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Updated: Jun 16, 2026

In Situ Lithiated Reference Electrode: Four Electrode Design for In-operando Impedance Spectroscopy
Published on: September 12, 2018
Note: Characterization of electrode materials for dielectric spectroscopy
D Malleo1, J T Nevill, A van Ooyen
1Nanoscale Systems Integration Group, School of Electronics and Computer Science, University of Southampton, Hampshire SO17 1BJ, United Kingdom. daniele.malleo@ogt.co.uk
Abstract:
When measuring the dielectric properties of aqueous samples, the impedance of the electrode/sample interface can limit low frequency measurements. The electrode polarization problem can be reduced by increasing the effective surface area of the electrodes. In this work, impedance spectroscopy was used to characterize and compare three different electrode surfaces that can be used to mitigate this effect: platinum black, iridium oxide, and [polypyrrole/poly(styrenesulphonate)] (PPy/PSS) conducting polymer. All three materials were directly compared with a bright platinum electrode. Equivalent circuit models were used to extract the increase in the effective surface area of the electrodes: platinum black, iridium oxide and PPy/PSS increase the effective capacitance of the electrode by factors of approximately 240, 75, and 790, respectively. The practical aspects of all electrode materials are discussed. These results suggest that iridium oxide and PPy/PSS are good alternatives to the commonly used platinum black, which is prone to mechanical damage (scratches) and is potentially toxic to cells.
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