Tailoring Unconventional Cyanogen Defect in High-Entropy Prussian Blue Cathode Material for Advanced Sodium-Ion Batteries

High-entropy Prussian blue analogues (PBAs) are promising cathodes for sodium-ion batteries (SIBs). However, inherent [Fe(CN)₆]^4– defects deteriorate electrochemical kinetics and phase stability. Herein, an unusual cyanide (CN^–) vacancy is tailored in high-entropy PBA (HE-Cu-PA, Na_1.58Mn_0.191Fe_0.2Co_0.195Ni_0.2Cu_0.19[Fe(CN)_5.85]), constructed via a phytic acid (PA) assisted coprecipitation method, as cathode material for SIBs. The precisely designed high-entropy composition with CN^– defects create adaptive coordination flexible sites and local electronic delocalization regions, synergistically enhancing structural stability, electrochemical dynamics, and redox reversibility. The large-sized [Fe(CN)₆]^4– vacancy in PA-free high-entropy PBA (HE-Cu) exhibits poor electronic transfer capability and accumulated lattice strain, while static local lattice distortion generated by Ti³⁺N₆ octahedron in high-entropy composition (HE-Ti-PA) causes large lattice stress and Na-ion diffusion barrier. The complex structural evolution (monoclinic ↔ cubic ↔ tetragonal) originated from Jahn–Teller effect and octahedron instability can be completely restrained in HE-Cu-PA, achieving a zero-strain solid-solution Na-ion storage mechanism, where Mn, Fe, Co, and Cu-ions act as redox sites for charge compensation. Therefore, HE-Cu-PA delivers high initial capacity of 117.6 mAh·g⁻¹, superior rate capability and ultra-long lifespan over 6000 cycles with ultra-low decay-rate of 0.0085% per cycle. And ultra-long cycling lifetime over 4000 cycles can be acquired for high-energy-density (338.0 Wh·kg⁻¹) quasi-solid-state Na-ion full batteries.