Integrating Dissociating Stators and Conducting Rotors Within an Amphidynamic COF-Based Solid-State Polymer...

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.