Surface modification of graphitized carbonaceous materials by electropolymerization of thiophene and their effects on electrochemical properties

Highly oriented pyrolytic graphite (HOPG) and graphitized carbonaceous thin films prepared by plasma-assisted chemical vapor deposition (PACVD) were surface-modified by electropolymerization of thiophene. The electrochemical properties of the carbonaceous materials were studied by cyclic voltammetry and ac impedance spectroscopy. Irreversible cathodic current of the carbonaceous materials above 0.5 V (vs. Li/Li⁺) in the cyclic voltammograms significantly decreased by electropolymerization of thiophene, indicating that electropolymerization of thiophene suppress the decomposition of electrolytes on the carbonaceous materials. On the Nyquist plots, a semi-circle due to surface film resistance was observed, and the value significantly decreased at around 1.5 V. At potentials below 0.9 V, another semi-circle appeared in the middle to lower frequency region, which was assigned to the charge transfer resistance due to lithium-ion transfer at the surface-modified carbon electrode/electrolyte interface. The charge-transfer resistances were dependent on electrode potentials. The activation energy for lithium-ion transfer through interface between the surface-modified HOPG electrode and electrolyte was evaluated, and the value was almost identical to that obtained for an untreated HOPG electrode. Based on these results, it is concluded that electropolymerization of thiophene played an important role not in the phase transfer kinetics of lithium-ion but in reduction of the electrolyte decomposition at a graphite electrode.