Probing the active sites of 2D nanosheets with Fe-N-C carbon shell encapsulated Fe x C/Fe species for boosting sodium-ion storage performances

Developing stable but high active metal-nitrogen-carbon (M-N-C)-based hard carbon anode is a promising way to be the alternatives to graphene and blank hard carbon for sodium-ion batteries (SIBs), requiring the precise tailoring of the electronic structure for optimizing the Na + intercalation behavior, yet is greatly challenging. Herein, Fe-N-C graphitic layer-encapsulating Fe 3 C species within hard carbon nanosheets (Fe-N-C/Fe 3 C@HCNs) are rationally engineered by pyrolysis of self-assembled polymer. Impressively, the Fe-N-C/Fe 3 C@HCNs exhibit outstanding rate capacity (242 mAh·g −1 at 2,000 mA·g −1 ), which is 2.1 and 4.2 times higher than that of Fe-N-C and N-doped carbon (N-C), respectively, and prolonged cycling stability (176 mAh·g −1 at 2,000 mA·g −1 after 2,000 cycles). Theoretical calculations unveil that the Fe 3 C species enhance the electronic transfer from Na to Fe-N-C, resulting in the charge redistribution between the interfaces of Fe 3 C and Fe-N-C. Thus, the optimized adsorption behavior towards Na + reduces the thermodynamic energy barriers. The synergistic effect of Fe 3 C and Fe-N-C species maintains the structural integrity of electrode materials during the sodiation/desodiation process. The in-depth insight into the advanced Na + storage mechanisms of Fe 3 C@Fe-N-C offers precise guidance for the rational establishment of confinement heterostructures in SIBs.