Corrosion of current cullector materials in the molten carbonate fuel cell
Sammanfattning: The corrosion of current collector materials in MoltenCarbonate Fuel Cells (MCFC) is investigated. The essential aimsof this investigation were to study the corrosion behaviour ofdifferent materials, in varying cathode and anode MCFCenvironments, and to study the contact corrosion resistancesbetween the MCFC current collector and electrodes. For thesepurposes, pure iron, iron-chromium binary alloys and severalcommercial steels were investigated in molten carbonate meltswithin the pot-cell laboratory set-up. In addition, the contactcorrosion resistances, between an AISI 310 current collectorand two cathodes (NiO and LiCoO2), were studied in a laboratory fuel cell.Post-tests were done to study the corrosion products formed atthe surfaces.In cathode environments, corrosion potential increased overtime as a protective corrosion layer slowly formed. Eventually,the potential reached a stable value close to the cathodeoperating potential. The main cathode reaction, as corrosionpotential increased, changed from water reduction to oxygenreduction. Corrosion rate under the operating cathode conditiondepended on the chromium content; the higher the concentrationof chromium, the lower the corrosion rate. The corrosion ratesof ferritic steels, with high chromium content, and AISI 310were higher at the so-called outlet operating condition incomparison to the standard and so-called inlet conditions. Thecorrosion rate was higher at the beginning of the exposure,which resulted in a relatively fast corrosion layer growth thatslowed as the protective layer was formed. It was shown thatthe corrosion layers, formed on iron-chromium alloys, AISI 310and ferritic high chromium-containing steels, consisted of twolayers. The outer layer was porous and iron rich, while theinner layer was quite compact and rich in chromium and/oraluminiumTherefore, the corrosion behaviour was dependent onthe corrosion layer structure at the metal surface.In anode environments, the beneficial behaviour of aluminiumin ferritic alloys, with high aluminium contents, was due tothe formation of aluminium oxide and/or lithium aluminium oxideat the surface. The corrosion rates at the standard and outletconditions were of the same order of magnitude, while thecorrosion rates at the inlet conditions were considerablyhigher. The lower temperatures and higher carbon dioxideconcentrations in the inlet conditions appeared to result in asurface layer deficient in aluminium. A modified theoreticalmodel was developed to evaluate the corrosion current densitiesfrom experimental polarisation curves or linear polarisationresistance measurements in anode environments. The fittingswere found to be very good.An experimental method was developed forin-situmeasurements of the contributions to the totalohmic losses at the cathode in a laboratory scale MCFC. Thecontact resistance between the cathode and current collectorcontributed quite a large value to the total cathodepolarization. The corrosion layer, formed between the LiCoO2cathode and AISI 310 current collector, wasiron-rich and more porous, and contained a small amount ofcobalt. This was deemed to consist of a two-phase oxide, whichresulted in a lower conductivity. The corrosion layer, formedbetween the NiO cathode and AISI 310 current collector, wasrich in nickel. The corrosion layers on the AISI 310, incontact with the cathode, had a different composition comparedto samples immersed in carbonate melts.Key words: molten carbonate fuel cell (MCFC), corrosion,current collector, contact corrosion resistance.
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