Aqueous zinc-ion batteries (ZIBs) with the characteristics of low production costs and good safety have been regarded as ideal candidates for large-scale energy storage applications. However, the nonconductive and non-redox active polymer used as the binder in the traditional preparation of electrodes hinders the exposure of active sites and limits the diffusion of ions, compromising the energy density of the electrode in ZIBs. Herein, we fabricated vanadium pentoxide nanofibers/carbon nanotubes (V₂O₅/CNTs) hybrid films as binder-free cathodes for ZIBs. High ionic conductivity and electronic conductivity were enabled in the V₂O₅/CNTs film due to the porous structure of the film and the introduction of carbon nanotubes with high electronic conductivity. As a result, the batteries based on the V₂O₅/CNTs film exhibited a higher capacity of 390 mAh g⁻¹ at 1 A g⁻¹, as compared to batteries based on V₂O₅ (263 mAh g⁻¹). Even at 5 A g⁻¹, the battery based on the V₂O₅/CNTs film maintained a capacity of 250 mAh g⁻¹ after 2000 cycles with a capacity retention of 94%. In addition, the V₂O₅/CNTs film electrode also showed a high energy/power density (e.g., 67 kW kg⁻¹/267 Wh kg⁻¹). The capacitance response and rapid diffusion coefficient of Zn²⁺ (~10⁻⁸ cm⁻² s⁻¹) can explain the excellent rate capability of V₂O₅/CNTs. The vanadium pentoxide nanofibers/carbon nanotubes hybrid film as binder-free cathodes showed a high capability and a stable cyclability, demonstrating that it is highly promising for large-scale energy storage applications.

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.