Structural characterization and electrochemical behaviour of Li(4−x)/3Ti(5−2x)/3MnxO4 solid solution with spinel-structure

• Lithium spinels anodes in batteries.
• Influence of Ti/Mn ratio in the electrochemical behaviour.
• Li1.3Ti1.6Mn0.1O4: a promising zero-strain material.
• Influence of disorder–order transitions on the physical properties.

A series of new oxides Li(4−x)/3Ti(5−2x)/3MnxO4 (0.1 ≤ x ≤ 0.9) have been synthesized by solid state reactions and characterized by thermal analysis and X-ray and neutron diffraction. In all phases, Li+ cations mainly occupy tetrahedral sites and transition metals cations are located on the octahedral ones. These phases show a structural disorder–order transition associated to the proportion of manganese in the samples and to its oxidation state. All these factors have a marked influence on the electrochemical properties and the phase x = 0.1 shows the best characteristics to be used as anode in a solid state battery.