Homogeneous and Nanogranular Prussian Blue to Enable Long-Term-Stable Electrochromic Devices

The increasing demand for the state-of-the-art electrochromic devices has received great interest in synthesizing Prussian blue (PB) nanoparticles with a uniform diameter that exhibit excellent electrochromism, electrochemistry, and cyclability. Herein, we report the controllable synthesis of sub-100 nm PB nanoparticles via the coprecipitation method. The diameter of PB nanoparticles can be modulated by adjusting the reactant concentration, the selection of a chelator, and their purification. The self-assembled nanogranular thin films, homogeneously fabricated by using optimized PB nanoparticles with an average diameter of 50 nm as building blocks via the blade coating technique enable excellent performance with a large optical modulation of 80% and a high coloration efficiency of 417.79 cm² C^-1. It is also demonstrated by in situ and ex situ observations that the nanogranular PB thin films possess outstanding structural and electrochemical reversibility. Furthermore, such nanogranular PB thin films can enjoy the enhanced long-term cycling stability of the PB-WO₃ complementary electrochromic devices having a 91.4% optical contrast retention after 16,000 consecutive cycles. This work provides a newly and industrially compatible approach to producing a complementary electrochromic device with extraordinary durability for various practical applications.