Abstract
Based on the specific structure of tubular solid oxide fuel cells, good chemical, microstructural, and phase stabilities for the protective coating are required in both the oxidizing and reducing environments. In this work, MnCo2O4 coatings were deposited onto porous Ni50Cr50-Al2O3 substrate by atmospheric plasma spray. The coated samples were tested at 800 °C with the coating exposed in air environment and the substrate in H2 environment. Reducing and pre-oxidizing treatments were performed prior to the stability test. The microstructural stability, phase composition, and electrical properties of the tested coatings were investigated. The surface morphology exhibited an excellent surface stability, and no obvious crystal coarsening was observed. With enhancement of the testing duration, the area-specific resistance presented a decreasing trend attributed to increase in the contact interface and densification of the upper layer. The cross-section views presented a dense upper layer and a relatively porous bottom layer. The x-ray diffraction results also indicated a single MnCo2O4 phase in the upper layer exposed to air environment and a reduced phase structure in the bottom layer from the substrate side. The evolution mechanism between the oxidation frontier and the reduction interface was then discussed.
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E. Ballée, A. Ringuedé, M. Cassir, M. Putkonen, and L. Niinistö, Synthesis of a Thin-Layered Ionic Conductor, CeO2-Y2O3, by Atomic Layer Deposition in View of Solid Oxide Fuel Cell Applications, Chem. Mater., 2009, 21(19), p 4614-4619
A. Evans, A. Bieberle-Hütter, J.L.M. Rupp, and L.J. Gauckler, Review on Microfabricated Micro-Solid Oxide Fuel Cell Membranes, J. Power Sour., 2009, 194(1), p 119-129
J.W. Fergus, Metallic Interconnects for Solid Oxide Fuel Cells, Mater. Sci. Eng. A, 2005, 397(1-2), p 271-283
J.W. Fergus, Synergism in the Design of Interconnect Alloy-Coating Combinations Solid for Oxide Fuel Cells, Scr. Mater., 2011, 65(2), p 73-77
I. Antepara, I. Villarreal, L.M. Rodríguez-Martínez, N. Lecanda, U. Castro, and A. Laresgoiti, Evaluation of Ferritic Steels for Use as Interconnects and Porous Metal Supports in IT-SOFCs, J. Power Sour., 2005, 151, p 103-107
J. Froitzheim, G.H. Meier, L. Niewolak, P.J. Ennis, H. Hattendorf, L. Singheiser, and W.J. Quadakkers, Development of High Strength Ferritic Steel for Interconnect Application in SOFCs, J. Power Sour., 2008, 178(1), p 163-173
P. Gannon, V. Gorokhovsky, M. Deibert, R. Smith, A. Kayani, P. White, S. Sofie, Z. Yang, D. McCready, and S. Visco, Enabling Inexpensive Metallic Alloys as SOFC Interconnects: An Investigation into Hybrid Coating Technologies to Deposit Nanocomposite Functional Coatings on Ferritic Stainless Steels, Int. J. Hydrog. Energy, 2007, 32(16), p 3672-3681
M. Stanislowski, E. Wessel, K. Hilpert, T. Markus, and L. Singheiser, Chromium Vaporization from High-Temperature Alloys: I. Chromia-Forming Steels and the Influence of Outer Oxide Layers, J. Electrochem. Soc., 2007, 154(4), p A295-A306
