A Reversible Zinc Metal Anode with an Inorganic/Organic Solid Electrolyte Interphase Enriched for Epitaxial Deposition Along the Zn (101) Plane

Abstract Aqueous zinc‐metal batteries (AZMBs) have triggered extensive attention by virtue of their intrinsic safety and high theoretical capacity. However, the unstable electrode/electrolyte interface hinders its further industrialization. Herein, chelating additive (GLDA‐4Na) is incorporated into 2 M ZnSO ₄ electrolyte to prolong Zn anode lifespan. Theoretical calculations and experimental results show that GLDA‐4Na additive can induce a robust solid electrolyte interphase (SEI) to stabilize zinc anodes. Meanwhile, its multiple COO ⁻ polar groups can act as solvation sites to coordinate with Zn ²⁺ , reducing the H ₂ O molecules in the Zn ²⁺ solvation sheaths. Finally, GLDA anions exhibit strong adsorption on the Zn(101) crystal plane, inducing preferential Zn deposition along the (101) plane. Such synergistic regulation constructs a Zn ²⁺ ‐rich and H ₂ O‐poor Helmholtz plane to regulate Zn deposition chemistry. As a result, the Zn anode can deliver an ultralong cycle life of over 5500 h at 8 mA cm ⁻² . Even under extreme conditions (−10 °C), the Zn anodes are still able to cycle stably for over 2800 h at 0.5 mA cm ⁻² . Furthermore, the NH ₄ V ₄ O ₁₀ ||Zn full cells with GLDA‐4Na exhibit a capacity retention of 84.47% after 1260 cycles at 4.66 A g ⁻¹ . This work presents a simple, viable approach to a stable Zn anode for high‐performance AZMBs.