Spatially Integrated Intercalation–Conversion Hybrid Cathode for Durable, High‐Capacity Lithium Metal Batteries

ABSTRACT The fundamental trade‐off between structural stability and high capacity remains a key challenge in Li‐ion battery cathode design, especially in cost‐sensitive, large‐scale applications. Here, we present a spatially integrated intercalation–conversion hybrid cathode that combines LiFePO 4 and sulfur‐based materials within a monolayer architecture. This earth‐abundant composition synchronizes Li‐ion intercalation with the solid‐liquid sulfur conversion reaction: LiFePO 4 serves as a mechanically robust Li host and a chemical regulator that suppresses polysulfide shuttles, while sulfur‐based materials provide high specific capacity. By rationally tailoring the cathode composition and electrolyte solvation chemistry, we reveal how electrolyte–cathode synergistic interactions govern active material utilization, interfacial kinetics, and long‐term stability. The optimized Li‐metal battery delivers stable cycling over 3000 cycles with a low‐capacity decay rate of 0.016% per cycle at 5 C and also demonstrates stable cycling under practical asymmetric cycling protocols. This work provides a new design principle for hybrid cathodes, offering a scalable pathway toward ultra‐durable and high‐capacity Li‐metal batteries.