Heterointerfacial and Architectural Engineering in MOF‐Templated Corn‐Like FePS ₃ ‐ZnPS ₃ ‐C@NC Anode for Durable Sodium Storage

ABSTRACT 2D layered transition metal thiophosphites (MPS 3 ) are promising high‐capacity anodes for sodium‐ion batteries (SIBs) but are plagued by poor conductivity and severe volume changes. To address these challenges, we report a corn‐like multi‐MPS 3 heterostructure engineered via a sophisticated MOF‐on‐MOF templating strategy. This unique architecture, comprising a FePS 3 /ZnPS 3 heterojunction and a conformal N‐doped carbon (NC) coating, establishes an interfacial field and spatial confinement synergy that facilitates rapid ion/electron transport and ensures exceptional structural integrity. The designed FePS 3 ‐ZnPS 3 ‐C@NC anode delivers remarkable sodium storage performance: a high initial discharge capacity of 1294.5 mAh g −1 at 0.1 A g −1 and long cycling stability with 87.6% capacity retention after 1200 cycles at 2 A g −1 . Such superior performance is attributed to: (i) the elastic carbon coating, which effectively buffers mechanical strain and preserves structural stability; and (ii) the heterointerfacial synergy, which enhances charge carrier mobility and reaction kinetics. Ex situ characterizations unravel a multi‐mechanistic sodium storage process, accounting for the high capacity. Density functional theory (DFT) calculations confirm that the built‐in electric field at the FePS 3 /ZnPS 3 interface optimizes Na + adsorption energy and interfacial charge transfer. This study provides a generalizable design paradigm for high‐performance anodes through the rational integration of architectural control and interfacial engineering.