Fermi Potential across Working Solid Oxide Cells with Zirconia or Ceria Electrolytes

A solid electrolyte will always possess a finite electronic conductivity, in particular electrolytes like doped ceria that easily get reduced and become mixed ionic and electronic conductors. This given rise too high leak currents through the solid oxide cell (SOC). Especially, problems have been observed for ceria based electrolytes, but also in case of solid oxide electrolyser cells (SOEC) with yttria stabilized zirconia (YSZ) big electronic leak currents have been observed for very high overvoltages on one or both electrodes.

Furthermore, it is important to realize that the potential gradient driving the O^2-ions is not the Fermi potential, which is the potential of the electrons, but the Galvani potential (or inner potential) (1). The concepts of potentials describing the electrical situation of a solid electrolyte is shown i Fig. 1, and an example of the Fermi potential (π) and Galvani potential (φ) profiles are shown in Fig. 2. The Fermi potential will be affected directly by the Galvani potential, whereas the Galvani potential need not necessarily be affected by the Fermi potential because the concentration of “free” electrons may be very low. 

 The paper gives illustrative examples at various temperatures and operation conditions. Furthermore, the situation within cells based on gadolinia doped ceria (CGO) and on YSZ electrolytes are compared. Finally, it is discussed how the Fermi potential and electron conductivity will be affected by the various parameters including operation conditions.

Reference

[1] T. Jacobsen and M. Mogensen, ECS Transactions, 13 (no.26), 259 (2008).