Quasi‐Topological Intercalation Mechanism of Bi_0.67NbS₂ Enabling 100 C Fast‐Charging for Sodium‐Ion Batteries

Abstract Alloying‐type bismuth with high volumetric capacity has emerged as a promising anode for sodium‐ion batteries but suffers from large volume expansion and continuous pulverization. Herein, a coordination constraint strategy is proposed, that is, chemically confining atomic Bi in an intercalation host framework via reconstruction‐favorable linear coordination bonds, enabling a novel quasi‐topological intercalation mechanism. Specifically, micron‐sized Bi 0.67 NbS 2 is synthesized, in which the Bi atom is linearly coordinated with two S atoms in the interlayer of NbS 2 . The robust Nb−S host framework provides fast ion/electron diffusion channels and buffers the volume expansion of Na + insertion, endowing Bi 0.67 NbS 2 with a lower energy barrier (0.141 vs . 0.504 eV of Bi). In situ and ex situ characterizations reveal that Bi atom alloys with Na + via a solid‐solution process and is constrained by the reconstructed Bi−S bonds after dealloying, realizing complete recovery of crystalline Bi 0.67 NbS 2 phase to avoid the migration and aggregation of atomic Bi. Accordingly, the Bi 0.67 NbS 2 anode delivers a reversible capacity of 325 mAh g −1 at 1 C and an extraordinary ultrahigh‐rate stability of 226 mAh g −1 at 100 C over 25 000 cycles. The proposed quasi‐topological intercalation mechanism induced by coordinated mode modulation is expected to be be conducive to the practical electrode design for fast‐charging batteries.