Interfacial Electrochemistry

Abstract

Basic principles of electrochemical measurements of solid, rigid, and semirigid (nonfluid) systems performed in the absence of liquid electrolyte phase typically at room temperatures are discussed. Special attention has been paid to the discussion of the mechanisms of charge propagation, including bulk charge transport and interfacial electron transfer. The theory is supported with the examples of representative systems such as solid solutions, organic polymers, redox melts, inorganic mixed-valence materials, sol-gel processed structures, and materials containing catalytically reactive centers. The emphasis is also on experimental requirements, and configurations of common cells for solid-state voltammetry are provided. Application of microdimensional electrodes, including ultramicrodisk electrodes and interdigitated arrays, has led to the improvement in the quality of solid-state electrochemical data and has provided new diagnostic and analytical possibilities. Possible applications of the area are mentioned.