Design of NH 2 ‐ MIL‐101(Fe) Derived N, S Co‐Doped Carbon Encapsulated Iron Pyrrhotite Anode for Sodium‐Ion Batteries: Mechanistic Correlation of Degradation Pathways

Abstract Metal sulfides are promising anode materials for sodium‐ion batteries owing to their high theoretical specific capacity, low cost, and abundance. However, issues including poor conductivity, sluggish Na + kinetics, and pulverization limit their electrochemical performance. Beyond these, the intrinsic polysulfide generation triggers multifaceted degradation pathways, like polysulfide shuttle, current collector corrosion, and sodium dendrite formation, which collectively are the causes behind the “under voltage failure” phenomena, resulting in limited cycle life. Herein, a rational development of metal‐organic framework derived N, S co‐doped carbon encapsulated iron pyrrhotite (FS) is presented. Fe 1−x S‐carbon composites are developed by varying the carbon to iron ratio, denoted as FS‐1, FS‐3, and FS‐6, to understand the interplay of composite constituents with electrochemical performance and degradation pathways. Polar nature of Fe 1−x S and N, S co‐doped carbon traps polysulfides, and carbon matrix alleviates Cu corrosion and volume expansion, augmenting the long‐term stability. FS‐6 delivers a higher capacity of 439 mAh g −1 with stable ≈180 cycles, while FS‐1 delivers 293 mAh g −1 with stable ≈360 cycles at 0.5 A g −1 . Intermediate FS‐3 delivers a balanced specific capacity of 370 mAh g −1 with stable ≈280 charge‐discharge cycles. This work demonstrates the design and role of carbon‐metal sulfide composites to alleviate the multifaceted degradation pathways.