Sodium sulfide (Na₂S) as an initial cathode material in room-temperature sodium-sulfur batteries is conducive to get rid of the dependence on Na-metal anode. However, the micron-sized Na₂S that accords with the practical requirements is obstructed due to poor kinetics and severe shuttle effect. Herein, a subtle strategy is proposed via regulating Na₂S redeposition behaviours. By the synergistic effect from both conductive structure and cuprous sulfide (Cu₂S) catalysis, the micron-sized Na₂S particles are broken down and redeposited to nano-size during the initial cycle which can be fully utilized in subsequent cycles. Consequently, the Na₂S/CPVP@Cu₂S||Na cell delivers excellent cyclability (670 mAh g_S⁻¹ after 500 cycles) with a remarkable average Coulombic efficiency over 99.7% and rate capability (480 mAh g_S⁻¹ at 4 A g_S⁻¹). Besides, the Na-free anodes are used to prove the application prospects. This work provides an innovative idea for utilizing micron-sized Na₂S and offers insights into its conversion pathway.

硫化钠 （Na₂S） 作为室温钠硫电池中的初始正极材料，有利于摆脱对 Na 金属负极的依赖。然而，符合实际要求的微米级 Na₂S 由于动力学差和严重的穿梭效应而受到阻碍。在此，通过调节 Na₂S 再沉积行为提出了一种微妙的策略。通过导电结构和硫化亚铜 （Cu₂S） 催化的协同作用，微米级的 Na₂S 颗粒在初始循环中被分解并重新沉积成纳米级，可以在后续循环中充分利用。因此，Na₂S/CPVP@Cu₂S||钠电池具有出色的可循环性（500 次循环后为 670 mAh g ^S-1），具有超过 99.7% 的显着平均库仑效率和倍率能力（4 A g S-1 时为 480 mAh g ^S-1）。此外，无 Na 阳极用于证明应用前景。这项工作为利用微米级 Na₂S 提供了创新思路，并提供了对其转化途径的见解。