Atomic‐Level Matching Metal‐Ion Organic Hybrid Interface to Enhance Energy Storage of Polymer‐Based Composite Dielectrics

Abstract In this work, a distinctive “metal‐ion organic hybrid interface” (MOHI) between polyimide (PI) and calcium niobate (CNO) nanosheets is designed. The metal ions in the MOHI can achieve atomic‐level matching not only with the inorganic CNO, but also with the PI chains, forming uniform and strong chemical bonds. These results are demonstrated by experiment and theory calculations. Significantly, the MOHI reduces the free volume and introduces deep traps across the filler‐matrix interfacial area, thus suppressing the electric field distortion in PI‐based composite dielectrics. Consequently, PI‐based dielectric containing the MOHI exhibits excellent energy storage performance. The energy storage densities (U_e) of the composite dielectric reach 9.42 J cm⁻³ and 4.75 J cm⁻³ with energy storage efficiency (η) of 90% at 25 °C and 150 °C respectively, which are 2.6 and 11.6 times higher than those of pure PI. This study provides new ideas for polymer‐based composite dielectrics in high energy storage.