LT-LiMn0.5Ni0.5O2: A Unique Co-Free Cathode for High Energy Li-Ion Cells

A new Li-ion battery cathode, ‘LT-LiMn0.5Ni0.5O2’, where LT refers to its relatively low synthesis temperature (400 oC), has been identified. Electrochemical data indicate that Li/LT-LiMn0.5Ni0.5O2 cells operate between 5.0 and 2.5 V with good cycling stability, yielding a cathode capacity of 225 mAh/g. The electrochemical reactions occur in two distinct steps centered at ~3.75 V and ~4.7 V during charge, and at ~4.6 V and ~3.5 V during discharge. High-angle, annular-dark-field (HAADF) scanning-transmission electron microscopy (STEM) provide evidence that LT-LiMn0.5Ni0.5O2 consists of a unique, partially-disordered LiMn0.5Ni0.5O2 structure with predominant lithiated-spinel- and layered-like character. Structural analysis of LT-LiMn0.5Ni0.5O2 with synchrotron X-ray diffraction data shows, surprisingly, that lithiated-spinel and layered models with approximately 16% (~1/6) disorder between the lithium and manganese/nickel ions, yield an identical fit to the data, complicating the determination of the exact nature and level of disorder in each structural model. We believe that this is the first report of a Mn-stabilized, lithium-nickel-oxide spinel-related structure in which the redox reactions occur almost entirely on the nickel ions, with the likelihood that oxygen redox also contributes to some capacity above 4.7 V.