No abstract

Rechargeable Na‐ion batteries (NIBs) are attractive large‐scale energy storage systems compared to Li‐ion batteries due to the substantial reserve and low cost of sodium resources. The recent rapid development of NIBs will no doubt accelerate the commercialization process. As one of the indispensable components in current battery systems, organic liquid electrolytes are widely used for their high ionic conductivity and good wettability, but the low thermal stability, especially the easy flammability and leakage make them at risk of safety issues. The booming solid‐state batteries with solid‐state electrolytes (SSEs) show promise as alternatives to organic liquid systems due to their improved safety and higher energy density. However, several challenges including low ionic conductivity, poor wettability, low stability/incompatibility between electrodes and electrolytes, etc., may degrade performance, hindering the development of practical applications. In this review, an overview of Na‐ion SSEs is first outlined according to the classification of solid polymer electrolytes, composite polymer electrolytes, inorganic solid electrolytes, etc. Furthermore, the current challenges and critical perspectives for the potential development of solid‐state sodium batteries are discussed in detail.

Water‐in‐salt (WiS) electrolytes provide a new pathway to widen the electrochemical window of aqueous electrolytes. However, their formulation strongly depends on the solubility of the chosen salts, imposing a stringent restriction on the number of possible WiS systems. This issue becomes more severe for aqueous Na‐ion batteries (ANIBs) owing to the relatively lower solubility of sodium salts compared to its alkaline cousins (Li, K, and Cs). A new class of the inert‐cation‐assisted WiS (IC‐WiS) electrolytes containing the tetraethylammonium (TEA+) inert cation is reported. The Na IC‐WiS electrolyte at a superhigh concentration of 31 mol kg–1 exhibits a wide electrochemical window of 3.3 V, suppresses transition metal dissolution from the cathode, and ensures singular intercalation of Na into both cathode and anode electrodes during cycling, which is often problematic in mixed alkali cation systems such as K–Na and Li–Na. Owing to these unique advantages of the IC‐WiS electrolyte, the NaTiOPO4 anode and Prussian blue analog Na1.88Mn[Fe(CN)6]0.97·1.35H2O cathode can be coupled to construct a full ANIB, delivering an average voltage of 1.74 V and a high energy density of 71 Wh kg−1 with a capacity retention of 90% after 200 cycles at 0.25C and of 76% over 800 cycles at 1C.