The development of stable and buffered reference electrodes (REs) is crucial for molten salt electrochemistry, particularly in pyrochemical processing, such as electrorefining. These REs must maintain a stable potential to ensure precise control over electrorefining processes by preventing unwanted shifts in the potential that could lead to impurity deposition. This study evaluated metal chlorides and metal oxides as potential candidates for REs, with their stability assessed via electrochemical methods over extended durations. While metal chloride-based REs exhibited stable potential behavior over time, their response followed the Nernst equation, leading to potential shifts with varying concentrations of oxidized species. Metal oxide-based REs were explored to address the need for both stability and concentration-independent potential. These REs demonstrated the ability to maintain a constant potential regardless of concentration changes. The introduction of this metal oxide-based RE presents a promising advancement for use in binary chloride molten salts, offering robust, stable performance in electrorefining applications, particularly in the electrorefining of plutonium within equimolar sodium chloride and potassium chloride (NaCl-KCl) molten salt systems.

中文翻译：

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用于二元熔融氯化物盐的稳定缓冲参比电极的开发


稳定和缓冲参比电极 （RE） 的开发对于熔盐电化学至关重要，尤其是在热化学加工（如电解精炼）中。这些稀土必须保持稳定的电位，以防止电位发生可能导致杂质沉积的意外变化，从而确保对电解精炼过程的精确控制。本研究评估了金属氯化物和金属氧化物作为 RE 的潜在候选物，并通过电化学方法评估了它们在较长时间内的稳定性。虽然基于金属氯化物的 RE 随时间表现出稳定的电位行为，但它们的响应遵循 Nernst 方程，导致氧化物质浓度的变化电位变化。探索了基于金属氧化物的 RE 以满足对稳定性和浓度无关电位的需求。这些 RE 表现出无论浓度变化如何都能保持恒定电位的能力。这种基于金属氧化物的稀土的推出为二元氯化物熔盐的使用带来了有前途的进步，在电解精炼应用中提供了稳定、稳定的性能，特别是在等摩尔氯化钠和氯化钾 （NaCl-KCl） 熔盐系统中钚的电解精炼中。