In-situ preparation and electrochromic properties of TiO₂/PTPA-HTAN core-shell nanocomposite film

A new star-shaped structure conjugated microporous polymers, poly (2,8,14-tri[4-diphenyl-benzene]-hexaazatrinaphthylene) (PTPA-HATN), was designed and in-situ electrochemically polymerized on the surfaces of FTO electrodes with a directional alignment TiO2 nanorod array to obtain TiO2/PTPA-HATN core-shell nanocomposite films. Compared with the PTPA-HATN film, the TiO2/PTPA-HATN composite film exhibits higher optical contrast and faster response time, with contrast of 57% at 783 nm, coloring time of 3.62 s and discoloring time of 2.55 s (43%, 4.63 s and 4.77 s for PTPA-HATN film, respectively). After 400 cycles, the contrast of nanocomposite film decreased by 28%, while the PTPA-HATN film basically lost its electrochromic properties. A simple three-layer EC prototype device based on TiO2/PTPA-HATN nanocomposite film constructed with hydrogel electrolyte clearly shows color changes at different voltages. On the one hand, the formation of core-shell porous nanostructure of TiO2/PTPA-HATN composite film provides a larger ion doping/de-doping interface, shortening the average diffusion length of ions. On the other hand, the large indented polymer-nanorods contact interface makes it difficult for the polymer to detach from the electrode, thus significantly improving the cyclic stability of the composite film.