Art [1] This application claims the benefit of priority based on the date of September 30, Korea Patent Application No. 10-2016-0127015, and September 29, 2017 Korea Patent Application No. 10-2017-0126709, 2016, and of the Korea Patent Application It includes all contents disclosed in the literature as part of the specification. [2] The present invention relates to a double protective layer is formed, a negative electrode for a lithium secondary battery, more particularly to a lithium secondary battery comprising a negative electrode and this lithium secondary battery having a polymer protective layer and the carbon-based protective layer. BACKGROUND [3] Recently, increasing interest in energy storage technology. Mobile phones, camcorders and notebook PC, furthermore there is a commitment to research and development of electrochemical devices embodied as applications are increasingly extended to the electric vehicle energy. [4] [5] The electrochemical device is a field that receives the most attention in this respect, the development of secondary batteries that can be charged, discharged, among has become the focus of attention, in recent years, in order to improve capacity density and energy efficiency in developing such a battery it is proceeding with research and development for the design of new electrodes and batteries. [6] [7] The lithium secondary battery is Ni-MH, Ni-Cd, sulfuric acid using an aqueous electrolyte solution developed in the early 1990's from the secondary batteries that are currently being applied - a high operating voltage as compared to conventional batteries such as lead battery, the energy density significantly greater advantages as it has been highlighted. [8] [9] In general, the lithium secondary battery is an electrode assembly including a separator interposed between the positive electrode, a negative electrode and the positive electrode and the negative electrode incorporated in the battery case in a stacked or wound structure, is configured by being a non-aqueous electrolytic solution is injected therein. Lithium electrode as a cathode is used by attaching a lithium foil on the entire plane on the house. [10] [11] Lithium secondary batteries using lithium ions emitted from the positive electrode active material, such as during the initial charging, the lithium metal oxide is moved to the negative electrode comprising a carbon-based material, it is inserted between the layers of carbon-based material. In this case, Li is lithium and the electrolyte and the carbon react at the carbon-based material surface is so reactive steel 2 CO 3 , Li 2 to produce a compound such as O, or LiOH. These compounds will form a film on the surface of the carbon-based material a kind of solid electrolyte interface (Solid Electrolyte Interface, SEI). To play the role of such a SEI film is passed through the ion tunnel only lithium ions. As the effect of the ion tunnel SEI film, a large molecular weight organic solvent moving with lithium ions in an electrolyte molecule is inserted between the layers of the negative electrode active material prevents the cathode structure is destroyed. Thus, the decomposition of the electrolytic solution does not occur by preventing the contact of the electrolytic solution and the negative electrode active material, it has been reported that the amount of lithium ions in the electrolyte is reversibly maintained by maintaining a stable charge-discharge. [12] [13] In addition, the lithium secondary battery is formed of a lithium dendrite and irregular formation and removal of Li during charging and discharging proceeds, which leads to continuous capacity is lowered. To solve this problem, the introduction of a polymeric protective layer or inorganic solid protective layer on the lithium metal current, or to increase or decrease the salt concentration of the electrolytic solution was carried out to study the application of the appropriate additives. But inhibiting lithium dendrites of these studies minor effects are the actual circumstances. So that through the deformation or structural modification of the battery of the lithium metal anode itself solve the problem it can be an effective alternative. [14] [15] [Prior art document] [16] Patent Document 1: Republic of Korea Patent Application Publication No. 2016-0052351 call "stable protective layer of lithium metal electrode and a lithium secondary battery including the same has a" Detailed Description of the Invention SUMMARY [17] An object of the present invention to provide a high utilization for a lithium secondary battery negative electrode to control the reactivity of the lithium metal, and to inhibit the growth of lithium dendrites. [18] A further object of the invention is that by using the lithium metal as the negative electrode provide an energy-efficient nopeumyeonseo FIG lithium secondary battery excellent in life characteristics and safety due to the repeated charge and discharge cycle. Problem solving means [19] The present invention in order to attain the object of the lithium metal; Polymer protection layer formed on at least one surface of the lithium electrode layer; And the carbon-based protective layer formed on the polymer protective layer, and provides a lithium secondary battery anode comprising a. [20] In another aspect, the present invention provides a lithium secondary battery including the cathode. Effects of the Invention [21] Lithium secondary cell comprising a negative electrode according to the present invention is a stable solid-electrolyte