Ti₄O₇ supported IrO_x for anode reversal tolerance in proton exchange membrane fuel cell

Abstract

Fuel starvation can occur and cause damage to the cell when proton exchange membrane fuel cells operate under complex working conditions. In this case, carbon corrosion occurs. Oxygen evolution reaction (OER) catalysts can alleviate carbon corrosion by introducing water electrolysis at a lower potential at the anode in fuel shortage. The mixture of hydrogen oxidation reaction (HOR) and unsupported OER catalyst not only reduces the electrolysis efficiency, but also influences the initial performance of the fuel cell. Herein, Ti₄O₇ supported IrO_x is synthesized by utilizing the surfactant-assistant method and serves as reversal tolerant components in the anode. When the cell reverse time is less than 100 min, the cell voltage of the MEA added with IrO_x/Ti₄O₇ has almost no attenuation. Besides, the MEA has a longer reversal time (530 min) than IrO_x (75 min), showing an excellent reversal tolerance. The results of electron microscopy spectroscopy show that IrO_x particles have a good dispersity on the surface of Ti₄O₇ and IrO_x/Ti₄O₇ particles are uniformly dispersed on the anode catalytic layer. After the stability test, the Ti₄O₇ support has little decay, demonstrating a high electrochemical stability. IrO_x/Ti₄O₇ with a high dispersity has a great potential to the application on the reversal tolerance anode of the fuel cell.

Graphical abstract

Keywords

proton exchange membrane fuel cell (PEMFC) / fuel starvation / cell reverse / reversal tolerance anode / oxygen evolution reaction

References

[1] Hong B K, Mandal P, Oh J G, On the impact of water activity on reversal tolerant fuel cell anode performance and durability. Journal of Power Sources, 2016, 328: 280–288

[2] Polagani R K, Suryawanshi P L, Gumfekar S P, Ultrasound-assisted synthesis of Pt–Co/C bimetallic alloys for oxygen reduction in PEM fuel cells. Sustainable Energy & Fuels, 2018, 2(7): 1491–1499

[3] Debe M K. Electrocatalyst approaches and challenges for automotive fuel cells. Nature, 2012, 486(7401): 43–51

[4] Jang J, Sharma M, Choi D, Boosting fuel cell durability under shut-down/start-up conditions using a hydrogen oxidation-selective metal-carbon hybrid core-shell catalyst. ACS Applied Materials & Interfaces, 2019, 11(31): 27735–27742

[5] Huang Z, Shen J, Chan S H, Transient response of performance in a proton exchange membrane fuel cell under dynamic loading. Energy Conversion and Management, 2020, 226: 113492

[6] Zhou X, Ji H, Li B, High-repetitive reversal tolerant performance of proton-exchange membrane fuel cell by designing a suitable anode. ACS Omega, 2020, 5(17): 10099–10105

[7] Shen J, Xu L, Chang H, Partial flooding and its effect on the performance of a proton exchange membrane fuel cell. Energy Conversion and Management, 2020, 207: 112537

[8] Liang D, Shen Q, Hou M, Study of the cell reversal process of large area proton exchange membrane fuel cells under fuel starvation. Journal of Power Sources, 2009, 194(2): 847–853

[9] Taniguchi A, Akita T, Yasuda K, Analysis of electrocatalyst degradation in PEMFC caused by cell reversal during fuel starvation. Journal of Power Sources, 2004, 130(1–2): 42–49

[10] Zhou F, Andreasen S J, Kær S K, Analysis of accelerated degradation of a HT-PEM fuel cell caused by cell reversal in fuel starvation condition. International Journal of Hydrogen Energy, 2015, 40(6): 2833–2839

[11] Mandal P, Hong B K, Oh J G, Understanding the voltage reversal behavior of automotive fuel cells. Journal of Power Sources, 2018, 397: 397–404

[12] Lim K H, Lee W H, Jeong Y, Analysis of carbon corrosion in anode under fuel starvation using on-line mass spectrometry in polymer electrolyte membrane fuel cells. Journal of the Electrochemical Society, 2017, 164(14): F1580–F1586

[13] Hu L, Hong B K, Oh J G, Robust operation of fuel cell systems in subfreezing conditions: a material-based solution to achieve better anode durability. ACS Applied Energy Materials, 2019, 2(10): 7152–7161

[14] Cai C, Rao Y, Zhou J, Carbon corrosion: a novel termination mechanism of the water electrolysis plateau during voltage reversal. Journal of Power Sources, 2020, 473: 228542

[15] Moore C E, Eastcott J, Cimenti M, Novel methodology for ex situ characterization of iridium oxide catalysts in voltage reversal tolerant proton exchange membrane fuel cell anodes. Journal of Power Sources, 2019, 417: 53–60

[16] Joo T, Hu L, Hong B K, On the origin of deactivation of reversal-tolerant fuel cell anodes under voltage reversal conditions. Journal of Power Sources, 2020, 472: 228439

[17] Zhao J, Tu Z, Chan S H. Carbon corrosion mechanism and mitigation strategies in a proton exchange membrane fuel cell (PEMFC): a review. Journal of Power Sources, 2021, 488: 229434

[18] Ghosh S, Ohashi H, Tabata H, In-plane and through-plane non-uniform carbon corrosion of polymer electrolyte fuel cell cathode catalyst layer during extended potential cycles. Journal of Power Sources, 2017, 362: 291–298

[19] Lü W, Liu Z, Wang C, The effects of pinholes on proton exchange membrane fuel cell performance. International Journal of Energy Research, 2011, 35(1): 24–30

