Alkali metal ion induced lattice regulation for all climate NASICON-type cathode with superior Na-storage performance

Na-ion batteries have been considered as promising candidates for future energy storage owing to Na availability and high-cost performance. However, their wide application is still hindered by poor rate capabilities, insufficient cycle lifespan and inferior variable-temperature performance. Here, we report an aliovalent-ion induced lattice regulation protocol with Li⁺, Na⁺, and K⁺ replacing V³⁺, which motivates the generation of electronic defects and expands the Na⁺ migration pathways. With the partial activation of V⁴⁺/V⁵⁺ redox, the prepared Na₃V_1.94K_0.06(PO₄)₃ cathode exhibits capacity of 120.3 mAh g⁻¹ at 0.1 C with remarkable capability (100.5 mAh g⁻¹) and ultralong cycle stability (99.1 % capacity retention over 3000 cycles) at 20 C. Moreover, 96.9 % capacity retention after 200 cycles at 0.2 C for − 30 °C and discharge capacity of 127.8 mAh g⁻¹ at 0.1 C for 55 °C were achieved for K⁺-substituted cathode_. This work sheds lights on improving Na⁺ migration kinetics and clarifying the objective law for alkali metal ion doping in Na superionic conductor cathodes for wide-temperature batteries.