Montmorillonite Interfacial Chemistry Regulation on Homogeneous Zn Deposition: A Microenvironment‐Controlled Additive Strategy for Sustainable Zinc Metal Anodes

Aqueous zinc (Zn) metal batteries (AZBs) have emerged as highly promising candidates for large‐scale energy storage systems because of their inherent safety and cost‐effectiveness. However, their practical implementation remains constrained by parasitic side reactions and uncontrolled dendrite growth at the metallic Zn anode. Herein, a microenvironment‐controlled additive strategy is proposed via employing phytic acid‐functionalized montmorillonite (MPA) nanosheets as electrolyte additives for highly durable AZBs. The MPA nanosheets spontaneously assemble onto the surface of the Zn anode through interfacial self‐adsorption, effectively suppressing parasitic reactions. Moreover, the regulation of interfacial chemistry enhances the zincophilic characteristic, enabling precise modulation of Zn 2+ flux distribution and directing homogeneous Zn electrodeposition through spatially controlled ion coordination. As a result, the Zn||Zn symmetric cell with the MPA additives achieves a stable cycle for over 2800 h at 2 mA cm −2 . The assembled Zn||VO 2 full cell within the modified electrolyte maintains exceptional cycling stability of 89.5% after 1000 cycles. This work presents a facile and efficient microenvironment‐regulated additive strategy for homogeneous Zn deposition, aimed at achieving highly reversible AZBs.