Methods of preparing a cathode/separator assembly for use in electrochemical cells in which a protective coating layer is coated on a temporary carrier substrate, a microporous separator layer is then coated on the protective coating layer, and a cathode is then coated or laminated on the separator layer, prior to removing the temporary carrier substrate from the protective coating layer. Also, methods of preparing electrochemical cells utilizing cathode/separator assemblies prepared by such methods, and cathode/separator assemblies and electrochemical cells prepared by such methods.