Unshared Pair Electrons of Zincophilic Lewis Base Enable Long‐life Zn Anodes under “Three High” Conditions

Abstract The hydrogen evolution and dendrite issues are the notorious culprits of the limited lifespan and Coulombic efficiency (CE) of Zn anodes, particularly at harsh test conditions. Herein, considering the Lewis acidic feature of Zn 2+ , abundant unshared pair electrons of zincophilic Lewis bases are proposed as decent electrolyte additives to stabilize Zn anodes at “Three High” conditions (high depth of discharge, high areal capacity and high current). The unshared pair electrons can remove H 2 O from Zn 2+ solvated sheaths and confine the activity of H 2 O by breaking its hydrogen bonding network. The combination of these factors effectively restricts H 2 O‐involved side reactions and enables dendrite‐free Zn deposition, even at harsh conditions. The effectiveness of this strategy is fully proved by a series of Lewis base molecules. Noticeably, the Zn||Zn cell with an area of 20 cm 2 , using DMF‐containing electrolyte can be stably cycled over 1000 h at 60 % DOD, with a 100 % CE.