Molecular Configuration Engineering of Electrolyte Additives Enables Adaptive Zinc Anodes and Highly Reversible Zn‐S Batteries

ABSTRACT Aqueous zinc−sulfur batteries (AZSBs) suffer from zinc anode parasitic reactions and slow sulfur cathode kinetics. In this study, we propose a coupled spatial−electronic configuration effect strategy. By selecting additive molecules with different spatial−electronic configurations, we successfully revealed the influence of molecular spatial−electronic configuration on the electrode–electrolyte interfacial adsorption layer. The spatial−electronic configuration of benzyltrimethylammonium iodide (BTA) enables the formation of a stable adsorption layer at the anode interface, showing an effectively repulsive effect on hydrated protons and suppressing side reactions. Moreover, BTA is a dual‐functional additive, and the I − ions released from BTA further catalyze sulfur redox conversion, thereby enhancing the capacity of Zn–S batteries. As a result, this functional additive electrolyte enables stable cycling for over 10000 h in Zn||Zn symmetric cells, the Zn||Cu cells exhibit an extended cycle life of over 3800 cycles with an average CE exceeding 99.44%, and Zn−S full cells deliver 422 mAh g −1 after 4000 cycles at 3 A g −1 . This study demonstrates a holistic electrolyte design strategy for highly reversible AZSBs.