Journal of Electroanalytical Chemistry, Vol.527, No.1-2, 93-102, 2002
Lithium transport through the Li1-delta CoO2 film electrode prepared by RF magnetron sputtering
Lithium transport through the Li1-deltaCoO2 film electrode prepared by RE magnetron sputtering was investigated in a 1 M solution of LiClO4 in propylene carbonate using the galvanostatic intermittent titration technique (GITT), electrochemical impedance spectroscopy (EIS), and the potentiostatic current transient technique. The experimental cathodic and anodic current transients in the presence of a single phase Li1-deltaCoO2 did not follow Cottrell behaviour, but Ohmic behaviour. This means the relationship between the initial current level and the potential step obeys Ohm's law. In addition, the current transients obtained in the case of coexistence of two phases alpha and beta were characterised by a flatter shape, as compared to those transients in the presence of the respective alpha and beta phases. Also, during phase transformation, the instantaneous current level was proportional to the potential step, in compliance with Ohm's law. From these results, it was suggested that the flux of lithium ion at the electrode I electrolyte interface during lithium transport is limited purely by the 'cell-impedance', not only in the presence of a single phase, but also when the two phases coexist. The value of the 'cell-impedance' calculated from the current transient was almost equal to the values obtained from the impedance spectra and the galvanostatic discharge curve. The current transients were modelled under the assumption of the 'cell-impedance-controlled' lithium intercalation and deintercalation. The current transients calculated theoretically coincided well in value and shape with those measured experimentally.
Keywords:Li1-delta CoO2 film electrode;non-Cottrell behaviour;Ohmic behaviour;current transient;cell-impedance;numerical simulation