Abstract The practical implementation of aqueous Zn‐ion batteries (ZIBs) for large‐scale energy storage is impeded by the challenges of water‐induced parasitic reactions and uncontrolled dendrite growth. Herein, we propose a strategy to regulate both anions and cations of electrolyte solvation structures to address above challenges, by introducing an electrolyte additive of 3‐hydroxy‐4‐(trimethylammonio)butyrate (HTMAB) into ZnSO4 electrolyte. Consequently, the deposition of Zn is significantly improved leading to a highly reversible Zn anode with paralleled texture. The Zn/Zn cells with ZnSO4/HTMAB exhibit outstanding cycling performance, showcasing a lifespan exceeding 7500 h and an exceptionally high accumulative capacity of 16.47 Ah cm−2. Zn/NaV3O8·1.5H2O full cell displays a specific capacity of ~130 mAh g−1 at 5 A g−1 maintaining a capacity retention of 93% after 2000 cycles. This work highlights the regulation on both cations and anions of electrolyte solvation structures in optimizing interfacial stability during Zn plating/stripping for high performance ZIBs.
