Prussian Blue‐Type Sodium‐ion Conducting Solid Electrolytes for All Solid‐State Batteries

Abstract Conventional solid electrolyte frameworks typically consist of anions such as sulphur, oxygen, chlorine, and others, leading to inherent limitations in their properties. Despite the emergence of sulphide, oxide, and halide‐based solid electrolytes for all‐solid‐state batteries, their utilization is hampered by issues, including the evolution of H 2 S gas, the need for expensive elements, and poor contact. Here, we first introduce Prussian Blue analogue (PBA) open‐framework structures as a solid electrolyte that demonstrates appreciable Na + conductivity (>10 −2 mS cm −1 ). We delve into the relationship between Na + conductivity and the lattice parameter of N‐coordinated transition metal, which is attributed to the reduced interaction between Na + and the framework, corroborated by the distribution of relaxation times and density functional theory calculations. Among the five PBAs studied, Mn‐PBA have exhibited the highest Na + conductivity of 9.1×10 −2 mS cm −1 . Feasibility tests have revealed that Mn‐PBA have maintained a cycle retention of 95.1 % after 80cycles at 30 °C and a C‐rate of 0.2C. Our investigation into the underlying mechanisms that play a significant role in governing the conductivity and kinetics of these materials contributes valuable insights for the development of alternative strategies to realize all‐solid‐state batteries.