Dipole Orientation Engineering in Crosslinking Polymer Blends for High‐Temperature Energy Storage Applications

Abstract Polymer dielectrics that perform efficiently under harsh electrification conditions are critical elements of advanced electronic and power systems. However, developing polymer dielectrics capable of reliably withstanding harsh temperatures and electric fields remains a fundamental challenge, requiring a delicate balance in dielectric constant ( K ), breakdown strength ( E b ), and thermal parameters. Here, amide crosslinking networks into cyano polymers is introduced, forming asymmetric dipole pairs with differing dipole moments. This strategy weakens the original electrostatic interactions between dipoles, thereby reducing the dipole orientation barriers of cyano groups, achieving dipole activation while suppressing polarization losses. The resulting styrene‐acrylonitrile/crosslinking styrene‐maleic anhydride (SAN/CSMA) blends exhibit a K of 4.35 and an E b of 670 MV m −1 simultaneously at 120 °C, and ultrahigh discharged energy densities ( U e ) with 90% efficiency of 8.6 and 7.4 J cm −3 at 120 and 150 °C are achieved, respectively, more than ten times that of the original dielectric at the same conditions. The SAN/CSMA blends show excellent cyclic stability in harsh conditions. Combining the results with SAN/CSMA and ABS (acrylonitrile‐butadiene‐styrene copolymer)/CSMA blends, it is demonstrated that this novel strategy can meet the demands of high‐performing dielectric polymers at elevated temperatures.