Pressureless all‐solid‐state Na/S batteries with self‐supporting Na₅YSi₄O₁₂ scaffolds

Abstract The development of reliable and affordable all‐solid‐state sodium metal batteries (ASS‐SMBs) requires suitable solid‐state electrolytes with cost‐efficient processing and stabilized electrode/electrolyte interfaces. Here, an integrated porous/dense/porous Na₅YSi₄O₁₂ (NYS) trilayered scaffold is designed and fabricated by tape casting using aqueous slurries. In this template‐based NYS scaffold, the dense layer in the middle serves as a separator and the porous layers on both sides accommodate the active materials with their volume changes during the charge/discharge processes, increasing the contact area and thus enhancing the utilization rate and homogenizing the current distribution. The Na/NYS/Na symmetric cells with the Pb‐coated NYS scaffold exhibit significantly reduced interfacial impedance and superior critical current density of up to 3.0 mA cm⁻² against Na metal owing to enhanced wettability. Furthermore, the assembled Na/NYS/S full cells operated without external pressure at room temperature showed a high initial discharge capacity of 970 mAh g⁻¹ and good cycling stability with a capacity of 600 mAh g⁻¹ after 150 cycles (based on the mass of sulfur). This approach paves the way for the realization of economical and practical ASS‐SMBs from the perspective of ceramic manufacturing.