Scalable Polyimide‐Organosilicate Hybrid Films for High‐Temperature Capacitive Energy Storage

High-temperature polymer dielectrics have broad application prospects in next-generation microelectronics and electrical power systems. However, the capacitive energy densities of dielectric polymers at elevated temperatures are severely limited by carrier excitation and transport. Herein, a molecular engineering strategy is presented to regulate the bulk-limited conduction in the polymer by bonding amino polyhedral oligomeric silsesquioxane (NH2 -POSS) with the chain ends of polyimide (PI). Experimental studies and density functional theory (DFT) calculations demonstrate that the terminal group NH2 -POSS with a wide-bandgap of Eg ≈ 6.6 eV increases the band energy levels of the PI and induces the formation of local deep traps in the hybrid films, which significantly restrains carrier transport. At 200 °C, the hybrid film exhibits concurrently an ultrahigh discharged energy density of 3.45 J cm-3 and a high gravimetric energy density of 2.74 J g-1 , with the charge-discharge efficiency >90%, far exceeding those achieved in the dielectric polymers and nearly all other polymer nanocomposites. Moreover, the NH2 -POSS terminated PI film exhibits excellent charge-discharge cyclability (>50000) and power density (0.39 MW cm-3 ) at 200 °C, making it a promising candidate for high-temperature high-energy-density capacitors. This work represents a novel strategy to scalable polymer dielectrics with superior capacitive performance operating in harsh environments.