Elemental fluorine, F2, is used in the nuclear fuel cycle for the isotopic separation of uranium-235 and 238, as well as for the purification of LiF-BeF2 in molten salt reactors. F2 is generated on an industrial scale by an electrochemical process using carbon electrodes in a KF-2HF molten salt. Carbon electrodes are used for industrial F2 generation due to its chemical stability, high conductivity, and relatively low cost. One of the main issues faced when using carbon electrodes in this chemical system is passivation through the formation of C-F compounds on the surface of the electrode. This results in a loss of anode wettability to the electrolyte and diminished charge transfer rate. The voltage needed for the fluorine evolution reaction increases which negatively impacts the safety of the system, increases the operating costs, and leads to faster degradation of the electrode.
The degradation of electrical properties during passivation is progressive, eventually leading to electrode deactivation. The process of deactivation begins with a passivating C-F layer at potentials above the equilibrium potential (2.92 V). The layer is both non-wetting to the KF-2HF media and insulating. Deactivation begins with inhibited F2 bubble detachment, formation of a persistent gas layer, and finally deactivation as the electrode surface is completely covered by a thick, insulating C-F layer causing charge transfer to cease. Only a small current is able to flow, even at high potentials (up to 9 V), indicating F2 generation is completely inhibited. The purpose of this study is to manufacture and test model carbon electrodes and, to examine the non-wetting properties of a partially fluorinated surface. The electrodes will be prepared by mixing PTFE-particles with Vulcan carbon powder and then pressing to form pellets. These electrodes should have a reproducible surface for electrochemical performance studies that will lead to a better understanding of the surface chemistry. The research will develop novel electrodes with a goal to minimize the voltage required for F2 production. This will enhance the efficiency in the overall process and lower the manufacturing costs for F2.
Carbon electrodes with different PTFE-content (20 w.% and 35 w.%) were synthesized. Electrochemical fluorination was then carried out at different potentials in the F2 generation region (4 to 8 V) in molten KF·2HF electrolyte at ∼90 °C. The electrochemical behaviour of the carbon-PTFE electrodes was examined and compared for both fluorine passivated and non-passivated graphite, amorphous carbon, and vitreous carbon electrodes. The growth of the electrical double-layer capacitance between the carbon electrodes and the KF·2HF molten salt was studied. The effects of composition of fluorinated and non-fluorinated carbon on electrode performance are presented.
On the Dimensions Required for a Molten Salt Zero Power Reactor Operating on Chloride Salts