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 Li₂C₂O₄@SPAN composite delivers a delithiation voltage of 3.90 V and a highly efficient Li utilization of 99.5%. When paired with the LiNi_0.8Co_0.1Mn_0.1O₂ 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 ROSO₃Li 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.