Competitive Coordination Structure Regulation in Deep Eutectic Electrolyte for Stable Zinc Batteries

Abstract Rechargeable zinc‐based batteries are finding their niche in energy storage applications where cost, safety, scalability matter, yet they are plagued by rapid performance degradation due to the lack of suitable electrolytes to stabilize Zn anode. Herein, we report a competitive coordination structure to form unique quaternary hydrated eutectic electrolyte with ligand‐cation‐anion cluster. Unraveled by experiment and calculation results, the competing component can enter initial primary coordination shell of Zn 2+ ion, partially substituting Lewis basic eutectic ligands and reinforcing cation‐anion interaction. The hydration‐deficient complexes induced between competing eutectic as hydrogen bond donor‐accepter and water also broaden the electrochemical window and confine free water activity. The altered coordination further leads to robust hybrid organic‐inorganic enriched solid electrolyte interphase, enabling passivated surface and suppressed dendrite growth. Noticeably, stable Zn plating/stripping for 8000 cycles with high Coulombic efficiencies of 99.6 % and long cycling life of 10000 cycles for Zn‐organic batteries are obtained. Even under harsh conditions (small N/P ratio, low temperature), the profits brought by the competitive eutectic electrolyte are still very prominent. This design principle leveraged by eutectic electrolytes with competitive coordination offers a new approach to improve battery performance.