A 252Cf-PDMS time-of-flight mass spectrometer was used for the accomplishment of three activities: a) improvement of the spectrometer by introducing new devices; b) analysis of the LiF cluster ion secondary emission; c) analysis of the (LiF)nLi+ metastable íon fragmentation, in flight. The spectrometer improvement consists of: i) the shielding of the start detector to increase its stability, ii) the characterization of two existing deflecting- plate pairs, iii) the installation of a new type of position-sensitive delay line detector for secundary ions, and iv) the project and manufacture of a Einzel lens to increase the transmission of the secondary íons between the sample and the detector. The secondary cluster ion emission of policrystalline LiF, induced by the impact of fission fragments (60 MeV), is analyzed by the time-of-flight technique (TOF). The new position sensitive delay-line detector allows the use of the XY-TOF technique to analyze angular distributions of Li ions and (LiF)nLi+ clusters. Event by event, their axial and radial velocities are measured simultaneously, allowing the angular distributions measurement of clusters with n = 0 to 3. Mean lives of metastable clusters are determined through the measurement of the detection rate dependence on the target bias. After been emitted, the monocharged metatable ions are acelerated by a 2 kV/mm electric field towards a field-free region, where they can spontaneously dissociateinto two fragments, one ion and another neutral. To facilitate the data analysis, it is avoided the detection of ionic fragments by placing an electrostatic filter in front of the detector. Mean lives values of 30 to 100 ns are determined for ionic clusters with n = 1 to 5. The production of neutral species by collision of the (LiF)nLi+ clusters with the gas molecules is also discussed.