This paper deals with the initialization of a non linear identification algorithm used to accurately estimate the physical parameters of Lithium-ion battery. A Randles electric equivalent circuit is used to describe the internal impedance of the battery. The diffusion phenomenon related to this modeling is presented using a fractional order method. The battery model is thus reformulated into a transfer function which can be identified through Levenberg–Marquardt algorithm to ensure the algorithm’s convergence to the physical parameters. An initialization method is proposed in this paper by taking into account previously acquired information about the static and dynamic system behavior. The method is validated using noisy voltage response, while precision of the final identification results is evaluated using Monte-Carlo method.