Double-layered protective coatings for lithium metal electrodes, as well as methods of formation relating thereto, are provided. The negative electrode assembly includes an electroactive material layer including lithium metal and a protective dual-layered coating. The protective dual-layered coating includes a polymeric layer disposed on a surface of the electroactive material layer and an inorganic layer disposed on an exposed surface of the polymeric layer. The polymeric layer has an elastic modulus of greater than or equal to about 0.01 GPa to less than or equal to about 410 GPa. The inorganic layer has an elastic modulus of greater than or equal to about 10 GPa to less than or equal to about 1000 GPa.