On the electric double-layer structure at carbon electrode/organic electrolyte solution interface analyzed by ac impedance and electrochemical quartz-crystal microbalance responses

Abstract

ac impedance and electrochemical quartz crystal microbalance (EQCM) techniques have been applied to analyze the structure of electric double-layer formed at carbon/organic electrolyte solution interface using a sputtered carbon electrode. The mass changes caused by electrochemical adsorption (accumulation) of ions have been estimated in the solutions of propylene carbonate (PC) dissolving tetrafluoroborate (BF 4 −) salts of lithium (Li +), tetraethylammonium (TEA +) and tetra- n-butylammonium (TBA +) cations. The observed mass changes during the cathodic polarization in the solutions containing TEA + and TBA + were well consistent with those expected by the calculation based on mono-layer adsorption of the cations with giving the consideration to the surface roughness. On the other hand, the mass change observed in the solution containing Li + salt showed that the solvation of Li + with three or four molecules of PC would be the charge compensation species at the interface. Comparison of the quantity of the electricity passed during the EQCM measurements with that from theoretical calculation with simple Helmholtz-layer model revealed that the major part of the double-layer capacitance would be based on the electrostatic polarization of the solvent molecule directly adsorbed at the carbon surface.