Fluorine generation systems are provided that can include, in exemplary embodiments, a reactor configured to decompose a fluorine-comprising material. The reactor can include a plurality of chambers with at least one of the chambers being configured to receive the fluorine-comprising material. The chamber includes sidewalls with the exterior of the sidewalls being at least partially encompassed by heating elements. The system can also include a fluorine reservoir coupled to the reactor with the reservoir configured to receive fluorine upon the decomposition of the fluorine-comprising materials. Fluorine-generation processes are provided that can include, in exemplary embodiments, decomposing pellets of a fluorine-comprising material with the pellets having an average size of from about 1.0 mm to about 3.0 mm. Processes can also include decomposing a composition comprising manganese-fluoride.