Activated Carbon (AC) and multi-walled carbon nanotubes (CNT) are investigated as components of LiFePO4 (LFP)-based bi-material electrodes for hybrid devices. Firstly, the influence of their different morphological and porosimetric characteristics is correlated to the electrochemical performance. Furthermore, kinetic aspects are carefully studied (by means of galvanostatic cycling and cyclic voltammetry), in order to address the processes which determine the power performance. The results indicate that, independently from the carbon, under high current loads the electrode kinetics are limited by the transport of reactant to the LFP particles. In such conditions CNT allow, better than AC, rapid electrons and Li+ ions flow through the open network established in the electrode, thus enabling superior high rate performance, especially during pulsed operation.