Geometrically‐Screened, Sterically‐Hindered Additive for Wide‐Temperature Aqueous Zinc‐Ion Batteries

Abstract Aqueous zinc‐ion batteries (AZIBs) are emerging as a highly promising alternative to lithium‐ion batteries for next‐generation energy storage, owing to their intrinsic safety, low cost, and environmental friendliness. In order to overcome these limitations, herein, a representative set of saccharide‐based electrolyte additives is systematically screened, aiming to precisely tune the steric hindrance and molecular geometry by varying their glycosidic linkages. Cellobiose (CBS), with its unique β‐1,4‐glycosidic bond, is identified as a superior additive. Theoretical and spectroscopic analyses reveal that CBS manipulates the hydrogen‐bond network, enhancing low‐temperature performance. Its zincophilic nature promotes adsorption, forming a robust hybrid solid electrolyte interphase that orients deposition to the Zn (002) plane and mitigates parasitic side reactions. Consequently, symmetric cells with the CBS additive achieved an exceptional lifespan exceeding 4000 h and stable operation at a high depth of discharge (46.97%). Furthermore, Zn||NH 4 V 4 O 10 pouch cell delivered 89.21% of capacity retention after 400 cycles with a high cathode mass loading (7.82 g cm −2 ) and a low N/P ratio (2.9). This work establishes a rational design strategy using a sustainable additive to develop high‐performance, wide‐temperature AZIBs.