Electrochemical performance and kinetics of Li1+x(Co1/3Ni1/3Mn1/3)1−xO2 cathodes and graphite anodes in low-temperature electrolytes

Lithium-ion batteries have started replacing the conventional aqueous nickel-based battery systems in space applications, such as planetary landers, rovers, orbiters and satellites. The reasons for such widespread use of these batteries are the savings in mass and volume of the power subsystems, resulting from their high gravimetric and volumetric energy densities, and their ability to operate at extreme temperatures. In our pursuit to further enhance the specific energy as well as low-temperature performance of Li-ion batteries, we have been investigating various layered lithiated metal oxides, e.g., LiCoO₂, LiNi_0.8Co_0.2 and LiNi_0.8Co_0.15Al_0.05O₂, as well as different low-temperature electrolytes, including ternary and quaternary carbonate mixtures with various co-solvents. In this paper, we report our recent studies on Li_1+x(Co_1/3Ni_1/3Mn_1/3)_1−xO₂ cathodes, combined with three different low-temperature electrolytes, i.e.: (1) 1.0 M LiPF₆ in EC:EMC (20:80), (2) 1.2 M LiPF₆ in EC:EMC (20:80) and (3) 1.2 M LiPF₆ in EC:EMC (30:70). Electrical performance characteristics were determined in laboratory glass cells at different discharge rates and different temperatures. Further, individual electrode kinetics of both Li_1+x(Co_1/3Ni_1/3Mn_1/3)_1−xO₂ cathodes and MCMB graphite anodes were determined at different temperatures, using dc micropolarization, Tafel polarization and electrochemical impedance spectroscopy (EIS). Analysis of these data has led to interesting trends relative to the effects of solvent composition and salt concentration, on the electrical performance and on the kinetics of cathode and anode.