M. Hydrogen electro-oxidation on platinum catalysts in the presence of trace carbon monoxide[J]. Journal of Electroanalytical Chemistry, 1995, 391(1/2): 119-123.
13	OETJEN H F, SCHMIDT V M, STIMMING U, et al. Performance data of a proton exchange membrane fuel cell using H₂ / CO as fuel gas[J]. Journal of the Electrochemical Society, 1996, 143(12): 3838-3842.
14	CIUREANU M, ROBERGE R. Electrochemical impedance study of PEM fuel cells. experimental diagnostics and modeling of air cathodes[J]. The Journal of Physical Chemistry B, 2001, 105(17): 3531-3539.
15	MURTHY A M, ESAYIAN M, HOBSON A, et al. Performance of a polymer electrolyte membrane fuel cell exposed to transient CO concentrations[J]. Journal of the Electrochemical Society, 2001, 148(10): A1141.
16	BECKER H, BACQUART T, PERKINS M, et al. Operando characterisation of the impact of carbon monoxide on PEMFC performance using isotopic labelling and gas analysis[J]. Journal of Power Sources Advances, 2020, 6: 100036.
17	MATSUDA Y, SHIMIZU T, HASHIMASA Y. Effect of carbon monoxide on polymer electrolyte fuel cell performance with a hydrogen circulation system[J]. Journal of the Electrochemical Society, 2020, 167(4): 044509.
18	BERNASEK S L, SOMORJAI G A. Molecular beam study of the mechanism of catalyzed hydrogen-deuterium exchange on platinum single crystal surfaces[J]. The Journal of Chemical Physics, 1975, 62(8): 3149-3161.
19	MONTANO M, BRATLIE K, SALMERON M, et al. Hydrogen and deuterium exchange on Pt(111) and its poisoning by carbon monoxide studied by surface sensitive high-pressure techniques[J]. Journal of the American Chemical Society, 2006, 128(40): 13229-13234.
20	ZHANG J Z, HONGSIRIKARN K, GOODWIN J G. The effect of low concentrations of CO on H₂ adsorption and activation on Pt/C: Part 2—In the presence of H₂O vapor[J]. Journal of Power Sources, 2011, 196(15): 6186-6195.
21	BENDER G, ANGELO M, BETHUNE K, et al. Quantitative analysis of the performance impact of low-level carbon monoxide exposure in proton exchange membrane fuel cells[J]. Journal of Power Sources, 2013, 228: 159-169.
22	ZAMEL N, LI X G. Transient analysis of carbon monoxide poisoning and oxygen bleeding in a PEM fuel cell anode catalyst layer[J]. International Journal of Hydrogen Energy, 2008, 33(4): 1335-1344.
23	PETUKHOV A V, AKEMANN W, FRIEDRICH K A, et al. Kinetics of electrooxidation of a CO monolayer at the platinum/electrolyte interface[J]. Surface Science, 1998, 402/403/404: 182-186.
24	WANG Q, WANG G X, TAO H L, et al. Highly CO tolerant PtRu/PtNi/C catalyst for polymer electrolyte membrane fuel cell[J]. RSC Advances, 2017, 7(14): 8453-8459.
25	BORTOLOTI F, GARCIA A C, ANGELO A C D. Electronic effect in intermetallic electrocatalysts with low susceptibility to CO poisoning during hydrogen oxidation[J]. International Journal of Hydrogen Energy, 2015, 40(34): 10816-10824.
26	HU J E, LIU Z F, EICHHORN B W, et al. CO tolerance of nano-architectured Pt-Mo anode electrocatalysts for PEM fuel cells[J]. International Journal of Hydrogen Energy, 2012, 37(15): 11268-11275.
27	DAI Y, LIU Y W, CHEN S L. Pt-W bimetallic alloys as CO-tolerant PEMFC anode catalysts[J]. Electrochimica Acta, 2013, 89: 744-748.
28	MATHIEU M V, PRIMET M. Sulfurization and regeneration of platinum[J]. Applied Catalysis, 1984, 9(3): 361-370.
29	MOHTADI R, LEE W K, COWAN S, et al. Effects of hydrogen sulfide on the performance of a PEMFC[J]. Electrochemical and Solid-State Letters, 2003, 6(12): A272.
30	LOUČKA T. The formation and reduction of an oxide layer on a platinum electrode partially covered with adsorbed sulphur[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1973, 44(2): 221-227.
