Catalyst‐Mediated Interfacial Prelithiation for Energy/Power‐Dense and Ultralong‐Life Lithium Batteries

The irreversible cation depletion and interfacial degradation fundamentally limit the practical energy output and cycling endurance of lithium‐free anode batteries. Here, we propose a catalyst‐mediated interfacial prelithiation strategy that offsets irreversible lithium loss, precisely optimizes Li + kinetics and interfacial stability for energy/power‐dense cell prototypes. The sulfurized polyacrylonitrile (SPAN) catalyst, featuring electron‐withdrawing sulfur sites, facilitates C‐C bond cleavage through S‐Li interactions. The Li 2 C 2 O 4 @SPAN composite delivers a delithiation voltage of 3.90 V and a highly efficient Li utilization of 99.5%. When paired with the LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode, the prelithiation layer achieves Li + replenishment areal capacities up to 1.1 mAh cm −2 . Furthermore, the bilayer configuration spatially isolates prelithiation agents from the cathode's redox center, alleviating the gas‐induced structural collapse and stress accumulation. Meanwhile, the SPAN‐derived ROSO 3 Li species form a robust cathode interphase with LiF domains, accelerating Li + transport and stabilizing the 4.5 V charging process. Under the lean‐electrolyte condition (1.7 g Ah −1 ) in 1.28 Ah pouch cells, the Cu||NCM811‐LS prototype achieves gravimetric/volumetric energy densities of 460 Wh kg −1 /1083 Wh L −1 and a peak power output of 858 W kg −1 . In addition, a 2.8 Ah Gr||NCM811 cell incorporating this prelithiation reservoir maintains a capacity retention of 88.2% over 1000 cycles. As a “drop‐in” solution requiring no changes to cell assembly, this interfacial prelithiation paradigm aligns with scalable industrial manufacturing, affording a readily adoptable path toward energy/power‐dense lithium batteries.