Aromatic Ketones as Mild Presodiating Reagents toward Cathodes for High‐Performance Sodium‐Ion Batteries

Abstract Chemical presodiation (CP) is an effective strategy to enhance energy density of sodium ion batteries. However, the sodiation reagents reported so far are basically polycyclic aromatic hydrocarbons (PAHs) wth low reductive potential (~0.1 V vs . Na + /Na), which could easily cause over‐sodiation and structural deterioration of the presodiated cathodes. In this work, Aromatic ketones (AKs) are rationally designed as mild presodiating reagents by introducing a carbonyl group (C=O) into PAHs to balance the conjugated and inductive effect. As the representatives, two compounds 9‐Fluorenoneb (9‐FN) and Benzophenone (BP) manifest favorable equilibrium potential of 1.55 V and 1.07 V ( vs . Na + /Na), respectively. Note that 9‐FN demonstrates versatile presodiating capability toward multiple Na uptake hosts (tunneled Na 0.44 MnO 2 , layered Na 0.67 Ni 0.33 Mn 0.67 O 2 , polyanionic Na 4 Fe 2.91 (PO 4 ) 2 P 2 O 7 , Na 3 V 2 (PO 4 ) 3 and Na 3 V 2 (PO 4 ) 2 F 3 ), enabling greatly improved initial charging capacity of the cathode to balance the irrevisible capacity of the anode. Our results indicate that the Aromatic ketones are competitive presodiating cathodic reagents for high‐performance sodium‐ion batteries, and will inspire more studies and application attempts in the future.