Jm. Elliott et Jr. Owen, Electrochemical impedance characterisation of a nanostructured (mesoporous) platinum film, PHYS CHEM P, 2(24), 2000, pp. 5653-5659
Nanostructured platinum films with an hexagonal array of uniform, regularly
-sized pores were grown on platinum substrates by electrochemical plating f
rom a liquid crystalline electrolyte. The films were characterised as model
s for nanoporous electrodes, first by cyclic voltammetry in dilute sulfuric
acid, showing enhanced currents due to the internal area of the pore struc
ture. Complex impedance spectroscopy was then used to determine the access
time of the capacitance and pseudocapacitance in the double layer and hydro
gen adsorption regions, respectively. The results were analysed in terms of
a transmission line model, showing capacitance at low frequencies and diff
usive behaviour above 1 kHz. Capacitance values were as expected from the i
nternal surface area and in agreement with the cyclic voltammetry results.
The pore resistance was higher than predicted from a straight pore model, a
nd showed apparent tortuosity factors of about 10. Nevertheless, the nanost
ructured material gave a very impressive performance as a supercapacitor, w
ith a volumetric capacitance of 110 F cm(-3) and an effective diffusion coe
fficient of 5 x 10(-5) cm(2) s(-1) in the double layer region.