Life Testing and Redox Cycling of Ni- and Ru-Doped Strontium Iron Titanate Exsolution Fuel Electrodes in Electrolyte-Supported Solid Oxide Cells

Abstract

Recently perovskite materials have gained much attention as potential candidates for solid oxide cell (SOC) fuel electrodes due to their advantages of redox stability, coking resistance and sulfur resistance over their cermet counterparts. Enhanced electrochemical performance has also been observed for some of these perovskite materials resulting from exsolution, where nano-sized metal particles are formed on the material surface under reducing conditions. However, the degradation mechanism of these perovskite fuel electrodes has yet to be fully understood and the relationship between their long-term stability and operating envrionments (fuel-cell/electrolysis, fuel compositions, redox cycles, operating pressure, etc.) has not been fully investigated.Here, life tests were conducted in open-circuit and reversible operation at 850oC on electrolyte-supported symmetric and full cells with Ni and Ru-doped strontium iron titanate (Sr0.95Ti0.3Fe0.63Ni0.07O3 and Sr0.95Ti0.03Fe0.63Ru0.07O3) as fuel electrodes (SrTi0.3Fe0.6Co0.1O3 used as the air electrode in the full cells). For both materials, higher degradation rate was observed when operated with 97% H2 + 3% H2O compared with 50% H2 + 50% H2O as fuel; an increase in ohmic resistance and gas adsorption/desorption resistance contributed to most of the degradation observed. STFN also showed higher degradation rates than STFRu in both fuel compositions. Exsolution from both compositions was confirmed by scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM) with both fuel compositions and in situ X-ray Diffraction (XRD) showed the simultaneous perovskite to Ruddlesden-Popper (RP) phase transformation. The faster perovskite-RP phase transformation is believed to be responsible for the higher degradation rates observed for cells using fuel electrode materials with less stable perovskite structure (STFN over STFRu) and tested in more reducing fuel compositions (97% H2 over 50% H2). Moreover, redox cycles were introduced for STFN and STFRu during life tests and partial performance recovery was observed; in situ XRD and SEM microstructural analysis suggests that the recovery resulted from a transformation from RP back to perovskite for both materials. Finally full cell reversible operation durability tests (6 hrs each in fuel cell and electrolysis modes at 0.8 A/cm2) conducted at 850oC with 50% H2 + 50% H2O as fuel at 1 atm showed reasonably good stability over 1000 h. Initial reversible life testing at 3 atm operating pressure showed higher degradation rates, and the possible reasons for this will be discussed.