Electrochemical methods for probing solid polymer electrolyte surface coatings on electrically conducting, active, three-dimensional electrode materials for use in lithium-ion batteries, to quantitatively determine the conformity, uniformity, and the presence of pinholes, and/or other defects in coatings, without requiring the detachment of the coating from the electrode or otherwise inducing damage to the coating, are described. Coated electrodes are submersed in an electrolyte solution containing a redox-active probe species which does not induce electrochemical damage to either the working electrode or the solid polymer electrolyte surface coating. For coated Cu2Sb working electrodes, molecules including a water-soluble redox active viologen moiety have been found to be effective. The current as a function of the applied potential for an uncoated working electrode is used as a baseline for testing solid polymer surface coatings on working electrodes, and the difference in the observed current between the electrodes for a given potential is a quantitative indicator of the ability of the probe species to access the surface of the working electrode through the solid polymer electrolyte coating.