MnS@N,S Co-Doped Carbon Core/Shell Nanocubes: Sulfur-Bridged Bonds Enhanced Na-Storage Properties Revealed by In Situ Raman Spectroscopy and Transmission Electron Microscopy.

Rational structure and morphology design are of great significance to realize excellent Na storage for advanced electrode materials in sodium-ion batteries (SIBs). Herein, a cube-like core/shell composite of single MnS nanocubes (≈50 nm) encapsulated in N, S co-doped carbon (MnS@NSC) with strong CSMn bond interactions is successfully prepared as outstanding anode material for SIBs. The carbon shell significantly restricts the expansion of the MnS volume in successive sodiation/desodiation processes, as demonstrated by in situ transmission electron microscopy (TEM) of one single MnS@NSC nanocube. Moreover, the in situ generated CSMn bonds between the MnS core and carbon shell play a significant role in improving the Na-storage stability and reversibility of MnS@NSC, as revealed by in situ Raman and TEM. As a result, MnS@NSC exhibits a high reversible specific capacity of 594.2 mAh g-1 at a current density of 100 mA g-1 and an excellent rate performance. It also achieves a remarkable cycling stability of 329.1 mAh g-1 after 3000 charge/discharge cycles at 1 A g-1 corresponding to a low capacity attenuation rate of 0.0068% per cycle, which is superior to that of pristine MnS and most of the reported Mn-based anode materials in SIBs.