A galvanic cell and methods of using the galvanic cell is described for the recovery of uranium from used nuclear fuel according to an electrofluorination process. The galvanic cell requires no input energy and can utilize relatively benign gaseous fluorinating agents. Uranium can be recovered from used nuclear fuel in the form of gaseous uranium compound such as uranium hexafluoride, which can then be converted to metallic uranium or UO2 and processed according to known methodology to form a useful product, e.g., fuel pellets for use in a commercial energy production system.