Vacancy‐Driven Antistites Healing Enables Spent LiFePO ₄ Cathodes Regeneration

Lithium iron phosphate (LiFePO 4 , LFP) batteries are being retired at increasing rates due to their widespread use in electric vehicles. Conventional pyrometallurgical and hydrometallurgical recycling routes remain energy‐intensive and economically challenging, while direct regeneration often fails because antisite defects (Fe M1 ) block Li + diffusion. Here we report a vacancy‐driven regeneration strategy that destabilizes these kinetically persistent defects. Pre‐generated Li vacancies (Li v ) trigger selective oxidation of adjacent to , inducing electronic redistribution across the Fe M2 ‐O‐Fe M1 bridge and weakening the antisite configuration. This local electronic modulation lowers the migration barrier of Fe M1 , enabling its low‐temperature back‐migration to native lattice sites and reopening Li + diffusion pathways prior to relithiation. The regenerated LFP exhibits markedly improved electrochemical performance and achieves stoichiometric homogenization across spent cathodes with diverse degradation histories. Lithium resources on the lithiated anode can be gently extracted and utilized as a lithium supplement for cathode materials, with simultaneous regeneration of the anode. Techno‐economic and environmental analyses reveal substantial advantages of this process over both hydrometallurgical recycling and mineral mining processes.