High-Precision Surface Tension Measurements of Sodium, Potassium, and Their Alloys via Du Noüy Ring Tensiometry

Abstract

The development of post-lithium-ion batteries has sparked significant interest in alkali-metal anodes, particularly sodium (Na), potassium (K), and sodium–potassium (Na–K) alloys. Na–K alloys are promising for partially liquid anodes due to their unique low melting points. A critical factor influencing Na–K-based anode performance is wetting behavior, which governs electrical conductivity, mechanical contact, and long-term stability. At the heart of wetting lies surface tension, a fundamental property of solid–liquid–gas interactions. However, the surface tension of alkali metals and their alloys, particularly Na–K systems, remains poorly understood due to experimental and theoretical challenges. This study bridged these gaps by employing Du Noüy ring tensiometry for the first time in alkali-metal systems to measure the surface tension of Na, K, and Na–K alloys across temperatures from ambient to 180 °C. A key innovation in this work is the development of the push-in Du Noüy method, which provided significantly higher precision and reliability compared to the traditional pull-out technique, without requiring a correction factor. The measured surface tension decreased with increasing temperature for the studied Na–K alloys. For instance, for a eutectic Na–K mixture, the surface tension decreases from 121.7 mN m^–1 to 112.2 mN m^–1 when increasing the temperature from ambient to 180 °C. Additionally, this study presented the first use of Gibbs free energy minimization to model the surface tension of the Na–K system. The robust method significantly enhanced the predictive accuracy compared to the previous simplified model, reducing deviations from 25% to 2%. Our findings reveal that surface tension increases with sodium mole fraction in the bulk phase, yet the surface monolayer remains potassium-rich, indicating non-ideal surface behavior. This study deepens the understanding of alkali-metal wetting behavior, providing valuable insights for designing optimized interfaces in next-generation semi-solid alkali-metal batteries.