Opening and Constructing Stable Lithium‐ion Channels within Polymer Electrolytes

Lithium‐ion batteries play an integral role in various aspects of daily life, yet there is a pressing need to enhance their safety and cycling stability. In this study, we have successfully developed a highly secure and flexible solid‐state polymer electrolyte (SPE) through the in situ polymerization of allyl acetoacetate (AAA) monomers. This SPE constructed an efficient Li + transport channel inside and effectively improved the solid‐solid interface contact of solid‐state batteries to reduce interfacial impedance. Furthermore, it exhibited excellent thermal stability, an ionic conductivity of 3.82×10 −4 S cm −1 at room temperature (RT), and a Li + transport number ( t Li+ ) of 0.66. The numerous oxygen vacancies on layered inorganic SiO 2 created an excellent environment for TFSI − immobilization. Free Li + migrated rapidly at the C=O equivalence site with the poly(allyl acetoacetate) (PAAA) matrix. Consequently, when cycled at 0.5C and RT, it displayed an initial discharge specific capacity of 140.6 mAh g −1 with a discharge specific capacity retention rate of 70 % even after 500 cycles. Similarly, when cycled at a higher rate of 5C, it demonstrated an initial discharge specific capacity of 132.3 mAh g −1 while maintaining excellent cycling stability.