31	WANG Y R, YAN H Q, WANG E F. The electrochemical oxidation and the quantitative determination of hydrogen sulfide on a solid polymer electrolyte-based system[J]. Journal of Electroanalytical Chemistry, 2001, 497(1/2): 163-167.
32	MOHTADI R, LEE W K, VAN ZEE J W. The effect of temperature on the adsorption rate of hydrogen sulfide on Pt anodes in a PEMFC[J]. Applied Catalysis B: Environmental, 2005, 56(1/2): 37-42.
33	URDAMPILLETA I, URIBE F, ROCKWARD T, et al. PEMFC poisoning with H₂S: dependence on operating conditions[J]. ECS Transactions, 2019, 11(1): 831-842.
34	KAKATI B K, KUCERNAK A R J. Gas phase recovery of hydrogen sulfide contaminated polymer electrolyte membrane fuel cells[J]. Journal of Power Sources, 2014, 252: 317-326.
35	FRANCK-LACAZE L, BONNET C, BESSE S, et al. Effects of ozone on the performance of a polymer electrolyte membrane fuel cell[J]. Fuel Cells, 2009, 9(5): 562-569.
36	LOPES T, PAGANIN V A, GONZALEZ E R. Hydrogen sulfide tolerance of palladium-copper catalysts for PEM fuel cell anode applications[J]. International Journal of Hydrogen Energy, 2011, 36(21): 13703-13707.
37	URIBE F A, GOTTESFELD S, ZAWODZINSKI T A. Effect of ammonia as potential fuel impurity on proton exchange membrane fuel cell performance[J]. Journal of the Electrochemical Society, 2002, 149(3): A293.
38	HALSEID R, VIE P J S, TUNOLD R. Effect of ammonia on the performance of polymer electrolyte membrane fuel cells[J]. Journal of Power Sources, 2006, 154(2): 343-350.
39	HONGSIRIKARN K, GOODWIN J G, GREENWAY S, et al. Influence of ammonia on the conductivity of Nafion membranes[J]. Journal of Power Sources, 2010, 195(1): 30-38.
40	HONGSIRIKARN K, NAPAPRUEKCHART T, MO X H, et al. Effect of ammonium ion distribution on Nafion^® conductivity[J]. Journal of Power Sources, 2011, 196(2): 644-651.
41	JAMES G GOODWIN J, COLON-MERCADO H, HONGSIRIKARN K, et al. Final technical report: effects of impurities on fuel cell performance and durability[R]. Office of Scientific and Technical Information (OSTI), 2011.
42	GOMEZ Y A, OYARCE A, LINDBERGH G, et al. Ammonia contamination of a proton exchange membrane fuel cell[J]. Journal of the Electrochemical Society, 2018, 165(3): F189-F197.
43	TERLIP D TERLIP D. Hydrogen contaminant detector task ： requirements document and market survey[R]. National Renewable Energy Laboratory, 2015.
44	MATSUDA Y, SHIMIZU T, MITSUSHIMA S. Adsorption behavior of low concentration carbon monoxide on polymer electrolyte fuel cell anodes for automotive applications[J]. Journal of Power Sources, 2016, 318: 1-8.
45	CHEN C Y, CHEN C C, HSU S W, et al. Behavior of a proton exchange membrane fuel cell in reformate gas[J]. Energy Procedia, 2012, 29: 64-71.
46	SHI W Y, YI B L, HOU M, et al. The effect of H₂S and CO mixtures on PEMFC performance[J]. International Journal of Hydrogen Energy, 2007, 32(17): 4412-4417.
47	SHI W Y, YI B L, HOU M, et al. Hydrogen sulfide poisoning and recovery of PEMFC Pt-anodes[J]. Journal of Power Sources, 2007, 165(2): 814-818.
48	SHI Z, SONG D T, ZHANG J J, et al. Transient analysis of hydrogen sulfide contamination on the performance of a PEM fuel cell[J]. Journal of the Electrochemical Society, 2007, 154(7): B609.
49	GARZON F, LOPES T, ROCKWARD T, et al. The impact of impurities on long-term PEMFC performance[J]. ECS Transactions, 2019, 25(1): 1575-1583.
50	LOPES T, PAGANIN V A, GONZALEZ E R. The effects of hydrogen sulfide on the polymer electrolyte membrane fuel cell anode catalyst: H₂S-Pt/C interaction products[J]. Journal of Power Sources, 2011, 196(15): 6256-6263.
51	JEAN S P. PEMFC contaminant tolerance limit—CO in H₂[J]. Electrochimica Acta, 2010, 55(13): 4208-4211.

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