Methods of preparing a cathode/separator assembly for use in electrochemical cells in which a protective coating layer, such as a single ion conducting layer, is coated on a temporary carrier substrate, a microporous separator layer is then coated on the protective coating layer, and a cathode active layer is then coated on the separator layer, prior to removing the temporary carrier substrate from the protective coating layer. Additional layers, including an edge insulating layer, a cathode current collector layer, an electrode insulating layer, an anode current collector layer, an anode layer such as a lithium metal layer, and an anode protective layer, such as a single ion conducting layer, may be applied subsequent to the coating step of the microporous separator 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.