Kinetic behaviour of ion intercalation electrodes at elevated temperatures

Abstract

Electrochromic films undergo a colour change when small ions and electrons are inserted into them, under the influence of an applied electric field. These films are also known as ion-intercalation electrodes, and may be incorporated into glazing structures more commonly known as 'smart windows'. Smart windows are that which may be used to control the amount of heat and light entering a building and may therefore be used to minimise the energy consumption associated with heating, cooling and lighting. The commercial success of smart windows, requires that they operate reproducibly at temperatures up to approximately 70ºC, for many tens of thousands of colouring and bleaching cycles. An understanding of the underlying kinetic processes over a wide temperature range is therefore needed, in order to determine suitable control strategies and switching conditions capable of fulfilling these requirements.

The research detailed in this thesis has involved an investigation into the kinetic behaviour of ion-intercalation electrodes, and simulation of the electrical response as a means of developing a tool for predicting and then optimising electrochromic switching. More specifically, the electrical and optical properties of electrochromic thin films of WO3/TiO2 have been studied over a wide temperature range, appropriate for the operation of electrochromic windows. The magnitude of the voltages required for coloration and bleaching significantly reduces as temperature increases. Some irreversibility was observed at high temperature, as well as a reduction in coloration efficiency. Further investigation revealed that self-bleaching and irreversibility effects were caused by the presence of water, and this problem was exacerbated at high temperature. Post-experiment chemical analysis of a film sample revealed that some trapping of the inserted ions had occurred, however the amount of ions remaining in the film was much smaller than expected. The results suggested that a large quantity of the lithium ions injected into the film were lost to the electrolyte after many cycles, possibly accompanied by some film dissolution.

Experimental work carried out in a dry-box showed that films may be cycled reversibly in a very dry environment, and the optical properties were independent of temperature under these conditions. Unfortunately, the conditions which led to reversible cycling and good electrochromic memory, also resulted in very long response times for film bleaching. This result implies that a good electrochromic memory and a fast response are mutually competitive aims.

Data from high temperature experiments was simulated with a mathematical model and the mobility of lithium ions inside the electrochromic films was estimated in the process. The estimated diffusion coefficients agreed well with published values, and exhibited an Arrhenius dependence on temperature. Activation energies for diffusion were calculated and the results were very reasonable. Some deviation from ideal Arrhenius behaviour was observed for the estimated diffusion coefficients at high temperature. It is likely that the rate limiting mechanism changes from diffusive motion of ions at low temperature, to charge transfer at high temperature.