Fukui Function‐Engineered Gel Electrolytes: Thermodynamic/Kinetic‐Synergistic Regulation for Long‐Cycling Zinc Metal Batteries

Abstract While traditional gel electrolytes address critical issues such as electrolyte leakage and dendrite growth in zinc metal batteries (ZMBs), their intrinsic inability to suppress the competing hydrogen evolution reaction (HER) remains a fundamental limitation. Herein, a Fukui function‐guided molecular engineering approach is proposed to develop a gel electrolyte (HG‐3TP) with higher Gibbs free energy of HER ( ΔG HER ). The reduced electrophilic Fukui function inhibits Zn electron extraction while participating in Zn 2 ⁺ solvation to decrease free water activity. Simultaneously, attenuated nucleophilic Fukui function creates an inert barrier on Zn anodes, raising H⁺ desorption energy and lowering proton diffusion. These synergistic effects suppress the Volmer / Heyrovsky step, significantly increasing ΔG HER and inhibiting HER. Meanwhile, optimized interfacial energetics facilitate uniform Zn plating/stripping while maintaining cathode compatibility. As a result, Zn batteries with HG‐3TP exhibit excellent long‐term cycling stability, achieving 4,000 h in Zn||Zn symmetric cells and maintaining operation for 710 h at 60 °C, while demonstrating 83.5% capacity retention over 11 000 cycles in Zn||VO 2 full cells. This work establishes a thermodynamics‐kinetics orchestrated paradigm through Fukui function‐guided electrolyte design, advancing ultrastable ZMBs for scalable energy storage.