A High‐Voltage Organic Cathode Enabled by a Continuous Electronegativity Zone in Aqueous Zinc‐Organic Batteries

Abstract N‐type organics serve as cathode materials for aqueous zinc‐ion batteries, exhibiting high theoretical capacity. However, their operating voltage is typically lower than 1 V (vs Zn ²⁺ /Zn), which significantly restricts the enhancement of the energy density and the practical application of these batteries. To address this issue, an imine compound 3‐5,6,11,12‐tetraazanaphthacene (3TANC) is designed, characterized by a continuous negative electrostatic potential region. This feature results in lower lowest unoccupied molecular orbital (LUMO) energy levels and enables a high average discharge voltage of 1.05 V (vs Zn ²⁺ /Zn). The elevated operating voltage allows 3TANC to achieve an energy density of 215 Wh kg ⁻¹ at 0.1 A g ⁻¹ . Furthermore, the capacity is maintained at 94.38% after 1000 cycles at 2 A g ⁻¹ . Additionally, 3TANC demonstrates the ability for NH ₄ ⁺ storage, exhibiting a high average discharge voltage of −0.1 V (vs SCE) and offers a specific discharge capacity of 267.84 mAh g ⁻¹ at 0.1 A g ⁻¹ . Moreover, 3TANC's ammonium‐ion half‐cells maintain 100% capacity after 2100 cycles at 5 A g ⁻¹ . The Zn||3TANC hybrid ion cell exhibits exceptional cycling stability in 2 m (NH ₄ ) ₂ SO ₄ electrolyte, achieving 90.23% capacity retention over 13800 cycles at 2 A g ⁻¹ . This work presents a novel approach for designing high‐voltage organic cathodes.