Wei Bo, Chen Kongfa, Zhao Ling, Lü Zhe, Jiang San Ping
Fuels and Energy Technology Institute & Department of Chemical Engineering, Curtin University, Perth, WA 6102, Australia.
Phys Chem Chem Phys. 2015 Jan 21;17(3):1601-9. doi: 10.1039/c4cp05110f. Epub 2014 Dec 1.
The degradation of solid oxide electrolysis cells (SOECs) is an issue of both scientific and technical importance. In this study, chromium deposition and poisoning at the La0.6Sr0.4Co0.2Fe0.8O(3-δ) (LSCF) anode or the oxygen electrode of SOECs are studied for the first time under a current density of 200 mA cm(-2) at 900 and 800 °C. After polarization in the presence of the Fe-Cr interconnect at 900 °C for 20 h, electrode polarization resistance and overpotential of the O2 evolution reaction (OER) on the LSCF electrode are 0.413 Ω cm(-2) and 127 mV, respectively, which is nearly 7 and 18 times the initial values of the electrode before the polarization. Significant performance degradation was also observed for the reaction at 800 °C in the presence of the Fe-Cr alloy. XRD and XPS analyses clearly identified the deposition of SrCrO4, CrO2.5 and Cr2O3 phases on the surface of LSCF oxygen electrodes and their formation is closely related to the increased segregation of the SrO species under anodic polarization conditions. Sr segregation leads to Sr deficiency at the A-site, thus deteriorating the electrocatalytic activity of the LSCF oxygen electrodes for OER. The results indicate that Cr deposition is essentially a chemical reaction and is initiated by the nucleation reaction between the gaseous Cr species and segregated SrO on the surface region of the LSCF oxygen electrode.
固体氧化物电解槽(SOECs)的降解是一个具有科学和技术重要性的问题。在本研究中,首次在900℃和800℃下200 mA cm(-2)的电流密度下研究了SOECs的La0.6Sr0.4Co0.2Fe0.8O(3-δ)(LSCF)阳极或氧电极上的铬沉积和中毒情况。在900℃下与铁铬互连体一起极化20小时后,LSCF电极上的电极极化电阻和析氧反应(OER)的过电位分别为0.413 Ω cm(-2)和127 mV,几乎是极化前电极初始值的7倍和18倍。在800℃下存在铁铬合金时,该反应也观察到了显著的性能下降。XRD和XPS分析清楚地确定了SrCrO4、CrO2.5和Cr2O3相在LSCF氧电极表面的沉积,它们的形成与阳极极化条件下SrO物种的偏析增加密切相关。Sr偏析导致A位的Sr缺乏,从而降低了LSCF氧电极对OER的电催化活性。结果表明,Cr沉积本质上是一种化学反应,由气态Cr物种与LSCF氧电极表面区域偏析的SrO之间的成核反应引发。