M. Hänsel, W.J. Quadakkers, and D.J. Young, Role of Water Vapor in Chromia-Scale Growth at Low Oxygen Partial Pressure, Oxid. Met., 2003, 59(3-4), p 285-301 (in English)
A. Petric and H. Ling, Electrical Conductivity and Thermal Expansion of Spinels at Elevated Temperatures, J. Am. Ceram. Soc., 2007, 90(5), p 1515-1520
H. Bordeneuve, C. Tenailleau, S. Guillemet-Fritsch, R. Smith, E. Suard, and A. Rousset, Structural Variations and Cation Distributions in Mn3−xCoxO4 (0 ≤ x≤3) Dense Ceramics Using Neutron Diffraction Data, Solid State Sci., 2010, 12(3), p 379-386
H. Kurokawa, C. Jacobson, L. Dejonghe, and S. Visco, Chromium Vaporization of Bare and of Coated Iron-Chromium Alloys at 1073 K, Solid State Ion., 2007, 178(3-4), p 287-296
M. Pihlatie, J. Lagerbom, T. Salminen, J. Laakso, L. Hyvärinen, M. Kylmälahti, O. Himanen, J. Kiviaho, and P. Vuoristo, Influence of Powder Composition and Manufacturing Method on Electrical and Chromium Barrier Properties of Atmospheric Plasma Sprayed Spinel Coatings Prepared from MnCo2O4 and Mn2CoO4 + Co Powders on Crofer 22 APU Interconnectors, Int. J. Hydrog. Energy, 2014, 39(30), p 17246-17257
Z. Yang, G. Xia, X. Li, and J. Stevenson (Mn, Co)3O4 Spinel Coatings on Ferritic Stainless Steels for SOFC Interconnect Applications, Int. J. Hydrog. Energy, 2007, 32(16), p 3648-3654
J.W. Stevenson, Z.G. Yang, G.G. Xia, Z. Nie, and J.D. Templeton, Long-Term Oxidation Behavior of Spinel-Coated Ferritic Stainless Steel for Solid Oxide Fuel Cell Interconnect Applications, J. Power Sour., 2013, 231, p 256-263
Z. Yang, G.-G. Xia, G.D. Maupin, and J.W. Stevenson, Conductive Protection Layers on Oxidation Resistant Alloys for SOFC Interconnect Applications, Surf. Coat. Technol., 2006, 201(7), p 4476-4483
N.V. Gavrilov, V.V. Ivanov, A.S. Kamenetskikh, and A.V. Nikonov, Investigations of Mn-Co-O and Mn-Co-Y-O Coatings Deposited by the Magnetron Sputtering on Ferritic Stainless Steels, Surf. Coat. Technol., 2011, 206(6), p 1252-1258
W. Wei, W. Chen, and D.G. Ivey, Oxidation Resistance and Electrical Properties of Anodically Electrodeposited Mn-Co Oxide Coatings for Solid Oxide Fuel Cell Interconnect Applications, J. Power Sour., 2009, 186(2), p 428-434
H. Zhang, Z. Zhan, and X. Liu, Electrophoretic Deposition of (Mn, Co)3O4 Spinel Coating for Solid Oxide Fuel Cell Interconnects, J. Power Sour., 2011, 196(19), p 8041-8047
J. Wu, Y. Jiang, C. Johnson, and X. Liu, DC Electrodeposition of Mn-Co Alloys on Stainless Steels for SOFC Interconnect Application, J. Power Sour., 2008, 177(2), p 376-385
J. Puranen, J. Laakso, M. Kylmälahti, and P. Vuoristo, Characterization of High-Velocity Solution Precursor Flame-Sprayed Manganese Cobalt Oxide Spinel Coatings for Metallic SOFC Interconnectors, J. Therm. Spray Technol., 2013, 22(5), p 622-630
J. Puranen, J. Lagerbom, L. Hyvärinen, M. Kylmälahti, O. Himanen, M. Pihlatie, J. Kiviaho, and P. Vuoristo, The Structure and Properties of Plasma Sprayed Iron Oxide Doped Manganese Cobalt Oxide Spinel Coatings for SOFC Metallic Interconnectors, J. Therm. Spray Technol., 2010, 20(1-2), p 154-159
