Cell voltage of mixed conductors under partially frozen conditions

Partially frozen-in states are rather the rule than the exception. Coexistence between equilibrium states and frozen-in states is relevant in view of the diversity and complexity of charge carriers, or sublattices, especially in multinary compounds, but also with respect to differently equilibrated spatial regions. This contribution deals with the open circuit potential of samples where only surface-near regions feel the outer partial pressure, or more generally, the component chemical potentials, established by the electrodes. In view of the significance of such measurements for separating ionic and electronic conductivity contributions, and the kinetic difficulties in getting full equilibration near room-temperature, the value of these considerations is obvious. The necessary relations are derived, or their derivations are sketched within the framework of linear force–flux laws. An account is made of recent emf measurements of hybrid halide perovskites, and a refinement of their standard defect diagram is recommended.