Vladimir Shemet

Metallic materials in solid oxide fuel cells

Fe-Cr alloys with variations in chromium content and additions of different elements were studied for potential application in intermediate temperature Solid Oxide Fuel Cell (SOFC). Recently, a new type of FeCrMn(Ti/La) based ferritic steels has been developed to be used as construction material for SOFC interconnects. In the present paper, the long-term oxidation resistance of these class of steels in both air and simulated anode gas will be discussed and compared with the behaviour of a number of commercial available ferritic steels. Besides, in-situ studies were carried out to characterize the high temperature conductivity of the oxide scales formed under these conditions. Main emphasis will be put on the growth and adherence of the oxide scales formed during exposure, their contact resistance at service temperature as well as their interaction with various perovskite type contact materials. Additionally, parameters and protection methods in respect to the volatilization of chromia based oxide scales will be illustrated.

Oxidation of Metallic Materials in Simulated CO2/H2O-Rich Service Environments Relevant to an Oxyfuel Plant

In the present study the oxidation behaviour of a number of candidate alloys for heat exchanging components was investigated in model gas mixtures containing high amounts of CO2 and/or water vapour in the temperature range 550-700°C up to exposure times of 1000 h. During exposure in Ar/CO2 and Ar/CO2/H2O base gas mixtures at 550-650°C the oxidation rates and scale compositions of martensitic 9-12%Cr steels were similar to those previously observed in steam environments. Thin and protective Cr-rich oxide scales which are commonly found during air oxidation was observed locally on the specimens surfaces after oxidation in Ar-(1-3%)O2-CO2. The tendency for protective chromia base scale formation increased when 3% oxygen was added, especially for the 12%Cr steel. When iron base oxide scales were formed on the metal surface, the martensitic steels tended to exhibit carburisation whereby the extent was reduced by increasing the water vapour and oxygen contents. All three studied austenitic alloys exhibited very slow scale growth rates at 550°C, however, at and above 600°C the steels with lower Cr content started to form two-layered iron rich surface oxide scales whereby the outer oxide was prone to spallation upon thermal cycling. The high-Cr austenitic steel 310N and the nickel base alloy 617 formed very thin, Cr-rich oxide scales at all used test temperatures and atmospheres. For those two materials the oxidation behaviour in gases containing water vapour in combination with intentionally added oxygen was affected by formation of volatile chromium oxyhydroxide.

Hydrogen Uptake and Hydrogen Profiles in Chromia Scales Formed on Ni25Cr(Mn) in Low pO2 Test Gases at 1000°C

Two chromia forming materials have been exposed to different test gases at low pO2. All used test gases contained hydrogen species in the form of molecular hydrogen and water vapour. To insure the validity of the measured H-profiles H2 was replaced by with D2 and H2O by D2O. The Deuterium profiles in the oxides formed were established using SIMS and GDOES techniques. The profiles were quantified and correlated with the growth rate and the microstructures of the chromia scales formed on in low pO2 test gases. The presence of H2/H2O in the low pO2 test gas alters the properties of thermally growing chromia scales.

A Comparative Study Between Resistance Measurements in Model Experiments and Solid Oxide Fuel Cell Stack Performance Tests

Several combinations of glass-ceramic and steel compositions with excellent chemical and physical properties have been tested in the past in solid oxide fuel cell (SOFC) stacks, but there have also been some combinations exhibiting pronounced chemical interactions causing severe stack degradation. Parallel to the examination of these degradation and short-circuiting phenomena in stack tests, recently less complex model experiments have been developed to study the interaction of glass-ceramic sealants and interconnect steels. The sealants and steels were tested in the model experiments at operation temperature using a dual air/hydrogen atmosphere similar to stack conditions. The present work compares electrochemical performance under constant current load of SOFC stack tests with the resistance changes in model experiments. In addition, microstructural results of post-operation inspection of various sealant-steel combinations are presented. The model experiments have shown that under the chosen experimental conditions, distinct changes of the specific resistance of the specimens correlate well with the changes of the electrochemical performance of SOFC stacks, indicating that this method can be considered as an excellent comparative method to provide useful information on the physical and chemical interactions between glass-ceramic sealants and ferritic steels.

On Potential Application of Coated Ferritic Stainless Steel Grades K41X and K44X in SOFC/HTE Interconnects

K41X is a ferritic stainless steel grade which was successfully developed in exhaust gas manifold where the temperature could reach 950°C. It contains about 18% wt of chromium and it is stabilized with both titanium and niobium to warranty a good weldability, formability and high temperature corrosion resistance. Moreover, an addition of niobium improves high temperature mechanical properties, in particular the creep resistance. K44X, an enhanced version of K41X with 19%-wt. of Cr plus niobium and molybdenum, was recently developed to be used up to 1000°C. It exhibits better high temperature properties and oxidation resistance. Thanks to their high temperature resistance and their cost competitiveness, these two grades were recently considered as potential candidates to be used as interconnects for Solid Oxide Fuel Cells (SOFC) and High Temperature Electrolysis (HTE), either bare or more certainly coated in order to increase the life duration of the SOFC or HTE systems. This paper will present the high temperature properties of K41X and K44X, in particular oxidation behavior in isothermal and cyclic conditions under operating atmosphere. The positive effect of the addition of a protective coating on these steel grades in terms of oxidation resistance will then be presented. Most of the studied coatings are Mn-Co spinels deposited by sol-gel, atmospheric plasma spray or electroplating, their aim being to limit the chromium evaporation and to fit the severe performance requirements. They lead to low and stable contact resistance, which is a requirement necessary for long-term SOFC/HTE operation: for example a contact resistance of 22 mΩ.cm was obtained after 3500 h at 800°C in air with MnCoFe spinel coating. In this respect, K41X was recently chosen to be tested for the 3 generation stacks of SOFC in the European project “REAL SOFC” or the prototypes in French ANR projects. ECS Transactions, 35 (1) 2481-2488 (2011) 10.1149/1.3570246

Suitability of Metallic Materials for Interconnects in Solid Oxide Fuel Cells

FeCr model alloys with variation of chromium content, reactive element addition and spinel forming elements were studied in respect to oxidation resistance at 800°C. Additionally, in-situ studies were carried out to characterize the high temperature conductivity of the formed surface oxide scales. Based on these results, two model steels and a commercial material, alloy 446, were selected tor further qualification. First tests in respect to oxide scale formation, oxide conductivity, formation of volatile species and compatibility with contact materials showed potential suitability of these steels as construction material for SOFC interconnect.