J. Puranen, J. Lagerbom, L. Hyvärinen, T. Mäntylä, E. Levänen, M. Kylmälahti, and P. Vuoristo, Formation and Structure of Plasma Sprayed Manganese-Cobalt Spinel Coatings on Preheated Metallic Interconnector Plates, Surf. Coat. Technol., 2010, 205(4), p 1029-1033
O. Thomann, M. Pihlatie, M. Rautanen, O. Himanen, J. Lagerbom, M. Mäkinen, T. Varis, T. Suhonen, and J. Kiviaho, Development and Application of HVOF Sprayed Spinel Protective Coating for SOFC Interconnects, J. Therm. Spray Technol., 2013, 22(5), p 631-639
C.-X. Li, L.-L. Yun, Y. Zhang, C.-J. Li, and L.-J. Guo, Microstructure, Performance and Stability of Ni/Al2O3 Cermet-Supported SOFC Operating with Coal-Based Syngas Produced Using Supercritical Water, Int. J. Hydrog. Energy, 2012, 37(17), p 13001-13006
L.J.H. Kuo, S.D. Vora, and S.C. Singhal, Plasma Spraying of Lanthanum Chromite Films for Solid Oxide Fuel Cell Interconnection Application, J. Am. Ceram. Soc., 1997, 80(3), p 589-593
H. Tsukuda, A. Notomi, and N. Histatome, Application of Plasma Spraying to Tubular-Type Solid Oxide Fuel Cells Production, J. Therm. Spray Technol., 2000, 9(3), p 364-368
C.J. Li and A. Ohmori, Relationships Between the Microstructure and Properties of Thermally Sprayed Deposits, J. Therm. Spray Technol., 2002, 11(3), p 365-374
C.-J. Li, C.-X. Li, and M. Wang, Effect of Spray Parameters on the Electrical Conductivity of Plasma-Sprayed La1−xSrxMnO3 Coating for the Cathode of SOFCs, Surf. Coat. Technol., 2005, 198(1-3), p 278-282
X.-J. Ning, C.-X. Li, C.-J. Li, and G.-J. Yang, Modification of Microstructure and Electrical Conductivity of Plasma-Sprayed YSZ Deposit Through Post-Densification Process, Mater. Sci. Eng. A, 2006, 428(1-2), p 98-105
Y.-Z. Hu, C.-X. Li, G.-J. Yang, and C.-J. Li, Evolution of Microstructure During Annealing of Mn1.5Co1.5O4 Spinel Coatings Deposited by Atmospheric Plasma Spray, Int. J. Hydrog. Energy, 2014, 39(25), p 13844-13851
S.-L. Zhang, C.-X. Li, C.-J. Li, and G.-J. Yang, Microstructure and Properties of Porous Ni50Cr50-Al2O3 Cermet Support for Solid Oxide Fuel Cells, J. Therm. Spray Technol., 2012, 22(2-3), p 158-165
J. Puranen, M. Pihlatie, J. Lagerbom, G. Bolelli, J. Laakso, L. Hyvärinen, M. Kylmälahti, O. Himanen, J. Kiviaho, L. Lusvarghi, and P. Vuoristo, Post-Mortem Evaluation of Oxidized Atmospheric Plasma Sprayed Mn-Co-Fe Oxide Spinel Coatings on SOFC Interconnectors, Int. J. Hydrog. Energy, 2014, 39(30), p 17284-17294
K. Wang, Y. Liu, and J.W. Fergus, Interactions Between SOFC Interconnect Coating Materials and Chromia, J. Am. Ceram. Soc., 2011, 94(12), p 4490-4495
Acknowledgment
The present project was financially supported by the National Basic Research Program of China (No. 2012CB625100).
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Hu, YZ., Li, CX., Zhang, SL. et al. The Microstructure Stability of Atmospheric Plasma-Sprayed MnCo2O4 Coating Under Dual-Atmosphere (H2/Air) Exposure. J Therm Spray Tech 25, 301–310 (2016). https://doi.org/10.1007/s11666-015-0346-8
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DOI: https://doi.org/10.1007/s11666-015-0346-8