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Measuring Zn Transference with Precision: Insights for Dendrite-Free Zinc Metal Anodes
Dario Gomez Vazquez1, Julita Tabor1, Travis P Pollard2
1Department of Mechanical and Process Engineering, ETH Zurich, Zurich, 8092, Switzerland.
Advanced Materials (Deerfield Beach, Fla.)
|August 23, 2025
Summary
Optimizing zinc ion (Zn2+) transference in electrolytes is key for high-performance zinc-metal batteries. This study introduces a new method to measure Zn2+ transference, revealing that while co-salts boost conductivity, they can hinder Zn2+ transport, impacting battery efficiency.
Area of Science:
- Electrochemistry
- Materials Science
- Energy Storage
Background:
- Electrolyte additives like alkaline metal salts are used in zinc-metal batteries to improve conductivity and reduce overpotential.
- However, these additives can negatively impact the crucial zinc ion (Zn2+) transference number due to the presence of more mobile alkali cations.
- A high Zn2+ transference number is essential for efficient, safe, high-rate cycling by minimizing concentration polarization and dendrite formation.
Purpose of the Study:
- To develop and apply a reliable method for measuring Zn2+ transference numbers in complex, non-binary electrolytes.
- To investigate the impact of alkali co-salts on the transport properties and solvation environment of Zn2+ in zinc-metal battery electrolytes.
- To correlate electrolyte transport properties with electrochemical performance.
Main Methods:
- A modified Hittorf-type method was employed to measure transference numbers in complex electrolytes.
- Molecular dynamics simulations were used to support experimental findings.
- X-ray absorption spectroscopy was utilized to study the Zn solvation environment.
- Zn-K acetate electrolytes with varying Zn2+ fractions were analyzed.
Main Results:
- The modified Hittorf method successfully measured transference numbers for Zn2+, K+, and acetate ions in Zn-K acetate electrolytes.
- While adding potassium acetate (KOAc) increased ionic conductivity, it significantly decreased the Zn2+ transference number.
- Electrolytes with higher Zn2+ transference numbers demonstrated superior performance in high-rate cycling tests.
Conclusions:
- Optimizing the Zn2+ transference number, rather than just ionic conductivity, is critical for enhancing the performance of zinc-metal anodes.
- The study highlights the trade-off between conductivity enhancement and Zn2+ transport when using alkali co-salts.
- The developed method provides a pathway for designing advanced electrolytes for high-performance zinc-metal batteries.
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