氯化物熔盐体系中氧离子电极的制备及性能测试

Preparation and Performance Testing of Oxygen Ion Sensing Electrode in Chloride Molten Salt System

  • 摘要: 为实现高温氯化物熔盐体系中氧离子(O2−)浓度的精准实时监测,本文制备了一种钇稳定氧化锆(YSZ)氧离子测试电极(简称YSZ电极),并对其响应性、稳定性、重现性和平行性进行了评估。使用电化学工作站在不同温度、O2−浓度和气体流量条件下对电极的电化学性能进行了测试。结果表明,YSZ电极对温度和氧浓度的变化表现出高度灵敏的响应。在O2−浓度动态变化的条件下,电极能提供准确及时的响应。在相同条件下进行的单次和多次实验中,电极的电势测量具有优异的重现性。稳定性测试显示,在低氧和高氧条件下,电极均能长期输出稳定的电势信号,其波动范围分别为±10 mV和±4 mV。平行性测试结果表明,不同电极在相同条件下表现出较高的一致性,电势与O2−浓度的对数(pO2−)呈现线性关系,R2均大于0.996。以上结果表明,YSZ电极具有优异的性能,能在高温腐蚀性环境中稳定工作,适用于熔盐体系中O2−浓度的精确测量,为氧化物燃料干法后处理等高温电化学过程提供了重要技术支持。

     

    Abstract: The aim of this study is to develop yttria-stabilized zirconia (YSZ) oxygen ion sensing electrode (referred to as YSZ electrode) for the accurate and real-time monitoring of oxygen ion concentration in high-temperature chloride molten salt systems. Such systems are widely applied in processes such as dry processing of spent nuclear fuel, metal extraction, and molten salt energy storage due to their excellent thermal stability, electrochemical stability, and low vapor pressure. The role of oxygen ions is critical during the electrochemical reduction of uranium-plutonium mixed oxide fuels, where oxygen ions migrate to the anode and oxidize into oxygen gas. High oxygen ion concentrations can lead to platinum corrosion, while low concentrations may cause platinum dissolution. To address these challenges, it is essential to develop in-situ methods for oxygen ion detection in molten salt systems. YSZ electrodes were fabricated using a tubular YSZ membrane filled with reference molten salt containing AgCl and Li2CO3. The electrodes were designed to function in high-temperature environments, featuring robust sealing and miniaturized structures to facilitate usage in confined spaces. The electrodes were tested in LiCl-KCl molten salt under various conditions, including changes in temperature, oxygen ion concentration, and gas flow rates. Electrochemical measurements were performed using a potentiostat to evaluate the response, stability, reproducibility, and parallelism of the electrodes. The performance of the reference electrode was also verified to ensure accuracy and reliability. Additionally, system designs ensured compatibility with high-temperature dynamic environments. The results show that YSZ electrodes are highly sensitive to temperature and oxygen ion concentration variations, providing accurate real-time monitoring of oxygen ion changes. Stability tests indicate that the electrodes could operate reliably under low and high oxygen ion concentrations, with potential fluctuations of ±10 mV and ±4 mV, respectively. Reproducibility was validated through single and multiple experiments, with consistent potential measurements across different trials. Parallelism tests demonstrate that the output potentials of different electrodes are consistent under identical conditions, and the potential values are linearly related to logarithmic concentration of oxygen ion (pO2−), with R2 exceeding 0.996. Furthermore, response time tests show that the electrodes quickly adapt to dynamic changes in oxygen ion concentration, and their performance remains stable over long durations. In summary, YSZ electrodes have demonstrated excellent performance in high-temperature chloride molten salt environments. They provide reliable, accurate, and stable measurement of oxygen ion concentration, making them suitable for dry processing of oxide fuels, electrochemical reduction, and other high-temperature processes.

     

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