Li-ion battery fast-charging technology plays an important role in popularizing electric vehicles (EV), which critically need a charging process that is as simple and quick as pumping fuel for conventional internal combustion engine vehicles. To ensure stable and safe fast charging of Li-ion battery, understanding the electrochemical and thermal behaviors of battery electrodes under high rate charges is crucial, since it provides insight into the limiting factors that restrict the battery from acquiring energy at high rates. In this work, charging simulations are performed on Li-ion batteries that use the LiCoO2 (LCO), LiMn2O4 (LMO), and LiFePO4 (LFP) as the cathodes. An electrochemical-thermal coupling model is first developed and experimentally validated on a 2.6Ah LCO based Li-ion battery and is then adjusted to study the LMO and LFP based batteries. LCO, LMO, and LFP based Li-ion batteries exhibited different thermal responses during charges due to their different entropy profiles, and results show that the entropy change of the LCO battery plays a positive role in alleviating its temperature rise during charges. Among the batteries, the LFP battery is difficult to be charged at high rates due to the charge transfer limitation caused by the low electrical conductivity of the LFP cathode, which, however, can be improved through doping or adding conductive additives. A parametric study is also performed by considering different electrode thicknesses and secondary particle sizes. It reveals that the concentration polarization at the electrode and particle levels can be weaken by using thin electrodes and small solid particles, respectively. These changes are helpful to mitigate the diffusion limitation and improve the performance of Li-ion batteries during high rate charges, but careful consideration should be taken when applying these changes since they can reduce the energy density of the batteries.