The practical implementation of MnO‐based anode materials is still obstructed because of their short cyclic life and unsatisfactory rate performance, attributable to low conductivity, large volume variation and self‐aggregation of MnO during intense cycles. To overcome these obstacles, we successfully fabricated nitrogen‐doped carbon@MnO hierarchical hollow spheres through a novel approach. As anode nanomaterials for Li‐ion batteries, the nanocomposite possesses a highly reversible capacity of 1302 mAh g−1 after the 200th cycle at 0.1 Ag−1 and 964 mAh g−1 after the 500th cycle at 0.5 Ag−1, respectively. The prominent electrochemical performances of the nanocomposite may result from synthetic effects of nitrogen‐doped carbon hollow structures, nanosized MnO and the gradual generation of high‐oxide‐state manganese oxide on nitrogen‐doped carbon hollow spheres during intensive cycles. The aforementioned results also demonstrate that MnO nanocrystals can be well utilized by attaching to nitrogen‐doped carbon hollow spheres, which is a valid way to achieve excellent lithium storage properties for transition metal oxides.
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