Two different SnO-based glasses, Sn2B3O6.5 and Sn2B2AlO6.5, have been examined with FT-IR and Raman spectroscopy at different stages during the first electrochemical cycle. It was found that some disruption of the connection between borate units in the network occurred during cycling. There was also an irreversible formation of Li3BO3 that can be related to the large capacity loss.