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Use of hybridized transition-metal oxides nanostructures with a shell coating show promise for improving the electrochemical performance of sodium-ion batteries. Herein, a novel type of designed sodium vanadate @ polypyrrole (Na 5 V 12 O 32 @PPy) nanocomposites with a synergetic core-shell structure was fabricated using sequential hydrothermal and electrodeposition methods. When the Na 5 V 12 O 32 @PPy nanocomposites were employed as a cathode, the assembled sodium-ion batteries exhibited a high reversible discharge capacity of 213 mAh g −1 at a current density of 30 mA g −1 , high rate performance (133 mAh g −1 at 480 mA g −1 ) and superior cycling performance (202 mAh g −1 at 100 mA g −1 after 100 cycles with a capacity retention of 94%). By contrast, the cycling behavior of this novel material proved to be much better than the naked Na 5 V 12 O 32 nanowires. This research provides a new pathway to explore cathode materials for sodium-ion battery with enhanced electrochemical performance. [ABSTRACT FROM AUTHOR]