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Abstract Sodium‐ion batteries (SIBs) are considered as a promising alternative to lithium‐ion batteries, due to the abundant reserves and low price of Na sources. To date, the development of anode materials for SIBs is still confronted with many serious problems. In this work, encapsulation‐type structured MoSe 2 @hollow carbon nanosphere (HCNS) materials assembled with expanded (002) planes few‐layer MoSe 2 nanosheets confined in HCNS are successfully synthesized through a facile strategy. Notably, the interlayer spacing of the (002) planes is expanded to 1.02 nm, which is larger than the intrinsic value of pristine MoSe 2 (0.64 nm). Furthermore, the few‐layer nanosheets are space‐confined in the inner cavity of the HCNS, forming hybrid MoSe 2 @HCNS structures. When evaluated as anode materials for SIBs, it shows excellent rate capabilities, ultralong cycling life with exceptional Coulombic efficiency even at high current density, maintaining 501 and 471 mA h g −1 over 1000 cycles at 1 and 3 A g −1 , respectively. Even when cycled at current densities as high as 10 A g −1 , a capacity retention of 382 mA h g −1 can be achieved. The expanded (002) planes, 2D few‐layer nanosheets, and unique carbon shell structure are responsible for the ultralong cycling and high rate performance.
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