Multisite Cooperative Regulation of Solvation and Interface via Dynamic Additive Engineering for Highly Reversible Zinc Batteries

Inexhaustible additives have been reported to enhance the reversibility of aqueous zinc‐ion batteries (AZIBs). However, the structure–performance relationship of additive molecules remains elusive, particularly regarding multisite coordination‐mediated synergistic regulation of solvation and interface. Herein, a dynamic configuration reconstruction mechanism that orchestrates the multisite regulation of solvation and interface is unveiled by utilizing a series of polyhydroxy additive prototypes, demonstrating that the increase of functional groups and chain flexibility in multifunctional‐group molecules (MGMs) contributes to boosting battery performance. MGM with folded configuration engages in multisite Zn2+ coordination in the solvation shell, effectively minimizing active H2O molecule to suppress parasitic reactions, while its configuration transition to straight‐chain architecture enables multisite parallel adsorption on Zn anode interface, thus accelerating desolvation kinetics and steering (002)‐facet‐dominated Zn deposition. Remarkably, Zn//Zn cells achieve long cycle life of 7000 h and subzero‐temperature operation, and Zn//PANI pouch cell maintains nearly 100% capacity retention after 500 cycles. This work opens a fascinating avenue for developing high‐performance batteries via dynamic additive engineering.