The electrochemical behaviour and associated structural changes of Li4T5O12 have been investigated down to 0.01 V vs. Li/Li+. In addition, member of the solid solutions Li1+xM1-3xTi1+2xO4, M = Fe, Ni and Cr (x = 0.30) have been studied by a combination of electrochemical measurements and structural studies including neutron diffraction on as-prepared samples.