Avoiding Voltage-Induced Degradation in PET-ITO-Based Flexible Electrochromic Devices

The cycling stability of flexible electrochromic devices (ECDs) under humid atmospheres is limited by irreversible indium tin oxide (ITO) reduction. A strategy to limit this degradation was developed and tested for model ECDs based on a sidechain-modified poly­(3,4-ethylene dioxythiophene) (PEDOT) derivative and Prussian blue (PB). This work reveals that the cycling stability is reduced by dissolution of the ITO thin films and formation of metallic indium particles on the surface of the ITO layers. The ITO degradation strongly depends on the applied electrode potentials in combination with moisture ingress into the ECDs. To avoid ITO reduction in ECDs, efforts were made to adjust the electrode potentials. ECDs equipped with an auxiliary reference electrode were set up to gather knowledge on the actual electrode potentials. By adjusting the electrode charge density ratio, it was possible to narrow the overall cell voltage window to an extent in which irreversible ITO reduction no longer occurs. Detailed investigation of ECDs with the optimized cell configuration (charge density ratio) showed that the overall device performance with regard to visible light transmittance change and response time is not impaired and that the cycling stability under humid atmosphere (90% rH) is dramatically improved. Thus, the proposed strategy offers an excellent perspective for the commercialization of flexible ECDs upon their enhanced durability.