Thermodynamic considerations on Cr poisoning in SOFC cathodes

Yokokawa, Harumi; Horita, Teruhisa; Sakai, Natsuko; Yamaji, Katsuhiko; Brito, Manuel E.; Xiong, Yueping; Kishimoto, Haruo

doi:10.1016/j.ssi.2006.07.055

Cited by 254 publications

(187 citation statements)

References 28 publications

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“…Although thermodynamically predicted, chromium substitution into the perovskite lattice of (La,Sr)MnO 3 has not been observed during the course of chromium poisoning experiments, suggesting slow kinetics [21].…”

Section: Introductionmentioning

confidence: 91%

Conductivity and oxygen reduction activity changes in lanthanum strontium manganite upon low-level chromium substitution

Tsekouras

Braun

2014

Solid State Ionics

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On the timescale of solid oxide fuel cell (SOFC) system lifetime requirements, the thermodynamically predicted low-level substitution of chromium on the B-site of (La,Sr)MnO 3 could be a source of cathode degradation underlying more overt and well-known chromium poisoning mechanisms. To study this phenomenon in isolation, electronic conductivity (σ) and electrochemical oxygen reduction activity of the (La 0.8 Sr 0.2 ) 0.98 Cr x Mn 1−x O 3 model series (x = 0, 0.02, 0.05 or 0.1) were measured in air between 850 and 650 °C. Depending on the extent of chromium substitution and the measurement temperature, electrochemical impedance spectroscopy (EIS) results could be deconvoluted into a maximum of three contributions reflecting possible limiting processes such as oxide ion transport and dissociative adsorption. Chromium substitution resulted in lowered σ (from 174 S cm − 1 (x = 0) to 89 S cm − 1 (x = 0.1) at 850 °C) and a steady rise in associated activation energy (E a ) (from 0.105 ± 0.001 eV (x = 0) to 0.139 ± 0.001 eV (x = 0.1)). From EIS analyses, ohmic and polarisation resistances increased, whilst Ea for the overall oxygen reduction reaction also increased from 1.39 ± 0.04 eV (x = 0) to 1.48-1.54 ± 0.04 eV upon chromium substitution.Keywords level, conductivity, oxygen, reduction, activity, changes, chromium, lanthanum, substitution, strontium, manganite, upon, low Depending on the extent of chromium substitution and the measurement temperature, electrochemical impedance spectroscopy (EIS) results could be deconvoluted into a maximum of three contributions 2 reflecting possible limiting processes such as oxide ion transport and dissociative adsorption. Chromium substitution resulted in lowered  (from 174 S cm -1 (x = 0) to 89 S cm -1 (x = 0.1) at 850 °C) and a steady rise in associated activation energy (E a ) (from 0.105 ± 0.001 eV (x = 0) to 0.139 ± 0.001 eV (x = 0.1)). From EIS analysis, ohmic and polarisation resistances increased, whilst E a for the overall oxygen reduction reaction also increased from 1.39 ± 0.04 eV (x = 0) to 1.48-1.54 ± 0.04 eV upon chromium substitution.

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Section: Introductionmentioning

confidence: 91%

Conductivity and oxygen reduction activity changes in lanthanum strontium manganite upon low-level chromium substitution

Tsekouras

Braun

2014

Solid State Ionics

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“…An isothermal section of the La-Mn-Cr-O oxide system at 1073 K in air and pure oxygen has been published without further commenting of experimental evidences. 46 Complete solid solution between the LaMnO 3 and the LaCrO 3 perovskites was affirmed. 17 d of LaMn 0.9 Cr 0.1 O 3Àd was measured using thermogravimetry.…”

Section: B La-sr-cr-oxidementioning

confidence: 90%

Thermodynamic modeling of La₂O₃–SrO–Mn₂O₃–Cr₂O₃for solid oxide fuel cell applications

et al. 2012

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“…5) suggests that it is the former of the two. Indeed, the concept of Cr "poisoning" of alkali and alkaline earth containing metal oxides is a well known phenomenon within the solid oxide fuel cell community 27 . Table 2b for comparison to the results of the more accurate linear extrapolation method.…”

Section: Interface Composition and Evolutionmentioning

confidence: 99%

Characterization of the interface between an Fe–Cr alloy and the p-type thermoelectric oxide Ca3Co4O9

Holgate

Han

et al. 2014

Journal of Alloys and Compounds

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of the interface between an Fe-Cr alloy and the p-type thermoelectric oxide Ca 3 Co 4 O 9 , (2013), doi: http://dx.doi.org/10. 1016/j.jallcom.2013.08.096 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Characterization of the interface between an AbstractA customized Fe-Cr alloy that has been optimized for high temperature applications in oxidizing atmospheres has been interfaced via spark plasma sintering (SPS) with a p-type thermoelectric oxide material: calcium cobaltate (Ca 3 Co 4 O 9 ). The properties of the alloy have been analyzed for its compatibility with the Ca 3 Co 4 O 9 in terms of its thermal expansion and transport properties. The thermal and electrical contact resistances have been measured as a function of temperature, and the long term electronic integrity of the interface analyzed by measuring the resistance versus time at an elevated temperature. The kinetics of the interface have been analyzed through imaging with scanning electron microscopy (SEM), elemental analysis using energy dispersive spectroscopy (EDS), and phase identification with X-ray diffraction (XRD). The results reveal the formation of an intermediate phase containing calcium and chromium in the interface that is highly resistive at room temperature, but conducting at the intended thermoelectric device hot-side operating temperature of 800°C. As the alloy is well matched in terms of its thermal expansion and highly conducting compared to the Ca 3 Co 4 O 9 , it may be further considered as an interconnect material candidate at least with application on the hot-side of an oxide thermoelectric power generation module.

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Thermodynamic considerations on Cr poisoning in SOFC cathodes

Cited by 254 publications

References 28 publications

Conductivity and oxygen reduction activity changes in lanthanum strontium manganite upon low-level chromium substitution

Conductivity and oxygen reduction activity changes in lanthanum strontium manganite upon low-level chromium substitution

Thermodynamic modeling of La₂O₃–SrO–Mn₂O₃–Cr₂O₃for solid oxide fuel cell applications

Characterization of the interface between an Fe–Cr alloy and the p-type thermoelectric oxide Ca3Co4O9

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Thermodynamic considerations on Cr poisoning in SOFC cathodes

Cited by 254 publications

References 28 publications

Conductivity and oxygen reduction activity changes in lanthanum strontium manganite upon low-level chromium substitution

Conductivity and oxygen reduction activity changes in lanthanum strontium manganite upon low-level chromium substitution

Thermodynamic modeling of La2O3–SrO–Mn2O3–Cr2O3for solid oxide fuel cell applications

Characterization of the interface between an Fe–Cr alloy and the p-type thermoelectric oxide Ca3Co4O9

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Thermodynamic modeling of La₂O₃–SrO–Mn₂O₃–Cr₂O₃for solid oxide fuel cell applications