Synthesis and characterization of cathode, anode and electrolyte materials for rechargeable lithium batteries

Two new classes of cathode materials were studied: iron phosphate/sulfate materials and layered manganese oxides, both of which are low cost and had shown some potential. The first class of materials have poor conductivity and cyclability. I studied a number of methods for increasing the conductivity, and determined that grinding the material with carbon black was as effective as special in-situ coatings. The optimum carbon loading was determined to be between 6 and 15 wt%. Too much carbon reduces the volumetric energy density, whereas too little significantly increased cell polarization (reduced the rate of reaction). The kinetic and thermodynamic stability of LiFePO ₄ was also studied and it was determined that over discharge protection will be needed as irreversible Li₃PO₄ can be formed at low potentials. A novel hydrothermal synthesis method was developed, but the significant level of Fe on the Li site reduces the reaction rate too much. In the case of the layered manganese oxide, cation substitution with Co and Ni is found to be effective in avoiding Jahn-Teller effects and improving electrochemistry.; A wide range of tin compounds have been suggested as lithium storage media for advanced anode materials, as tin can store over 4 Li per Sn atom.; Lithium hexafluorophosphate, LiPF₆, is presently the salt of choice for LiCoO₂ batteries, but it is expensive and dissolves some manganese compounds. The lithium bis(oxolato)borate (BOB) salt was recently reported, and I made a study of its use in cells with the LiFePO₄ cathode and the tin anode. During its synthesis, it became clear that LiBOB is very reactive with many solvents, and these complexes were characterized to better understand this new material. In LiBOB the lithium is five coordinated, an unstable configuration for the lithium ion so that water and many other solvents rapidly react to make a six coordination. Only in the case of ethylene carbonate was the lithium found to be four coordinated. The LiBOB based electrolyte has a lower ionic conductivity than LiPF₆, thus providing a poorer performance, while the capacity retention is improved. Further improvement of conductivity is still needed.; Improved LiFePO₄ cathode materials have been formed, the behavior of pure tin in the form of foil has been determined and will serve as the base case for future studies of tin based anodes, and the structure and electrochemical behavior of the new LIBOB electrolyte salt has been determined. (Abstract shortened by UMI.)...