Interfacial Dual‐Modulation via Cationic Electrostatic Shielding and Anionic Preferential Adsorption toward Planar and Reversible Zinc Electrodeposition

Abstract Rechargeable aqueous zinc‐ion batteries (ZIBs) with low cost and high safety arouse most promises as next‐generation energy storage configurations. Yet the heterogeneous electric field distributions and interfacial side reactions are considered stumbling roadblocks toward the commercialization of ZIBs. Here, these challenges via cationic electrostatic shielding and anionic preferential adsorption by sodium gluconate (SG) additive are addressed. The polar functional groups (─COO − ) of SG anions preferentially anchor to the Zn anode, which can alter Zn 2+ migration pathways and restrain side reactions. Moreover, as per the smaller effective reduction potential, the separated cations (Na + ) from SG serve as a dynamic armor to provide strong electrostatic shielding effect for uniform Zn 2+ deposition on the [002] crystal plane, radically eliminating Zn dendrite growth and promoting anti‐corrosion behaviors of Zn. Consequently, the Zn//Zn symmetric cell with modified electrolyte confers a lifespan of up to 600 h at a high 80% depth of discharge. Furthermore, even under a record‐low negative/positive ratio of 2.11 and lean electrolyte of 30 µL mAh −1 , the Zn//VOX full cell remains enhanced capacity retention of 84.37% even after 800 cycles at 1 A g −1 . This work develops an interfacial dual‐modulation strategy and provides unique insights to enlighten the practical application of ZIBs.