Enhancing the Initial Coulombic Efficiency of Sodium‐Ion Batteries via Highly Active Na2S as Presodiation Additive

Abstract Recently, sodium‐ion batteries (SIBs) have received considerable attention for large‐scale energy storage applications. However, the low initial Coulombic efficiency of traditional SIBs severely impedes their further development. Here, a highly active Na 2 S‐based composite is employed as a self‐sacrificial additive for sodium compensation in SIBs. The in situ synthesized Na 2 S is wrapped in a carbon matrix with nanoscale particle size and good electrical conductivity, which helps it to achieve a significantly enhanced electrochemical activity as compare to commercial Na 2 S. As a highly efficient presodiation additive, the proposed Na 2 S/C composite can reach an initial charge capacity of 407 mAh g −1 . When 10 wt.% Na 2 S/C additive is dispersed in the Na 3 V 2 (PO 4 ) 3 cathode, and combined with a hard carbon anode, the full cell achieves 24.3% higher first discharge capacity, which corresponds to a 18.3% increase in the energy density from 117.2 to 138.6 Wh kg −1 . Meanwhile, it is found that the Na 2 S additive does not generate additional gas during the initial charging process, and under an appropriate content, its reaction product has no adverse impact on the cycling stability and rate performance of SIBs. Overall, this work establishes Na 2 S as a highly effective additive for the construction of advanced high‐energy‐density SIBs.