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

Area of Science:

• Electrochemistry
• Materials Science
• Energy Storage

Background:

• Traditional gel electrolytes for zinc metal batteries (ZMBs) struggle with hydrogen evolution reactions (HER).
• Electrolyte leakage and dendrite growth are critical issues in ZMBs.
• Suppressing HER is essential for ZMB stability.

Purpose of the Study:

• To engineer a gel electrolyte (HG-3TP) with enhanced Gibbs free energy of HER (ΔGHER) using Fukui function-guided molecular design.
• To inhibit HER by controlling Zn electron extraction, free water activity, and proton diffusion.
• To improve interfacial energetics for uniform Zn plating/stripping and cathode compatibility.

Main Methods:

• Utilized Fukui function analysis for molecular engineering of the gel electrolyte.
• Investigated the effect of reduced electrophilic and attenuated nucleophilic Fukui functions on electrochemical reactions.
• Assessed interfacial energetics and cathode compatibility.
• Performed long-term cycling tests on Zn||Zn symmetric cells and Zn||VO2 full cells.

Main Results:

• The HG-3TP electrolyte significantly increased ΔGHER, effectively suppressing HER.
• Achieved 4,000 hours of stable cycling in Zn||Zn symmetric cells and 710 hours at 60°C.
• Demonstrated 83.5% capacity retention over 11,000 cycles in Zn||VO2 full cells.
• Observed uniform Zn plating/stripping and maintained cathode compatibility.

Conclusions:

• Established a thermodynamics-kinetics orchestrated paradigm for electrolyte design via Fukui function guidance.
• Advanced ultrastable ZMBs through molecular engineering for scalable energy storage.
• The developed HG-3TP electrolyte offers a promising solution for overcoming HER limitations in ZMBs.