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Although metallic chalcogenides are deemed as attractive sodium anode materials recently, the electrochemical performance is severely confined by the liability of structural collapse and sluggish ion diffusion kinetics. Herein a composite of carbon-encapsulated bimetallic selenides MoSe2–Sb2Se3 was prepared by a hydrothermal method on the basis of abundant reaction sites, high activity, an extra built-in electric field generated from heterointerfaces, and synergistic effects between the different components. Equally important, the carbon coating is effective to support the structural stability by restraining the vast volumetric variation to achieve the purpose of improving the cycling performance. The density functional theory calculation results indicate that the band gap is narrowed and that the work function is decreased on the interface of the MoSe2–Sb2Se3 heterojunction, leading to an additional driving force stemming from the introduction of the built-in electric field and the formation of the Sb–Se (Se from MoSe2) bond. Therefore, the resultant composite presents increased reaction kinetics and good electrochemical properties by acquiring a capacity of 376.0 mA h g–1 over 580 cycles at 2.0 A g–1 for the half-cell and 276 mA h g–1 over 750 cycles at 2 A g–1 for the full-cell. This work highlights bimetallic selenides with facilitated ion transferability with high performance.

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