Anion‐Governed Microdomains Accelerate Cross‐Scale Li + Transport for Extremely Fast‐Charging Lithium‐Ion Batteries

ABSTRACT The fast‐charging capability of lithium‐ion batteries remains limited by multiscale Li + transport bottlenecks from electrolyte to graphite layers. Among them, the primary transport limitations arise from sluggish kinetics at the solid‐liquid interface and inefficient mass transport in the electrode bulk, which should be simultaneously addressed. Herein, we propose a pioneering strategy of anion‐governed microdomains with electrostatic guidance through the incorporation of anionic COF nanoparticles (aiCONs) into graphite anodes. This strategy simultaneously facilitates interfacial Li + desolvation processes by modifying Li + solvation structure and promotes Li + migration by creating continuous ion‐paths within electrode bulk. Consequently, the composited anode (aiCONs/Gr) exhibits facilitated cross‐scale Li + transport behavior and enhanced stability under harsh conditions. When assembled into full cells paired with LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathodes, the aiCONs/Gr anodes demonstrate extremely fast‐charging capability, achieving states of charge (SOC) of 81.6% and 75.9% at 6C and 10C, respectively, and retaining 91.4% of the capacity at 10C after 400 cycles. Moreover, a superior long‐term cycling performance at 4C in the high‐loading full cell (∼3.4 mAh cm −2 ) was realized (88.0% capacity retention after 500 cycles). This work demonstrates a pioneering strategy that enables the optimization of cross‐scale Li + transportation, establishing new design principles for accelerating ion transport in composite electrode architectures.