Lithium iron phosphate is a promising candidate material for Li-Ion batteries. In this study, the rate determining processes are assessed in more detail in order to separate performance limiting factors. Electrochemical impedance spectroscopy (EIS) data of experimental LiFePO4/Lithium-cells are deconvoluted by the method of distribution of relaxation times (DRT), what necessitates a pre-processing of the capacitive branch. This results in a separation into cathode and anode polarization processes and in a proposition of a physically motivated equivalent circuit model. We identify three different polarization processes of the LiFePO4-cathode (i) solid state diffusion, (ii) charge transfer (cathode/electrolyte) and (iii) contact resistance (cathode/current collector). Our model is then applied to EIS data sets covering varied temperature (0 degrees to 30 degrees C) and state of charge (10% to 100%). Activation energy, polarization resistance and frequency range are determined separately for all cathode processes involved. Finally, the tape-casted LiFePO4-cathode sheet is modified in porosity, thickness and contact area between cathode/electrolyte and cathode/current collector by a calendering process. Charge transfer resistance and contact resistance respond readily in polarization and relaxation frequency. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.030207jes] All rights reserved.