Oriented Porous NASICON 3D Framework via Freeze-Casting for Sodium-Metal Batteries

Sodium-metal batteries are promising candidates for low-cost, large-format energy storage systems. However, sodium-metal batteries suffer from high interfacial resistance between the electrodes and the solid electrolyte, leading to poor electrochemical performance. We demonstrate a sodium superionic conductor (NASICON) with an oriented porous framework of sodium aluminum titanium phosphate (NATP) fabricated by the freeze-casting technique, which shows excellent properties as a solid electrolyte. Using X-ray computed tomography, we confirm the uniform low-tortuosity channels present along the thickness of the scaffold. We infiltrated the porous NATP scaffolds with sodium vanadium phosphate (NVP) cathode nanoparticles achieving mass loadings of ∼3–4 mg cm –2, which enables short sodium ion diffusion path lengths. For the resulting hybrid cell, we achieved a capacity of ∼90 mAh g –1 at a specific current of 50 mA g –1 (∼300 Wh kg –1 ) for over 100 cycles with ∼94% capacity retention. Our study offers valuable insights for the design of hybrid solid electrolyte–cathode active material structures to achieve improved electrochemical performance through low-tortuosity ion transport networks.