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

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_0.6Mn_0.2Co_0.2O₂ 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. © 2026 Wiley-VCH GmbH.