Insight into Anionic Discrepancies in Bipolar Poly(Thionine) Organic Cathodes for Aqueous Zinc Ion Batteries

Abstract Electroactive organic electrode materials exhibit remarkable potential in aqueous zinc ion batteries (AZIBs) due to their abundant availability, customizable structures, sustainability, and high reversibility. However, the research on AZIBs has predominantly concentrated on unraveling the storage mechanism of zinc cations, often neglecting the significance of anions in this regard. Herein, bipolar poly(thionine) is synthesized by a simple and efficient polymerization reaction, and the kinetics of different anions are investigated using poly(thionine) as the cathode of AZIBs. Notably, poly(thionine) is a bipolar organic polymer electrode material and exhibits enhanced stability in aqueous solutions compared to thionine monomers. Kinetic analysis reveals that ClO ₄ ⁻ exhibits the fastest kinetics among SO ₄ ²⁻ , Cl ⁻ , and OTF ⁻ , demonstrating excellent rate performance (109 mAh g ⁻¹ @ 0.5 A g ⁻¹ and 92 mAh g ⁻¹ @ 20 A g ⁻¹ ). Mechanism studies reveal that the poly(thionine) cathode facilitates the co‐storage of both anions and cations in Zn(ClO ₄ ) ₂ . Furthermore, the lower electrostatic potential of ClO ₄ ⁻ influences the strength of hydrogen bonding with water molecules, thereby enhancing the overall kinetics in aqueous electrolytes. This work provides an effective strategy for synthesizing high‐quality organic materials and offers new insights into the kinetic behavior of anions in AZIBs.