Carbon Nanotubes Act as Conductive Additives in the cathode of Lithium Ion Batteries

The layered compounds LiCoO2, LiNiO2 and spinel compound LiMn2O4 have served as very effective cathode active materials in lithium ion rechargeable batteries. Generally, their high conductive resistance easily results in a serious polarization and poor utilization of active materials.In order to make full use of the active materials and increase the capacity, the charge-discharge rate and the cycle life of lithium ion batteries, conductive additives are often added into the above cathode materials to form a conductive network. Carbon materials, such as carbon black, graphite powders and chemical vapor deposit carbon fibers have been widely used as conductive additives owing to their high electrical conductivity and chemical inertness. To effectively utilize the active materials, the contents of these carbon additives in the cathode often reach up to 10～20wt%. This leads to a great need for binder, for example, 10wt% or more. It follows therefore a considerable increase in volume of the lithium batteries and lower energy density because of the large amount of carbon additives and binder in the cathode.By substituting carbon nanotubes (CNTs) for carbon black, graphite powders or chemical vapor deposit carbon fibers, much conductive additives and binder are saved, and the cathode with only 3～5wt% of conductive additives CNTs shows excellent rate capacity. At the discharge rate 0.5C,2.0C and 3.0C, the LiCoO2 cathode with CNTs exhibits discharge capacity up to 134mAh/g, 126 and 120mAh/g, respectively. The explanation is given as follows. Firstly, their microstructure and graphitic crystallinity are very important for electron transport. CNTs employed in the experiments comprise an array of complete graphite sheets seamlessly wrapped into cylindrical tubes which are concentrically nested like the rings of a tree trunk. Thus, the process of -electrons transport occurs in graphite sheet in super-conjugative manner when they move from one end to the other end in CNTs. Apparently, the CNTs' microstructure does good to electron transport. On the other hand,being highly graphitic (concluded from XRD patterns), CNTs also displays high electron conductivity. Secondly, being smaller in diameter, CNTs possess much larger number of primary particles in unit mass than other carbon materials. Hence, it results in a lower percolation threshold in the case of CNTs. Finally, owing to their high surface energy, CNTs fallen into nano-materials tend to aggregate and then form firm webs effectively entrapping LiCoO2 particles during the preparation of the cathode to guarantee their close contact with the active materials.Accordingly, effective electron channels are provided to lessen the polarization loss.