The sodium (Na) metal anode encounters issues such as volume expansion and dendrite growth during cycling. Herein, a novel three-dimensional flexible composite Na metal anode was constructed through the conversion-alloying reaction between Na and ultrafine SbS nanoparticles encapsulated within the electrospun carbon nanofibers (SbS@CNFs). The formed sodiophilic NaSb sites and the high Na-conducting NaS matrix, coupled with CNFs, establish a spatially confined "sodiophilic-conductive" network, which effectively reduces the Na nucleation barrier, improves the Na diffusion kinetics, and suppresses the volume expansion, thereby inhibiting the Na dendrite growth. Consequently, the Na/SbS@CNFs electrode exhibits a high Coulombic efficiency (99.94%), exceptional lifespan (up to 2800 h) at high current densities (up to 5 mA cm), and high areal capacities (up to 5 mAh cm) in symmetric cells. The coin-type full cells assembled with a NaV(PO)/C cathode demonstrate significant enhancement in electrochemical performance. The flexible pouch cell achieves an excellent energy density of 301 Wh kg.
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