A Safe Organic/Inorganic Composite Anode for Sodium‐Ion Batteries

Abstract Sodium‐ion batteries (SIBs), based on hard carbon anodes and Na + ‐intercalation compound cathodes, have gained significant attention. Nonetheless, hard carbon anodes involve the storage of Na + at a low potential, typically below 0.1 V (vs Na/Na + ), which increases the risk of dendritic Na growth on the anode surface during overcharging. Herein, a safe organic/inorganic composite anode containing tetrasodium 3,4,9,10‐perylenetetracarboxylate (Na 4 PTC) and Metallic bismuth (Bi) with a weight ratio of 7:2, which exhibits an average potential of 0.7 V (vs Na + /Na) and a capacity of 150 mAh g −1 is proposed. The electrode reaction involves a reversible coordination reaction within the organic host and alloying reactions within the metallic Bi component. Importantly, the organic component efficiently buffers the volume changes in Bi during the alloying reaction, while the metallic Bi enhances the electronic conductivity of the organic material. As a result, this composite anode shows high cycle stability and rate performance, even under high mass loadings ranging from 10 to 50 mg cm −2 . Furthermore, it is demonstrated that the Na‐ion full cell, consisting of the composite anode and the Na 3 V 2 O 2 (PO 4 ) 2 F cathode, exhibits minimal capacity degradation over 100 cycles while maintaining a high areal capacity of 1.1 mA cm −2 .