Colorless to Multicolored, Fast Switching, and Highly Stable Electrochromic Devices Based on Thermally Cross-Linking Copolymer

Transparent-to-colored electrochromic devices exhibit promising application prospects and have gained popularity. Herein, two triphenylamine derivatives TPA-OCH3 and TPA-CN with styryl moieties and different donor or acceptor units were designed and synthesized to further prepare solvent-resistant thermally cross-linking polymer P(TPA-OCH3) and P(TPA-CN) without any additional initiator. P(TPA-OCH3) and P(TPA-CN) possess two pairs of redox peaks, and P(TPA-OCH3) shows a lower onset oxidation potential compared to P(TPA-CN) because of the pendent donor unit. Correspondingly, both polymers exhibit multicolored changes from the neutral colorless state to noticeable oxidized colors under different potentials. Furthermore, the thermally cross-linking copolymer P(TPA-OCH3-co-TPA-CN) was obtained by TPA-OCH3 and TPA-CN (the molar ratio is 2:1) and presents outstanding electrochromism with four color changes (colorless–orange–blue–purple) due to the multistep redox process of TPA-OCH3 and TPA-CN units. It is more intriguing that the electrochromic device based on the copolymer films possesses a high optical contrast of 57.8% at 680 nm, fast switching time (0.52 and 0.66 s), and robust cyclic stability over 30 000 cycles with very little decay. Therefore, the thermally cross-linking copolymer is a promising candidate material for high-performance transmittive electrochromic devices, such as smart windows, sunglasses, and E-papers.