Slow, Steady-State Transport with "Loading" and Bulk Reactions: the Mixed Ionic Conductor La$_2$CuO$_{4+δ}$

Abstract

We consider slow, steady transport for the normal state of the superconductor La$_2$CuO$_{4+δ}$ in a one-dimensional geometry, with surface fluxes sufficiently general to permit oxygen to be driven into the sample (``loaded'') either by electrochemical means or by high oxygen partial pressure. We include the bulk reaction O$\to$O$^{2-}+2h$, where neutral atoms ($a$) go into ions ($i$) and holes ($h$). For slow, steady transport, the transport equations simplify because the bulk reaction rate density $r$ and the bulk loading rates $\partial_t n$ then are uniform in space and time. All three fluxes $j$ must be specified at each surface, which for a uniform current density $J$ corresponds to five independent fluxes. These fluxes generate two types of static modes at each surface and a bulk response with a voltage profile that varies quadratically in space, characterized by $J$ and the total oxygen flux $j_O$ (neutral plus ion) at each surface. One type of surface mode is associated with electrical screening; the other type is associated both with diffusion and drift, and with chemical reaction (the {\it diffusion-reaction mode}). The diffusion-reaction mode is accompanied by changes in the chemical potentials $μ$, and by reactions and fluxes, but it neither carries current (J=0) nor loads the system chemically ($j_O=0$). Generation of the diffusion-reaction mode may explain the phenomenon of ``turbulence in the voltage'' often observed near the electrodes of other mixed ionic electronic conductors (MIECs).