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From 2020 onwards the utilization of conventional gasoline engines is expected to be decreased and it will have been disappeared by 2050. Lithium – ion batteries constitute the most prevalent storage means in EVs and HEVs and their study is attracting more and more interest. Lithium – ion batteries require a proper thermal management system such that overheating phenomena and reduction of power rate capability at low temperatures are averted, as well as thermal losses are minimized and the battery’s lifespan is extended. The objective of this thesis includes the understanding of EV and HEV operation, the understanding of the lithium – ion battery’s operation, the simulation of common problems relevant to practical applications in EVs and HEVs, proposing solutions for tacking the problems and proposing topics for further research. An extensive literature review on EVs and HEVs, on batteries, on their operation and on special topics was carried out. As part of the thesis different types of modeling and models were simulated with the aid of software packages such as ANSYS Fluent, Matlab/Simulink, Comsol Multiphysics, LMS ImagineLab and detailed parametric studies were conducted. Last but not least, the results were summarized in the cause and effect form in order for the effects of several parameters on the battery’s and the vehicle’s performance to be reported.