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Title: Novel Composite Materials for SOFC Cathode-Interconnect Contact

Abstract

This report summarized the research efforts and major conclusions of our University Coal Research Project, which focused on developing a new class of electrically-conductive, Cr-blocking, damage-tolerant Ag-perovksite composite materials for the cathode-interconnect contact of intermediate-temperature solid oxide fuel cell (SOFC) stacks. The Ag evaporation rate increased linearly with air flow rate initially and became constant for the air flow rate {ge} {approx} 1.0 cm {center_dot} s{sup -1}. An activation energy of 280 KJ.mol{sup -1} was obtained for Ag evaporation in both air and Ar+5%H{sub 2}+3%H{sub 2}O. The exposure environment had no measurable influence on the Ag evaporation rate as well as its dependence on the gas flow rate, while different surface morphological features were developed after thermal exposure in the oxidizing and reducing environments. Pure Ag is too volatile at the SOFC operating temperature and its evaporation rate needs to be reduced to facilitate its application as the cathode-interconnect contact. Based on extensive evaporation testing, it was found that none of the alloying additions reduced the evaporation rate of Ag over the long-term exposure, except the noble metals Au, Pt, and Pd; however, these noble elements are too expensive to justify their practical use in contact materials. Furthermore, the additionmore » of La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LSM) into Ag to form a composite material also did not significantly modify the Ag evaporation rate. The Ag-perovskite composites with the perovskite being either (La{sub 0.6}Sr{sub 0.4})(Co{sub 0.8}Fe{sub 0.2})O{sub 3} (LSCF) or LSM were systematically evaluated as the contact material between the ferritic interconnect alloy Crofer 22 APU and the LSM cathode. The area specific resistances (ASRs) of the test specimens were shown to be highly dependent on the volume percentage and the type of the perovskite present in the composite contact material as well as the amount of thermal cycling that the specimens were subjected to during testing. The Ag-LSCF composite contact materials proved more effective in trapping Cr within the contact material and preventing Cr migration into the cathode than the Ag-LSM composites. Ag-perovskite composite contact materials are promising candidates for use in intermediate-temperature SOFC stacks with ferritic stainless steel interconnects due to their ability to maintain acceptably low ASRs while reducing Cr migration into the cathode material.« less

Authors:
Publication Date:
Research Org.:
Tennessee Technological University
Sponsoring Org.:
USDOE
OSTI Identifier:
981820
DOE Contract Number:
FG26-05NT42533
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 01 COAL, LIGNITE, AND PEAT; 30 DIRECT ENERGY CONVERSION; ACTIVATION ENERGY; AIR; AIR FLOW; ALLOYS; CATHODES; COAL; COMPOSITE MATERIALS; EVAPORATION; GAS FLOW; PEROVSKITE; SOLID OXIDE FUEL CELLS; STAINLESS STEELS; TESTING; THERMAL CYCLING; TRAPPING

Citation Formats

J. H. Zhu. Novel Composite Materials for SOFC Cathode-Interconnect Contact. United States: N. p., 2009. Web. doi:10.2172/981820.
J. H. Zhu. Novel Composite Materials for SOFC Cathode-Interconnect Contact. United States. doi:10.2172/981820.
J. H. Zhu. Fri . "Novel Composite Materials for SOFC Cathode-Interconnect Contact". United States. doi:10.2172/981820. https://www.osti.gov/servlets/purl/981820.
@article{osti_981820,
title = {Novel Composite Materials for SOFC Cathode-Interconnect Contact},
author = {J. H. Zhu},
abstractNote = {This report summarized the research efforts and major conclusions of our University Coal Research Project, which focused on developing a new class of electrically-conductive, Cr-blocking, damage-tolerant Ag-perovksite composite materials for the cathode-interconnect contact of intermediate-temperature solid oxide fuel cell (SOFC) stacks. The Ag evaporation rate increased linearly with air flow rate initially and became constant for the air flow rate {ge} {approx} 1.0 cm {center_dot} s{sup -1}. An activation energy of 280 KJ.mol{sup -1} was obtained for Ag evaporation in both air and Ar+5%H{sub 2}+3%H{sub 2}O. The exposure environment had no measurable influence on the Ag evaporation rate as well as its dependence on the gas flow rate, while different surface morphological features were developed after thermal exposure in the oxidizing and reducing environments. Pure Ag is too volatile at the SOFC operating temperature and its evaporation rate needs to be reduced to facilitate its application as the cathode-interconnect contact. Based on extensive evaporation testing, it was found that none of the alloying additions reduced the evaporation rate of Ag over the long-term exposure, except the noble metals Au, Pt, and Pd; however, these noble elements are too expensive to justify their practical use in contact materials. Furthermore, the addition of La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LSM) into Ag to form a composite material also did not significantly modify the Ag evaporation rate. The Ag-perovskite composites with the perovskite being either (La{sub 0.6}Sr{sub 0.4})(Co{sub 0.8}Fe{sub 0.2})O{sub 3} (LSCF) or LSM were systematically evaluated as the contact material between the ferritic interconnect alloy Crofer 22 APU and the LSM cathode. The area specific resistances (ASRs) of the test specimens were shown to be highly dependent on the volume percentage and the type of the perovskite present in the composite contact material as well as the amount of thermal cycling that the specimens were subjected to during testing. The Ag-LSCF composite contact materials proved more effective in trapping Cr within the contact material and preventing Cr migration into the cathode than the Ag-LSM composites. Ag-perovskite composite contact materials are promising candidates for use in intermediate-temperature SOFC stacks with ferritic stainless steel interconnects due to their ability to maintain acceptably low ASRs while reducing Cr migration into the cathode material.},
doi = {10.2172/981820},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Fri Jul 31 00:00:00 EDT 2009},
month = {Fri Jul 31 00:00:00 EDT 2009}
}

