Long term ageing experimental results show that degradation resulting from coupled DC and AC current waveforms lead to additional degradation of lithium-ion batteries above that experienced through pure DC cycling. More profoundly, such experiments show a dependency of battery degradation on the frequency of AC perturbation. This paper addresses the underlying causality of this frequency dependent degradation. Cell autopsy techniques, namely X-ray photoelectron spectroscopy (XPS) of the negative electrode surface film, show growth of surface film components with the superimposition of an AC waveform. XPS results show that high frequency AC perturbations lead to the increased formation of a passivating film. In order to determine the cause of this increased film formation, a heterogeneous electrochemical model for the LiNiCoAlO2/C6 lithium ion battery coupled with governing equations for the electrical double-layer and solid electrolyte interface film growth is developed. Simulation results suggest that the increased growth of surface film is attributed to frequency dependent heat generation. This is due to ion kinetics in the double layer which are governed by the Poisson-Boltzmann equation. Additional thermal and reference cell relaxation experiments are undertaken that further corroborates the conclusion that heat generation within the battery is a function of the AC excitation frequency through resistive dissipation and the entropy of the cell reaction.