| Summary: | Low electrical conductivity severely limits the application of Fe<sub>2</sub>O<sub>3</sub> in lithium- and sodium-ion batteries. In respect of this, we design and fabricate Fe<sub>2</sub>O<sub>3</sub>/Fe<sub>3</sub>O<sub>4</sub> nano-aggregates anchored on nitrogen-doped graphene as an anode for sodium-ion batteries with the assistance of microwave plasma. The highly conductive Fe<sub>3</sub>O<sub>4</sub> in the composite can function as a highway of electron transport, and the voids and phase boundaries in the Fe<sub>2</sub>O<sub>3</sub>/Fe<sub>3</sub>O<sub>4</sub> heterostructure facilitate Na<sup>+</sup> ion diffusion into the nano-aggregates. Furthermore, the Fe–O–C bonds between the nano-aggregates and graphene not only stabilize the structural integrity, but also enhance the charge transfer. Consequently, the Fe<sub>2</sub>O<sub>3</sub>/Fe<sub>3</sub>O<sub>4</sub>/NG anode exhibits specific capacity up to 362 mAh g<sup>−1</sup> at 100 mA g<sup>−1</sup>, excellent rate capability, and stable long-term cycling performance. This multi-component-based heterostructure design can be used in anode materials for lithium- and sodium-ion batteries, and potential opens a new path for energy storage electrodes.
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