Easy‐to‐Lay Poly‐N Heterocyclic Additives Enable Long‐Term Stabilization of Zinc‐Ion Capacitor Anodes under Deep Plating/Stripping

Abstract Addition of organic compounds containing O/N heteroatoms to aqueous electrolytes such as ZnSO 4 (ZS) solutions is one of the effective strategies to inhibit Zn anode dendrites and side reactions. However, addressing the stability of Zn plating/stripping at high current densities and areal capacities by this method is still a challenge, especially in capacitors known for high power and long life. Herein, an organic heterocyclic compound of 1, 4, 7, 10‐tetraazacyclododecane (TC) containing four symmetrically distributed N atoms is employed as ZS additive, expanding the life of Zn anodes from ≈ 30 h to 1000 and 240 h at deep plating/stripping conditions of 10 and 20 mA cm −2 /mAh cm −2 , respectively; the cumulative capacity is as high as 5.0 Ah cm −2 with 99% Coulombic efficiency, far exceeding reported additives. TC with higher binding energies than H 2 O for Zn species tends to adsorb to Zn (002) in a lying manner and participate in the solvation shell of Zn 2+ , thus avoiding Zn dendrites and side‐reaction damage, especially at high current densities. The TC‐endowed Zn anode's stability under such extreme conditions is verified in Zn‐ion capacitors (i.e., > 94.6% capacity retention after 28 000 cycles), providing new insights into the development of high‐power Zn‐based energy storage devices.