Hetero‐Solvation‐Diluted Strongly‐Coordinated Zn2+‐Cosolvent Pairs Downshifting Zn Electrode Potential for High‐Voltage Hybrid Batteries

Abstract Mild aqueous Zn batteries (AZBs) generally suffer a low‐voltage/energy dilemma, which compromises their competitiveness for large‐scale energy storage. Pushing Zn anode potential downshift is an admissible yet underappreciated approach for high‐voltage/energy AZBs. Herein, with a mild hybrid electrolyte containing in situ‐derived diluted strongly‐coordinated Zn 2+ ‐cosolvent pairs, a considerable Zn anode potential downshift is initially achieved for high‐voltage Zn‐based hybrid batteries. The chosen butylpyridine cosolvent not only strongly coordinates Zn 2+ ions but also acts as a hydrogen‐bond end‐capping agent to inhibit hydrogen evolution reaction (HER). The electrolyte environment with hetero‐solvation‐diluted strongly‐coordinated Zn 2+ ‐cosolvent pairs remarkably lowers Zn 2+ activity, responsible for the Zn electrode potential downshift (−0.330 V vs Zn), confirming to modified Nernst law (Δ E = ln[ a ( Zn 2 + )/a(coordinated solvent)]). With the diluted Zn 2+ ‐containing hybrid electrolyte, the Zn//Zn symmetric cell in the hybrid electrolyte shows a long lifespan over 1270 h at a stripping/plating capacity of 0.4 mA h cm −2 . Compared with in common hybrid electrolytes, the as‐assembled Zn‐MnO 2 hybrid battery delivers a ca. 0.278 V enhanced voltage plateau (1.57 V) and a long‐term cyclability of over 736 cycles. This work opens a new avenue toward Zn anode potential downshift for high‐voltage AZBs, which can extend to other mild metal batteries.