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5 - Kinetics of electrochromic operation

Published online by Cambridge University Press:  10 August 2009

Paul Monk ,
Roger Mortimer  and
David Rosseinsky
Paul Monk
Affiliation:
Manchester Metropolitan University
Roger Mortimer
Affiliation:
Loughborough University
David Rosseinsky
Affiliation:
University of Exeter
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Summary

Kinetic considerations for type-I and type-II electrochromes: transport of electrochrome through liquid solutions

Type-I and type-II electrochromes are dissolved in solution prior to the electron-transfer reaction that results in colour. Such electron-transfer reactions are said to be ‘nernstian’ or ‘reversible’ when uncomplicated and fast and in accord with the Nernst equation (Eq. (3.1), Chapter 3). When two conditions regarding the motions of electroactive species (or indeed other participant species) are met, there is a particular means, that needs definition, whereby the key electroactive species arrives at the electrode. These conditions are: the absence both of convection (i.e. the solution unstirred, ‘still’), and also of electroactive-species migration. Then ‘mass transport’ (directional motion) of any electroactive species is constrained to occur wholly by diffusion. On the one hand, the rate of forming coloured product can be dictated by the rate of electron transfer with rate constant ket, which if low may render the electrode response non-nernstian (the electrode potential EO,R diverges from the Nernst equation (3.1) in terms of bulk electroactive concentrations), and furthermore, the rate of the process governed by ket largely determines the current. On the other hand, if ket is high, then electroactive/electrode electron transfer is not the rate- and current-controlling bottleneck, and the overall rate of colour formation is dictated by the rate of mass transport of electroactive species toward the electrode.

The experimental context of these considerations arises as follows. An electrochromic cell is primed for use (‘polarised’) by applying an overpotential (Section 3.3, Chapter 3).

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Electrochromism and Electrochromic Devices , pp. 75 - 124
Publisher: Cambridge University Press
Print publication year: 2007

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