In Situ Insight into the Interfacial Dynamics in “Water‐in‐Salt” Electrolyte‐Based Aqueous Zinc Batteries

Abstract Water‐in‐salt (WIS) electrolyte is considered as one of most promising systems for aqueous zinc batteries (AZBs) due to its dendrite‐free plating/stripping with nearly 100% Coulombic efficiency. However, the understanding of the interfacial mechanisms remains elusive, which is crucial for further improvements in battery performance. Herein, the interfacial processes of solid electrolyte interphase (SEI) formation and subsequent Zn plating/stripping are monitored by in situ atomic force microscopy and in situ optical microscopy. The live formation of uniform and compact LiF‐rich SEI in WIS systems could induce the uniform hexagonal Zn deposition with preferential orientation growth in the (002) crystal plane, showing excellent plating/stripping reversibility. In contrast, the SEI formed in 1 m zinc bis(trifluoromethylsulfonyl)imide (Zn(TFSI) 2 ) is uneven and rich in inert ZnO, adversely triggering the dendrite propagation and successive “dead” Zn accumulation in repeated deposition/dissolution cycles. This work provides an in‐depth understanding of the relationship between SEI evolution and Zn‐deposited behaviors in AZBs, possibly stimulating more research on rational composition design and structural optimization of solid/liquid interface for advanced rechargeable aqueous multivalent‐ion batteries.