Enhancing Capacity Performance by Utilizing the Redox Chemistry of the Electrolyte in a Dual‐Electrolyte Sodium‐Ion Battery

: A strategy is described to increase charge storage in a dual electrolyte Na-ion battery (DESIB) by combining the redox chemistry of the electrolyte with a Na+ ion de-insertion/insertion cathode. Conventional electrolytes do not contribute to charge storage in battery systems, but redox-active electrolytes augment this property via charge transfer reactions at the electrode-electrolyte interface. The capacity of the cathode combined with that provided by the electrolyte redox reaction thus increases overall charge storage. An aqueous sodium hexacyanoferrate (Na4 Fe(CN)6 ) solution is employed as the redox-active electrolyte (Na-FC) and sodium nickel Prussian blue (Nax -NiBP) as the Na+ ion insertion/de-insertion cathode. The capacity of DESIB with Na-FC electrolyte is twice that of a battery using a conventional (Na2 SO4 ) electrolyte. The use of redox-active electrolytes in batteries of any kind is an efficient and scalable approach to develop advanced high-energy-density storage systems.