Integrating Dissociating Stators and Conducting Rotors Within an Amphidynamic COF‐Based Solid‐State Polymer Electrolyte for Rapid and Consecutive Li ⁺ Transport

ABSTRACT Solvent‐free solid polymer electrolytes (SPEs) suffer from sluggish and discontinuous Li + transport. Although high‐polarity fillers enhance dissociation, liberated Li + tends to be trapped on filler surfaces due to the spatial and dynamic mismatches, hindering Li + long‐range migration. To bridge this gap, we establish a consecutive Li + transport pathway by integrating dissociating stators and conducting rotors within an amphidynamic COF (AD COF)‐based polymer electrolyte. In the AD COF, the highly polar rigid skeletons (stators) facilitate ionic dissociation, while the tethered flexible oligo(ethylene oxide) side‐chains (rotors) with dynamic conformational mobility enable rapid short‐range Li + relay corresponding to a segmental relaxation time of 1.10 × 10 −5 s. Subsequently, Li + is directed into 1D channels of COFs where the confined polymer (PAPE) sustains long‐range migration. Benefiting from this rapid and seamless dissociation‐conduction synergy, the resulting dry polymer electrolyte (AD COF‐PAPE) achieves a room‐temperature ionic conductivity of 1.18 × 10 −4 S cm −1 , surpassing the PAPE and the all‐rigid COF‐based polymer counterparts by 460% and 150%, respectively. The AD COF‐PAPE enables enhanced electrochemical performance in both Li symmetric cells and NCM‐based full cells, underscoring the critical importance of molecularly orchestrating spatial proximity and dynamic matching to overcome the intrinsic trade‐offs in SPEs.