A manufacturing method of a lithium rechargeable battery, comprising: (i) preparing a lithium metal electrode in which metal lithium (Li) is formed on one surface or both surfaces of a current collector; (ii) applying an electrolyte solution for coating including one or more lithium salts, one or more non-aqueous organic solvents, and one or more additives on a surface of the metal lithium to form a passive film which is a stable coat; (iii) manufacturing an electrode assembly including a lithium metal electrode having the passive film formed thereon as a negative electrode; and (iv) housing the electrode assembly in a rechargeable battery case and injecting an electrolyte solution for injection including one or more lithium salts, one or more non-aqueous organic solvents, and one or more additives to manufacture a rechargeable battery; wherein the additive of the electrolyte solution for coating is one or more selected from the group consisting of vinylene carbonate (VC), vinyl ethylene carbonate (VEC), fluoroethylene carbonate (FEC), propane sultone (PS), 1,3-propane sultone (PRS), ethylene sulfate (ESa), succinonitrile (SN), adiponitrile (AN), hexane tricarbonitrile (HTCN), gamma-butyrolactone (GBL), biphenyl (BP), cyclohexyl benzene (CHB), and tert-amyl benzene (TAB), the additive of electrolyte solution for injection is one or more selected from the group consisting of pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, triamide hexaphosphate, nitrobenzene derivatives, sulfur, a quinone imine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-methoxy ethanol, aluminum trichloride, carbon tetrachloride, trifluoroethylene, fluoroethylene carbonate (FEC), and propane sultone (PS), and an additive composition of the electrolyte solution for coating is different from an additive composition of the electrolyte solution for injection. (i) preparing a lithium metal electrode in which metal lithium (Li) is formed on one surface or both surfaces of a current collector; (ii) applying an electrolyte solution for coating including one or more lithium salts, one or more non-aqueous organic solvents, and one or more additives on a surface of the metal lithium to form a passive film which is a stable coat; (iii) manufacturing an electrode assembly including a lithium metal electrode having the passive film formed thereon as a negative electrode; and (iv) housing the electrode assembly in a rechargeable battery case and injecting an electrolyte solution for injection including one or more lithium salts, one or more non-aqueous organic solvents, and one or more additives to manufacture a rechargeable battery; the additive of the electrolyte solution for coating is one or more selected from the group consisting of vinylene carbonate (VC), vinyl ethylene carbonate (VEC), fluoroethylene carbonate (FEC), propane sultone (PS), 1,3-propane sultone (PRS), ethylene sulfate (ESa), succinonitrile (SN), adiponitrile (AN), hexane tricarbonitrile (HTCN), gamma-butyrolactone (GBL), biphenyl (BP), cyclohexyl benzene (CHB), and tert-amyl benzene (TAB), the additive of electrolyte solution for injection is one or more selected from the group consisting of pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, triamide hexaphosphate, nitrobenzene derivatives, sulfur, a quinone imine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-methoxy ethanol, aluminum trichloride, carbon tetrachloride, trifluoroethylene, fluoroethylene carbonate (FEC), and propane sultone (PS), and an additive composition of the electrolyte solution for coating is different from an additive composition of the electrolyte solution for injection. <EOS>