Upcycling the Spent Graphite Anode Into the Prelithiation Catalyst: A Separator Strategy Toward Anode‐Free Cell Prototyping

The substantial manufacturing of lithium-ion batteries (LIBs) requires sustainable, circular, and decarbonized recycling strategies. While efforts are concentrated on extracting valuable metals from cathodes using intricate chemical process, the direct, efficient cathode regeneration remains a technological challenge. More urgently, the battery supply chain also requires the value-added exploitation of retired anodes. Here, a "closed-loop" approach is proposed to upcycle spent graphite into the prelithiation catalyst, namely the fewer-layer graphene flakes (FGF), upon the exquisite tuning of interlayer spacing and defect concentration. Since the catalytic FGF mitigates the delithiation energy barrier from calcinated Li₅FeO₄ nanocrystalline, the composite layer of which cast on the polyolefin substrate thus enables a customized prelithiation capability (98% Li⁺ utilization) for the retired LiFePO₄ recovery. Furthermore, the hydrophobic polymeric modification guarantees the moisture tolerance of Li₅FeO₄ agents, aligning with commercial battery manufacturing standards. The separator strategy well regulates the interfacial chemistry in the anode-free pouch cell (LiFePO₄||Cu), the prototype of which balances the robust cyclability, energy density up to 386.6 Wh kg^-1 as well as the extreme power output of 1159.8 W kg^-1. This study not only fulfills the sustainable supply chain with graphite upcycling, but also establishes a generic, viable protocol for the anode-free cell prototyping.