With high energy density and improved safety, rechargeable battery chemistries with a zinc (Zn) metal anode offer promising and sustainable alternatives to those based on lithium metal or lithium‐ion intercalation/alloying anode materials; however, the poor electrochemical reversibility of Zn plating/stripping, induced by parasitic reactions with both aqueous and non‐aqueous electrolytes, presently limits the practical appeal of these systems. Although recent efforts in rechargeable Zn metal batteries (RZMBs) have achieved certain advancements in Zn metal reversibility, as quantified by the Coulombic efficiency (CE), a standard protocol for CE has not been established, and results across chemistries and systems are often conflicting. More importantly, there is still an insufficient understanding regarding the critical factors dictating Zn reversibility. In this work, a rigorous, established protocol for determining CE of lithium metal anodes is transplanted to the Zn chemistry and is used for systematically examining how a series of factors including current collector chemistry, current density, temperature, and the upper voltage limit during stripping affect the measured reversibility of different Zn electrolytes. With support from density functional theory calculations, this standardized Zn CE protocol is then leveraged to identify an important correlation between electrolyte solvation strength toward Zn²⁺ and the measured Zn CE in the corresponding electrolyte, providing new guidance for future development and evaluation of Zn electrolytes.

An extended electrochemical stability window of 3.86 V is achieved at 12 mol kg ⁻¹ aqueous polymer electrolyte enabled 3 V full cells with an unprecedented high initial CE of 90.50% and average CE of 99.97%.