PNNL

Abstract

The influences of Mn3+ ions on the properties of high voltage spinel LiNi0.5Mn1.5O4 is systematically investigated in this work. The content of Mn3+ ions in the spinel is tuned by further annealing of the sample or partially substitution of Ni2+ in the lattice structure. The former decreases the amount of Mn3+ while the latter increases Mn3+ concentration, which has been confirmed by both X-ray diffraction (XRD) and electron diffraction analysis. It has also been experimentally and theoretically proven that Mn3+ ions are directly related to the disordering between Ni2+ and Mn4+ on the octahedral sites in the spinel structure which facilitates the transportation of Li+ ions especially at elevated current densities. An extremely cycling stability as well as good rate capability have been observed in the Cr-substituted spinel confirming that an appropriate amount of Mn3+ ions is the key for a high performance high voltage spinel.