Na3V2(PO4)3 Cathode for Room-Temperature Solid-State Sodium-Ion Batteries: Advanced In Situ Synchrotron X-ray Studies to Understand Intermediate Phase Evolution

Sodium-ion batteries (NIBs) can use elements that are abundantly present in Earth's crust and are technologically feasible for replacing lithium-ion batteries (LIBs). Hence, NIBs are essential components for sustainable energy storage applications. All-solid-state sodium batteries are among the most capable substitutes to LIBs because of their potential to have low price, great energy density, and consistent safety. Nevertheless, more advancements are needed to improve the electrochemical performance of the Na₃V₂(PO₄)₃ (NVP) cathode for NIBs, especially with regard to rate performance and operational lifespan. Herein, a core-shell NVP/C structure is accomplished by adopting a solid-state method. The initial reversible capacity of the NVP/C cathode is 106.6 mAh/g (current rate of C/10), which approaches the theoretical value (117.6 mAh/g). It also exhibits outstanding electrochemical characteristics with a reversible capacity of 85.3 mAh/g at 10C and a cyclic retention of roughly 94.2% after 1100 cycles. Using synchrotron-based operando X-ray diffraction, we present a complete examination of phase transitions during sodium extraction and intercalation in NVP/C. To improve safety and given its excellent ionic conductivity and broad electrochemical window, a Na superionic conductor (NASICON) solid electrolyte (Na_3.16Zr_1.84Y_0.16Si₂PO₁₂) has been integrated to obtain an all-solid-state NVP/C||Na battery, which provides an exceptional reversible capacity (95 mAh/g at C/10) and long-term cycling stability (retention of 78.3% after 1100 cycles).