Labile Coordination Interphase for Regulating Lean Ion Dynamics in Reversible Zn Batteries

Abstract Rechargeability in zinc (Zn) batteries is limited by anode irreversibility. The practical lean electrolytes exacerbate the issue, compromising the cost benefits of zinc batteries for large‐scale energy storage. In this study, a zinc‐coordinated interphase is developed to avoid chemical corrosion and stabilize zinc anodes. The interphase promotes Zn²⁺ ions to selectively bind with histidine and carboxylate ligands, creating a coordination environment with high affinity and fast diffusion due to thermodynamic stability and kinetic lability. Experiments and simulations indicate that interphase regulates dendrite‐free electrodeposition and reduces side reactions. Implementing such labile coordination interphase results in increased cycling at 20 mA cm⁻² and high reversibility of dendrite‐free zinc plating/stripping for over 200 hours. A Zn||LiMn₂O₄ cell with 74.7 mWh g⁻¹ energy density and 99.7% Coulombic efficiency after 500 cycles realized enhanced reversibility using the labile coordination interphase. A lean‐electrolyte full cell using only 10 µL mAh⁻¹ electrolyte is also demonstrated with an elongated lifespan of 100 cycles, five times longer than bare Zn anodes. The cell offers a higher energy density than most existing aqueous batteries. This study presents a proof‐of‐concept design for low‐electrolyte, high‐energy‐density batteries by modulating coordination interphases on Zn anodes.