Reversible Fuel Cells with Tri-Layer Electrolytes

Reversible solid oxide fuel cells (SOFC) are operated as solid oxide fuel cells and as solid oxide electrolyzer cells (SOEC). In SOFC mode, hydrogen is consumed at the fuel electrode to convert chemical energy of fuel oxidation into water vapor. In SOEC mode, water vapor is decomposed at the fuel electrode to generate hydrogen under an applied DC voltage. Much of the reported work on reversible solid oxide cells is based on yttria-stabilized zirconia (YSZ) electrolyte, Ni + YSZ fuel electrode, and a perovskite-based oxygen electrode. At high operating voltages in the SOEC mode, cell degradation can occur which involves oxygen electrode delamination, formation of cracks within the electrolyte, and also reduction of the electrode near the fuel electrode. The higher the applied voltage, the greater is the propensity to degradation. These observations are consistent with the chemical potential of oxygen in the electrolyte exceeding both electrode bounds under an applied voltage. It has been shown that a small amount of electronic conductivity can minimize degradation. The principal role of electronic conductivity is to smoothen out the variation in oxygen chemical  potential through the electrolyte such that it does not exceed electrode bounds. YSZ-based electrolyte if doped with sufficient amount of CeO₂ can create significant electronic conductivity such that the electrolyte becomes a mixed ionic electronic conductor. Doping with ceria also lowers the ionic transference number of the electrolyte. A possible bi-layer electrolyte consists of a thin layer of YSZ (or another purely oxygen ion conductor) deposited on a mixed ionic electronic conducting material. As long as electronic conduction through the blocking layer is negligible, the overall ionic transference number of the bi-layer electrolyte can approach unity. In this paper, theoretical analysis of the bi-layer electrolyte for reversible cells is presented. Two configurations of the bi-layer electrolyte are investigated. (1) The electron blocking layer adjacent to the oxygen electrode. (2) The electron blocking layer adjacent to the fuel electrode. For both configurations, the spatial distribution of oxygen chemical potential through the bi-layer electrolyte in both the SOFC and the SOEC modes are evaluated. The ionic transference number of the MIEC part of the bi-layer electrolyte is varied over a wide range. Theoretical analysis shows that such bi-layer electrolyte cells should exhibit good performance characterstics and excellent stability. The net variation of the oxygen chemical potential through the bi-layer electrolyte is determined as a function of transport properties of both layers, electrode polarizations and interfacial resistances to electron transfer.