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The flexible free‐standing cathodes with high energy density have been challenging toward wearable sodium‐ion batteries (SIBs). Herein, Na5V12O32 nanobelts (NVO‐NBs)‐based heterostructure is fabricated with boosting the sodium‐ion kinetic characteristics to address the challenges. In the heterostructure, the controllable VOC bonds are generated at the interface originating from the chemical conversion...