Lithium ion batteries provide a high energy density, higher voltage as well as a long shelf life compared to traditionally used lead acid, NiMH and NiCd batteries. Thus, they are a very promising energy storage system for our daily life. As one of the most important components in a battery, cathode materials have been investigated intensively in recent years as they play a key role in determining the cell voltage and discharge capacity in a battery. Both layered Li(Ni1/3Co1/3Mn1/3)O2 (NCM) and olivine-structured LiFePO4 (LFP) materials are promising cathode candidates. However, these cathodes also have some disadvantages that have hindered further commercialization. The main issue with NCM is its rapid performance decay upon cycling. In addition, LFP is hindered by a low rate capacity and low lithium ion diffusivity.

We studied the crystal growth behavior and performance of both Li(Ni1/3Co1/3Mn1/3)O2 and LiFePO4 cathodes in order to develop synthesis-structure-function relationships. Three different crystal growth behaviors were observed for the NCM annealing process: surface, volume and grain boundary diffusion. Further exploration of the mechanism of NCM performance decay revealed that microstructural changes were related to the strain accommodation ability in this system and that nanostructured materials were more stable during cycling. In the LFP synthesis, we observed both oriented attachment (OA) and Ostwald ripening (OR) during growth in a triethylene-glycol system. Both polycrystalline and single crystalline particles evolved as a function of a time-dependent pH change. Thus, the lithium ion diffusion rate of LiFePO4 was improved by tailoring the morphology and size though our modification of the precursor environment, revealing that polycrystalline LFP displayed better performance than single crystalline particles. Finally, the electronic conductivity of LiFePO4 was successfully increased via a polymer solution coating method. By producing more uniform, thin and coherent coatings on LiFePO4 particles, we were able to produce batteries with significantly less carbon (i.e., 0.41 wt.%) while has comparable performance (discharge capacity of 80mAh/g at 2C) compared to traditionally synthesized carbon-coated LiFePO4 with higher carbon loadings (ca. 2.64 wt.%). This will enable us to produce batteries with higher active material loading and therefore, significantly larger energy densities.