Structural and Electrochemical Characterization of Composite Layered-Spinel Electrodes Containing Ni and Mn for Li-Ion Batteries

The structural features of a series of intergrown "layered-spinel" composite materials with initial formulation xLi[Mn 1.5 Ni 0.5 ]O 4 ·(1 -x)(Li 2 MnO 3 ·Li[Mn 0.5 Ni 0.5 ]O 2 ), previously shown to have attractive properties as positive electrodes in lithium batteries, were studied. The existence of a layered and a spinel component in samples with 0 < x < 1 was confirmed by both X-ray diffraction and 6 Li magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The unit-cell volume of the layered component was shown to decrease as a function of x, while the unit-cell parameter of the cubic spinel phase did not vary significantly. The 6 Li MAS NMR spectra confirmed that the cation distribution in these layered-spinel composite structures is extremely complex; analysis of the data, particularly for intermediate values of x, suggested that Mn 4+ , Mn 3+ , Ni 3+ , and Ni 2+ ions are present, rather than just Mn 4+ and Ni 2+ as implied by the ideal formula xLi[Mn 1.5 Ni 0.5 ]O 4 ·(1-x) (Li 2 MnO 3 ·Li[Mn 0.5 Ni 0.5 ]O 2 ). The structural changes induced by the electrochemical removal and reinsertion of lithium in the composite electrode for x = 0.5 were followed by 6 Li MAS NMR and related to the different signatures in the composition-voltage profiles. The activity of both the layered and the spinel component within a 5-2 V voltage window was confirmed.

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