Despite the wide application of molten fluoride salts, such as 2LiF-BeF2 (FLiBe), as heat transfer fluids, fuel solvents, and fusion blanket materials in advanced nuclear power concepts, the mechanisms of ion transport, speciation, and reaction kinetics in these systems have not been comprehensively characterized. Though electrochemical methods are powerful tools for probing these properties of molten fluorides, current studies are limited by the lack of a reliable thermodynamic reference electrode (TRE) compatible with the fluoride environment. The reference electrode designs used in fluorides can be classified into three main categories: quasi-reference electrodes (qREs), dynamic reference electrodes (DREs), and thermodynamic reference electrodes. qREs and DREs are not well suited to in-line measurements of molten fluorides since the reference redox couple of the noble qRE material cannot be assumed to be constant and the time scale of the DRE’s relaxation of the transient redox system is too short. Therefore, explorations of the FLiBe system have pursued the development of a TRE which can hold a thermodynamically stable reference potential for an extended time. Current designs using the H2/HF or Ni/Ni2+ couples suffer from either difficult handling of gas electrodes at high temperatures [1] or long equilibriation times. Since pure NiF2 does not melt at reactor operating temperatures (~500-1000°C), the NiF2 used must dissolve into a reservoir of supporting FLiBe, a process which takes over 30 hours. In this study, the performance of a reference electrode using the Ag/Ag+ redox couple is assessed for long-term electrochemical stability. The Ag/AgF system was chosen to address the limitations of the Ni/Ni2+ TRE, as the low melting point of AgF (Tmelt = 435°C) allows for the direct use of the pure salt in the electrode, eliminating the time-consuming dissolution step required for NiF2. The Ag/AgF TRE was constructed by melting AgF salt into a boron-nitride crucible fitted with a LaF3 fluoride membrane and inserting a silver wire into the salt reservoir. The stability and reproducibility of the electrode potential were evaluated through long-term open circuit potential measurements against a platinum qRE in a FLiBe melt at 600°C. The reversibility of the Ag/Ag+ reaction was assessed using a linear polarization study. Finally, the location of the redox potential was found by comparing the open circuit potential of the Ag/AgF TRE against a beryllium rod electrode. The development of a reliable and easy-to-operate thermodynamic reference electrode will facilitate future studies on the thermochemical properties of molten FLiBe while laying the foundation for advancing in-line monitoring and redox control in nuclear technologies. [1] Jenkins, Howard W., "Electrochemical Measurements in Molten Fluorides. " PhD diss., University of Tennessee, 1969. https://trace.tennessee.edu/utk_graddiss/3072
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