Hydration effect on properties of the La2-xAxNi1-yFeyO4+δ (A=Ca, Sr) cathode materials for H+-SOFCs

• Published in: Journal of alloys and compounds 2021-04, Vol.860, p.1, Article 158452
• Main Authors: Gilev, A.R., Kiselev, E.A., Malyshkin, D.A., Sukhanov, K.S., Cherepanov, V.A.
• Format: Article
• Language: English
• Subjects: Activation energy; Charge transfer; Conductivity; Electrochemical impedance spectroscopy; Electrode materials; Exchanging; High temperature; Humidity; Hydration; Impedance spectroscopy; Ion diffusion; La2NiO4; Perovskites; Proton conduction; Relative humidity; Strontium; Thermogravimetric analysis; Transport properties; X ray powder diffraction; X-ray diffraction
• ISSN: 0925-8388; 1873-4669
• DOI: 10.1016/j.jallcom.2020.158452

The effect of air humidity on the transport properties of the La2-xAxNi1-yFeyO4+δ (A=Ca, Sr; x = 0.5, 0.6 and y = 0.4, 0.5) oxides was studied in the temperature range of 25–950 °C. Total conductivity of the samples decreased with increasing relative humidity (RH), most significantly in the range of 250–550 °C. Thermogravimetric analysis in dry and wet air indicated that the observed changes in conductivity could be attributed to the hydration of the samples. The high-temperature X-ray powder diffraction (HT-XRPD) results for La1.4Sr0.6Ni0.5Fe0.5O4+δ (LSNF0605) suggested that the hydration led to the insertion of hydroxide ions into the interstitial sites resulting in the expansion of the rock-salt type layers and shrinkage of the perovskite layers. The Electrochemical Impedance Spectroscopy (EIS) measurements for the LSNF0605/Ce0.8Sm0.2O2-δ (SDC) and LSNF0605/La28−zW4+zO54+1.5z (LWO) symmetrical cells showed that the hydration affected the surface exchange process in LSNF0605. The activation energy of surface exchange decreased with the increase in RH for the LSNF0605/LWO cell indicating that water could participate in the surface exchange. The activation energy of the charge transfer – ionic diffusion process in the LSNF0605 electrode for the LSNF0605/LWO cell possessed smaller values compared to that for the LSNF0605/SDC cell in wet air, suggesting the presence of proton conduction. •Effect of air humidity on properties of La2-xAxNi1-yFeyO4+δ was observed at T ≤ 700 °C.•Thermogravimetric analysis suggested hydration of the samples in wet air below 700 °C.•(La/A)O layer of La2-xAxNi1-yFeyO4+δ expanded with increasing air humidity.•The impedance studies showed that hydration affected the surface exchange process.•The results indicated the presence of proton conduction in La1.4Sr0.6Ni0.5Fe0.5O4+δ.