Electrochemical Characterization of Diffusion in Polymeric vs. Monomeric Solvents

Polymer electrolyte was used as a medium for testing the performance of microband electrodes under conditions of linear diffusion. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments were performed in a highly viscous medium, where diffusion rates are much slower than in fluid solutions. The log i vs. log v (CV) or log i vs. log t (CA) relationships with the current equation confirmed the existence of such conditions, yielding slope values that were lower than the expected 0.5. This could indicate an impure linear diffusion profile, i.e., some contribution from radial diffusion (edge effects). However, the desired value of 0.5 was obtained when performing these tests in monomeric solvents of similar viscosities, such as glycerol or propylene glycol. These results led to the conclusion that the current equations, which are based on Fick's laws, may not be applicable for polymer electrolytes, where various obstructions to free diffusion result in a more complicated process than for monomeric solvents.