High Throughput Discovery of Grotthuss‐Type Lithium‐Ion Transport Mechanism in Metallosalen Covalent Organic Frameworks

Covalent organic frameworks, with their tunable pore structures, chemical environments, and high stability, are promising candidates for next‐generation solid‐state battery separators. To uncover the fundamental Li + transport mechanisms and enable rational design, we performed high‐throughput molecular dynamics simulations and data‐driven screening on a library of 628 metallosalen‐based COFs across five representative lithium‐salt systems. Our results demonstrate that efficient Li + transport depends critically on matching the COF pore chemistry with anion characteristics: weakly coordinated BOB − anions favor lightweight, moderately confined pores, whereas flexible TFSI − anions perform better in large‐pore, open‐topology COFs. More importantly, our simulation data suggest a potential anion‐engaged cooperative transport mode. This mode is characterized by the formation of a dynamic coordination network when a significant proportion (> 50%) of anions exhibit spatially confined motion. These confined anions appear to repeatedly coordinate and release Li + ions, facilitating a relay‐style conduction along the pore channels. Simulation analyses indicate that this mode correlates with high Li + diffusion coefficients and uniform ionic flux. Based on these observations, we propose two material design guidelines: anion‐adaptive pore matching and confined‐anion dynamics regulation. This work offers a theoretical perspective and a computational screening strategy for the rational design of COF‐based solid electrolytes.