Temperature‐Responsive Electrical Double Layer for Self‐Adaptive Solid Electrolyte Interphase Unlocks Wide‐Temperature Aqueous Zinc Ion Batteries

ABSTRACT Constructing a self‐adaptive solid electrolyte interphase (SEI) for wide‐temperature aqueous zinc ion batteries (AZIBs) remains unexplored yet highly challenging. Herein, a temperature‐responsive electrical double layer (EDL) is designed via screening high donor‐number additive, and the EDL composition exhibits temperature‐responsive behavior where elevated temperatures promote anion accumulation and low‐to‐ambient temperatures favor additive enrichment, thereby driving distinct self‐adaptive interfacial chemistries. Experimental and theoretical analyses reveal that low‐to‐ambient temperatures facilitate organic‐inorganic hybrid SEI formation through preferential additive decomposition, whereas high temperatures yield a robust inorganic‐rich SEI via anion decomposition. The self‐adaptive SEIs can significantly modulate Zn 2+ nucleation kinetics across temperatures, promoting uniform Zn deposition with progressively increasing grain sizes during prolonged cycling. Consequently, Zn||Zn cell showcases highly reversible plating/stripping exceeding 5300 cycles at 50 mA cm −2 , while exhibiting broad thermal tolerance across a wide temperature range of −40°C to 60°C. Zn||I 2 full batteries deliver good cycling life of 1000–30 000 cycles, and Ah‐level pouch cell further validates practicality. This work builds the correlation among the temperature‐responsive EDL, interfacial chemistry, and electrochemical performance, advancing wide‐temperature batteries.