Exploring Lithium-Cobalt-Nickel Oxide Spinel Electrodes for ≥3.5 V Li-Ion Cells

Some recent reports have indicated that a manganese oxide spinel component, when embedded in a relatively small concentration in layered xLi₂MnO₃center dot(1-x)LiMO₂ (M = Ni, Mn, or Co) electrode systems, can act as a stabilizer that increases their capacity, rate capability, cycle life, and first-cycle efficiency. Our findings prompted us to explore the possibility of exploiting lithiated cobalt oxide spinel stabilizers by taking advantage of (1) the low mobility of cobalt ions relative to that of manganese and nickel ions in close-packed oxides and (2) their higher potential (similar to 3.6 V vs Li0) relative to manganese oxide spinels (similar to 2.9 V vs Li0) for the spinel-to-lithiated spinel electrochemical reaction. In particular, we revisited the structural and electrochemical properties of lithiated spinels in the LiCo_1-xNi_xO₂ (0 <= x <= 0.2) system, first reported almost 25 years ago, by means of high-resolution (synchrotron) X-ray diffraction, transmission electron microscopy, nuclear magnetic resonance spectroscopy, electrochemical cell tests, and theoretical calculations. These results provide a deeper understanding of the complexity of intergrown layered/lithiated spinel LiCo_1-xNi_xO₂ structures when prepared in air between 400 and 800 degrees C and the impact of structural variations on their electrochemical behavior. These structures, when used in low concentrations, offer the possibility of improving the cycling stability, energy, and power of high energy (>= 3.5 V) lithium-ion cells.