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Investigation of the phase diagram and the defect structure of nonstoichiometric Li1+xMn2-xO4-δ (0 < x ≤ 0.33) spinel

With the rapid development of electronic, information and energy industries, there has been a great demand for batteries with high energy density. As one of the promising cathode materials of lithium-ion batteries Li 1+x Mn 2-x O 4-δ spinel (0 ≤ x ≤ 0.33) was investigated in our work by using thermogravimetry (TG). The samples were prepared by the Pechini method. The composition of the samples was determined using AAS/AES analysis. It was confirmed that the upper critical temperature, T c1 , of the single phase region of Li 1+x Mn 2-x O 4-δ spinel is not only a function of the molar ratio of Li and Mn, n Li /n Mn , but also of the partial pressure of oxygen, p(O 2 ). The lower critical temperature, T cL , was also determined. It is a linear function of log(pO 2 ). The change of the non-stoichiometry, Δδ, in the Li i+x Mn 2-x O 4-δ spinel was measured as a function of p(O 2 ) change by using TG in the single spinel phase region determined previously. The experimental results for AS were discussed in terms of defect chemical models of the Li 1+x Mn 2-x O 4-δ spinel.