NASICON-structured Na₃Zr₂Si₂PO₁₂ ceramics are deemed as promising electrolytes for all-solid-state sodium metal batteries (ASSSB). However, their practical applications are extremely hindered by poor interfacial performance, especially at room temperature. Here, we report that the intrinsic features of the Na₃Zr₂Si₂PO₁₂-based electrolyte, i.e., microstructure and composition, prominently impact its interfacial electrochemical behavior. Sc³⁺-substituted Na₃Zr₂Si₂PO₁₂ ceramic with a refined microstructure shows significantly enhanced ionic conductivity and reduced activation energy. Consequently, a robust contact and stable interface with low interfacial resistance (63 Ω cm² at 25°C) are realized between Na electrode and the electrolyte ceramic. Both sodium symmetric and all-solid-state cells based on this ceramic electrolyte present notable cycling stability and rate performance at room temperature, further confirming the importance of the active microstructure control of electrolyte in improving the Na⁺ transport capability and accelerating the formation of kinetically stable interphase at the Na/ceramic electrolyte interface.

NASICON 结构的 Na ₃ Zr ₂ Si ₂ PO ₁₂陶瓷被认为是全固态钠金属电池 (ASSSB) 的有前途的电解质。然而，它们的实际应用受到界面性能差的极大阻碍，尤其是在室温下。在这里，我们报告了 Na ₃ Zr ₂ Si ₂ PO ₁₂基电解质的固有特征，即微观结构和组成，显着影响其界面电化学行为。Sc ³⁺ -取代的 Na ₃ Zr ₂ Si ₂ PO ₁₂具有精细微结构的陶瓷显示出显着增强的离子电导率和降低的活化能。因此，在 Na 电极和电解质陶瓷之间实现了坚固的接触和具有低界面电阻（25°C 时为63 Ω cm ²）的稳定界面。基于这种陶瓷电解质的钠对称电池和全固态电池在室温下均表现出显着的循环稳定性和倍率性能，进一步证实了电解质的主动微观结构控制在提高 Na ⁺传输能力和加速形成动力学方面的重要性Na/陶瓷电解质界面处稳定的界面。