[20] Lauritzen M V, He P, Young A P, Study of fuel cell corrosion processes using dynamic hydrogen reference electrodes. Journal of New Materials for Electrochemical Systems, 2007, 10(3): 143–145

[21] Baumgartner W R, Parz P, Fraser S D, Polarization study of a PEMFC with four reference electrodes at hydrogen starvation conditions. Journal of Power Sources, 2008, 182(2): 413–421

[22] Chen H, Zhao X, Zhang T, The reactant starvation of the proton exchange membrane fuel cells for vehicular applications: a review. Energy Conversion and Management, 2019, 182: 282–298

[23] Atanasoski R T, Cullen D A, Vernstrom G D, A materials-based mitigation strategy for SU/SD in PEM fuel cells: properties and performance-specific testing of IrRu OER catalysts. ECS Electrochemistry Letters, 2013, 2(3): F25–F28

[24] Knights S D, Colbow K M, St-Pierre J, Aging mechanisms and lifetime of PEFC and DMFC. Journal of Power Sources, 2004, 127(1–2): 127–134

[25] Kim T Y, Lee S W, Pak C. Optimization of carbon-supported Ir–Ru alloys for polymer electrolyte fuel cell anodes under cell reversal. Journal of Industrial and Engineering Chemistry, 2020, 85: 87–93

[26] You E, Min M, Jin S A, Highly durable, cost-effective, and multifunctional carbon-supported IrRu-based catalyst for automotive polymer electrolyte fuel cell anodes. Journal of the Electrochemical Society, 2018, 165(6): F3094–F3099

[27] Wang J, Zhou X, Li B, Highly efficient, cell reversal resistant PEMFC based on PtNi/C octahedral and OER composite catalyst. International Journal of Hydrogen Energy, 2020, 45(15): 8930–8940

[28] Kötz R, Lewerenz H J, Brüesch P, Oxygen evolution on Ru and Ir electrodes. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1983, 150(1–2): 209–216

[29] Trasatti S. Electrocatalysis in the anodic evolution of oxygen and chlorine. Electrochimica Acta, 1984, 29(11): 1503–1512

[30] Roh C W, Kim H E, Choi J, Monodisperse IrO_x deposited on Pt/C for reversal tolerant anode in proton exchange membrane fuel cell. Journal of Power Sources, 2019, 443: 227270

[31] Jang I, Hwang I, Tak Y. Attenuated degradation of a PEMFC cathode during fuel starvation by using carbon-supported IrO₂. Electrochimica Acta, 2013, 90: 148–156

[32] Krishnan P, Advani S G, Prasad A K. Magneli phase Ti_n O_2n−1 as corrosion-resistant PEM fuel cell catalyst support. Journal of Solid State Electrochemistry, 2012, 16(7): 2515–2521

[33] Ioroi T, Yasuda K. Highly reversal-tolerant anodes using Ti₄O₇-supported platinum with a very small amount of water-splitting catalyst. Journal of Power Sources, 2020, 450: 227656

[34] Won J E, Kwak D H, Han S B, PtIr/Ti₄O₇ as a bifunctional electrocatalyst for improved oxygen reduction and oxygen evolution reactions. Journal of Catalysis, 2018, 358: 287–294

[35] Li G, Yu H, Wang X, Highly effective Ir_xSn_1−xO₂ electrocatalysts for oxygen evolution reaction in the solid polymer electrolyte water electrolyser. Physical Chemistry Chemical Physics, 2013, 15(8): 2858–2866

[36] Wilson M S, Gottesfeld S. Thin-film catalyst layers for polymer electrolyte fuel cell electrodes. Journal of Applied Electrochemistry, 1992, 22(1): 1–7

[37] Lee Y, Suntivich J, May K J, Synthesis and activities of rutile IrO₂ and RuO₂ nanoparticles for oxygen evolution in acid and alkaline solutions. Journal of Physical Chemistry Letters, 2012, 3(3): 399–404

[38] da Silva G C, Perini N, Ticianelli E A. Effect of temperature on the activities and stabilities of hydrothermally prepared IrO_x nanocatalyst layers for the oxygen evolution reaction. Applied Catalysis B: Environmental, 2017, 218: 287–297

[39] Siracusano S, Baglio V, D’Urso C, Preparation and characterization of titanium suboxides as conductive supports of IrO₂ electrocatalysts for application in SPE electrolysers. Electrochimica Acta, 2009, 54(26): 6292–6299

[40] Wei G, Wang Y, Huang C, The stability of MEA in SPE water electrolysis for hydrogen production. International Journal of Hydrogen Energy, 2010, 35(9): 3951–3957

[41] Pfeifer V, Jones T E, Velasco Vélez J J, The electronic structure of iridium oxide electrodes active in water splitting. Physical Chemistry Chemical Physics, 2016, 18(4): 2292–2296

[42] Badam R, Hara M, Huang H H, Synthesis and electrochemical analysis of novel IrO₂ nanoparticle catalysts supported on carbon nanotube for oxygen evolution reaction. International Journal of Hydrogen Energy, 2018, 43(39): 18095–18104

[43] Abbott D F, Lebedev D, Waltar K, Iridium oxide for the oxygen evolution reaction: correlation between particle size, morphology, and the surface hydroxo layer from operando XAS. Chemistry of Materials, 2016, 28(18): 6591–6604

[44] Senevirathne K, Hui R, Campbell S, Electrocatalytic activity and durability of Pt/NbO₂ and Pt/Ti₄O₇ nanofibers for PEM fuel cell oxygen reduction reaction. Electrochimica Acta, 2012, 59: 538–547

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