Historical evolution of circuit models for the electrode-electrolyte interface

Electrodes are widely used to measure bioelectric events and to stimulate excitable tissues. In one form or another, electrodes have been around for nearly two centuries; yet our ability to predict their properties is extremely Limited, despite considerable research, especially during the last century. This paper chronicles the accumulation of knowledge about the electrode-electrolyte interface as a circuit element. Our understanding of this interface starts with the Helmholtz double layer of charge and progresses through the Warburg and Fricke low-current-density models, which demonstrated that the resistive and capacitive components are polarization elements, the values of which depend on frequency. The discovery by Schwan, showing that the components of the Warburg-Fricke model are current-density dependent, is recounted, along with the discovery of the rectifying properties of the electrode-electrolyte interface and how it was put to practical use. The very high current-density operation of the interface is discussed in terms of gas evolution, arcing, and shock-wave production. Finally the evolution of recording electrodes is traced. Because electrodes can be operated over a very wide range of current density, it is unlikely that a single model can be created for the electrode-electrolyte interface, although over a restricted current-density range such a model may be possible.