| The lithium ion battery occupies a dominant position in the portable battery market today. Intensive research has been carried out on every part of the battery to reduce cost, avoid environmental hazards, and improve battery performance. The commercial cathode material LiCoO2 has been partially replaced by LiNiyCo1- yO2 in the last two years, and mixed metal oxides have been introduced in the last quarter. From a resources point of view, only about 10 million tons of cobalt deposits are available from the world's minerals. However, there is about 500 times more manganese available than cobalt. Moreover, cobalt itself is not environmentally friendly. The purpose of this work is to find a promising alternative cathode material that can maintain good cycling performance, while at the same time reducing the cost and toxicity. When the cost is lowered, it is then possible to consider the larger scale use of lithium ion batteries in application such as hybrid electric vehicles (HEV).; The research work presented in this thesis has focused on a specific composition of a layered lithium transition metal oxide, LiMn0.4Ni 0.4Co0.2O2 with the R3¯m structure. The presence of cobalt plays a critical role in minimizing transition metal migration to the lithium layer, and perhaps also in enhancing the electronic conductivity; however, cobalt is in limited supply and it is therefore more costly than nickel or manganese. The performance of LiMn0.4Ni0.4Co 0.2O2 was investigated and characterized utilizing various techniques an its performance compared with cobalt free LiMn0.5N i0.5O2, as well as with LiMn1/3Ni1/3Co 1/3O2, which is the most extensively studied replacement candidate for LiNiyCo1- yO2, and may be in SONY'S new hybrid cells.; First, the structure and cation distribution in LiMn0.4Ni 0.4Co0.2O2 was studied by a combination of X-ray and neutron diffraction experiments. This combination study shows that about 3--5% nickel is present in the lithium layer, while manganese and cobalt are not observed in the lithium layer. In addition, the study did not reveal any ordering of the manganese, nickel, and cobalt, in the transition metal layer at room temperature. The structure changes during the first charge were also investigated both by ex situ and in situ X-ray diffractions. The same cell parameter trends are observed using both techniques. The hexagonal structure is maintained up to 4.6V, which is above the limit for normal cycling. Excess lithium addition reduces the cation disorder just as cobalt addition does. (Abstract shortened by UMI.)... |