Technical Report:

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  • This report summarizes the work conducted by UConn SOFC seal development team during the Phase I program and no cost extension. The work included composite seal sample fabrication, materials characterizations, leak testing, mechanical strength testing, chemical stability study and acoustic-based diagnostic methods. Materials characterization work revealed a set of attractive material properties including low bulk permeability, high electrical resistivity, good mechanical robustness. Composite seal samples made of a number of glasses and metallic fillers were tested for sealing performance under steady state and thermal cycling conditions. Mechanical testing included static strength (pull out) and interfacial fracture toughness measurements. Chemically stabilitymore » study evaluated composite seal material stability after aging at 800 C for 168 hrs. Acoustic based diagnostic test was conducted to help detect and understand the micro-cracking processes during thermal cycling test. The composite seal concept was successfully demonstrated and a set of material (coating composition & fillers) were identified to have excellent thermal cycling performance.« less
  • An interconnect for an SOFC stack is used to connect fuel cells into a stack. SOFC stacks are expected to run for 40,000 hours and 10 thermal cycles for the stationary application and 10,000 hours and 7000 thermal cycles for the transportation application. The interconnect of a stack must be economical and robust enough to survive the SOFC stack operation temperature of 750 C and must maintain the electrical connection to the fuel cells throughout the lifetime and under thermal cycling conditions. Ferritic and austenitic stainless steels, and nickel-based superalloys were investigated as possible interconnect materials for solid oxide fuelmore » cell (SOFC) stacks. The alloys were thermally cycled in air and in a wet nitrogen-argon-hydrogen (N2-Ar-H2-H2O) atmosphere. Thermogravimetry was used to determine the parabolic oxidation rate constants of the alloys in both atmospheres. The area-specific resistance of the oxide scale and metal substrates were measured using a two-probe technique with platinum contacts. The study identifies two new interconnect designs which can be used with both bonded and compressive stack sealing mechanisms. The new interconnect designs offer a solution to chromium vaporization, which can lead to degradation of some (chromium-sensitive) SOFC cathodes.« less
  • This report summarizes the interconnect work being performed at Delphi. Materials were chosen for this interconnect project were chosen from ferritic and austenitic stainless steels, and nickel-based superalloys. The alloys are thermally cycled in air and a wet hydrogen atmosphere. The oxide scale adherence, electrical resistance and oxidation resistance are determined after long-term oxidation of each alloy. The oxide scale adherence will be observed using a scanning electron microscope. The electrical resistance of the oxidized alloys will be determined using an electrical resistance measurement apparatus which has been designed and is currently being built. Data from the electrical resistance measurementmore » is expected to be provided in the second quarter.« less
  • This report summarized the research efforts and major conclusions for our SECA Phase I and II project focused on Cr-free or low Cr Fe-Ni based alloy development for intermediate temperature solid oxide fuel cell (SOFC) interconnect application. Electrical conductivity measurement on bulk (Fe,Ni){sub 3}O{sub 4} coupons indicated that this spinel phase possessed a higher electrical conductivity than Cr{sub 1.5}Mn{sub 1.5}O{sub 4} spinel and Cr{sub 2}O{sub 3}, which was consistent with the low area specific resistance (ASR) of the oxide scale formed on these Fe-Ni based alloys. For Cr-free Fe-Ni binary alloys, although the increase in Ni content in the alloysmore » improved the oxidation resistance, and the Fe-Ni binary alloys exhibited adequate CTE and oxide scale ASR, their oxidation resistance needs to be further improved. Systematic alloy design efforts have led to the identification of one low-Cr (6wt.%) Fe-Ni-Co based alloy which formed a protective, electrically-conductive Cr{sub 2}O{sub 3} inner layer underneath a Cr-free, highly conductive spinel outer layer. This low-Cr, Fe-Ni-Co alloy has demonstrated a good CTE match with other cell components; high oxidation resistance comparable to that of Crofer; low oxide scale ASR with the formation of electrically-insulating phases in the oxide scale; no scale spallation during thermal cycling; adequate compatibility with cathode materials; and comparable mechanical properties with Crofer. The existence of the Cr-free (Fe,Co,Ni){sub 3}O{sub 4} outer layer effectively reduced the Cr evaporation and in transpiration testing resulted in a 6-fold decrease in Cr evaporation as compared to a state-of-the-art ferritic interconnect alloy. In-cell testing using an anode supported cell with a configuration of Alloy/Pt/LSM/YSZ/Ni+YSZ indicates that the formation of the Cr-free spinel layer via thermal oxidation was effective in blocking the Cr migration and thus improving the cell performance stability. Electroplating of the Fe-Ni-Co alloys as precursor to synthesize a protective spinel layer on commercial ferritic steels has been initiated to facilitate the utilization of the Cr-free spinel as a surface seal to block Cr evaporation. It is suggested that low-cost Fe-Ni-Co alloy coating on commercial ferritic steels might be the best approach to completely eliminate the Cr poisoning problem in SOFC stacks, while maintaining the relatively low overall cost of the interconnect component.« less