Adaptive Electrochemical Self‐Cleaning via Surface Reconstruction Enables Fluoride‐Free and Batch‐Consistent Cathode Regeneration

Direct recycling of spent lithium‐ion battery (LIB) cathodes holds great promise for sustainable materials recovery. However, residual fluorinated impurities, including inorganic fluoride species and polyvinylidene fluoride (PVDF), remain a persistent challenge due to their chemical persistence and heterogeneous distribution. Here, we report an electrochemically driven self‐cleaning strategy that enables fluoride‐free adaptive direct recycling of spent cathodes. Using LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NMC532) as a model system, anodic polarization activates oxygen‐evolution‐driven surface reconstruction, generating hydroxylated transition metal (TM) interfaces that trigger the cooperative elimination of fluorinated contaminants. Specifically, the reconstruction promotes proton‐assisted dissolution of LiF and related inorganic fluoride species, while simultaneously inducing a hydrophobic‐to‐hydrophilic interfacial transition that weakens PVDF adhesion and facilitates its removal. These coupled redox‐hydrolysis‐interfacial processes synergistically eradicate fluorinated residues while preserving the bulk composition and structural integrity of the cathode. The regenerated NMC532 delivers a high discharge capacity of 145.1 mAh·g −1 , comparable to commercial material. When implemented in pouch cells, this strategy achieves an inter‑batch capacity variation of less than 1.3%, dramatically outperforming the ∼24.1% variation typical of conventional recycling and meeting commercial consistency standards (± 3%–5%). This reconstruction‐enabled self‐cleaning strategy is broadly applicable across diverse cathode chemistries, providing a scalable and chemically selective pathway toward impurity‑free, high‑performance battery material regeneration.