Published online by Cambridge University Press: 15 February 2011
A nonaqueous coprecipitation process has been developed to prepare controlled stoichiometry lithium manganese oxalate precipitates. The process involved mixing a methanolic Li-Mn nitrate solution with a methanolic solution containing tetramethylammonium oxalate as the precipitating agent. The resulting oxalates were readily converted to a variety of phase pure lithium manganese oxides at moderate temperatures (≤600°C), where the phase formed was determined by the initial Li/Mn ratio in the starting solution. Metal cation dopants have been incorporated into the oxalate precipitate by dissolving the appropriate metal nitrate in the Li-Mn precursor solution The various starting solutions, oxalate precipitates, and calcined oxides have been extensively characterized using a variety of techniques, including 7Li NMR, TGA/DTA, SEM, and XRD. Results indicate that a strong interaction occurs between Li and Mn in the nitrate solution which carries over into the oxalate phase during precipitation. The morphology and the crystallite size of the oxide powders were shown to be controlled by the morphology of the oxalate precursor and the oxalate calcination temperature, respectively. The results of initial cathode performance tests with respect to dopant type (Al, Ni, Co) and concentration for LiMn2O4 are also reported.