Assuming that by the term “surface redox processes” you refer to “pseudocapacitive” processes (i.e. solid state surface redox transitions occurring in an oxide film electrode) and not in a typical charge transfer reaction (i.e. surface oxide formation), a discrimination is rather difficult to be attained (since they have the same conceptual meaning).

Nevertheless, I would suggest to perform electrochemical impedance spectroscopy (EIS) experiments in the presence and absence of the precursor that “carries” the intercalated ion. An attempt to decouple contributions of the two processes may be made by modelling the EIS spectra obtained in the presence of the intercalated ion precursor with respect to the obtained AC response of your system in the absence of the latter (at first try to model the “pseudocapacitance” related to the “surface redox processes” when no parallel intercalation processes occur).

To clarify this, let us assume a simplified model of an electrochemically grown oxide film electrode immersed in an electrolytic solution containing Xn+ ions (intercalated ions). The film is formed by a phase A that contacts both the substrate (bulk material) and electrolyte, plus a phase B that contacts phase A and the electrolyte. Phase A is related to the “surface redox processes” while phase B to the intercalation of Xn+ ionic species. In this case, the capacitive behaviors of phases A and B, may be modeled by the parallel combination of the electrochemical “pseudo” capacitances CA and CB respectively (you might want to think of it as an imitation/modification of the standard adsorption model). The values of CA and CB is expected to be much larger than this of the double layer capacitance.  

J. Bisquert’s group has done an extended work upon this field.

Hope that helps a bit…                   

@George H. Lane

Thanks very much for your kind answer. I will try your suggested method in my future works.