interface as lithium fluoride (LiF) film formed: it is possible to improve battery performance and reliable performance expression by preventing the loss of (Solid electrolyte interface SEI) layer. In addition, the internal short circuit of the battery protection by absorbing the inert lithium or lithium dendrites improves the cycle life characteristics when charging and discharging. Brief Description of the Drawings [22] 1 is a cross-sectional view of a lithium secondary battery negative electrode according to the present invention. [23] Figure 2a is an electrochemical charge / discharge capacity, life characteristics data of the lithium secondary battery of the embodiment of the present invention Example 1 and Comparative Examples 1-3. In Figure 2a part filled inside shape is the absolute amount of charge, the shape inside the vacated portion of the absolute capacity during discharge. [24] Figure 2b is an electrochemical charge / discharge capacity, life characteristics data of a lithium secondary battery according to Example 2 and Comparative Example 4 of the present invention. In Figure 2b filled inside part shapes is the absolute amount of charge, the shape inside the vacated portion of the absolute capacity during discharge. [25] Figure 3a is an electrochemical charging / discharging efficiency of a lithium secondary battery in accordance with the data of Example 1 and Comparative Examples 1 to 3 of the present invention. [26] Figure 3b is the electrochemical charging / discharging efficiency of a lithium secondary battery in accordance with the data for Example 2 and Comparative Example 4 of the present invention. [27] Figure 4a is an electrochemical charge / discharge voltage of the lithium secondary battery according to Example 3 and Comparative Examples 5-7 of the present invention. [28] Figure 4b is an electrochemical charge / discharge voltage of the lithium secondary battery according to Example 4 and Comparative Example 8 of the present invention. [29] Figure 5 is a SEM image of the lithium secondary battery negative electrode according to a third embodiment of the invention. [30] Figure 6 is a SEM image of the lithium secondary battery negative electrode according to Comparative example 5 of the present invention. [31] 7 is a SEM image of the lithium secondary battery negative electrode according to Comparative Example 6 of the present invention. [32] Figure 8 is a SEM image of the lithium secondary battery negative electrode according to Comparative Example 7 of the present invention. Best Mode for Carrying Out the Invention [33] Or less, to the accompanying drawings so that the present invention can be easily self having ordinary skill in the art that belong to the reference embodiment will be described in detail. However, the present invention may be embodied in many different forms, and is not limited herein. [34] [35] In the drawing it was used. Like reference numerals designate like elements was omitted, the portion not related to the description in order to clearly describe the present invention, throughout the entire specification. Also, the size and relative sizes of the components shown in the figures may be reduced or exaggerated for clarity of illustration, and are independent from the actual scale. [36] [37] The present invention, the lithium metal layer 100, as shown in Figure 1; Polymer protection layer 200 formed on at least one surface of the lithium electrode layer 100; And the carbon-based protective layer 300 is formed on the polymer protective layer (200); provides a lithium secondary battery anode comprising a. When in accordance with the present invention the multilayer polymer protective layer 200 and the carbon-based protective layer 300 to the layer structure, the more stable electrochemical charge / discharge than when alone application of the polymeric protective layer or a carbon-based protective layer and is maximized to improve the cycle performance effects, such a protective layer is directly in water or oxygen in the air on the lithium metal surface, as well as to improve the life characteristics of the battery and prevent the formation of dendrites formed on the surface of the lithium metal during charging makes a contact can be prevented from oxidation of the lithium metal. [38] [39] It will be described in detail hereinafter lithium metal, a polymer protective layer, and a carbon-based protective layer constituting the lithium secondary battery anode of the present invention. [40] [41] Lithium metal layers [42] Lithium metal or a lithium metal sheet according to the present invention, may be a cathode current collector onto the lithium metal thin film is formed on the metal plate. The formation of a lithium metal thin film is not particularly limited, and the like methods well-known metal thin film forming the lamination method, a sputtering method can be used. In addition, when the after assembling the battery, they do not have the lithium thin film on the current collector while the lithium metal thin film on the metal sheet by the initial charging form is also included in the lithium-metal sheet of the present invention. [43] [44] The anode current collector is if it has suitable conductivity without causing chemical changes in the battery does not especially limited, copper, aluminum, stainless steel, zinc, titanium, silver, palladium, nickel, iron, chromium, alloys thereof, and as a combination may be selected from the group consisting. The stainless steel may be treated with carbon, nickel, titanium or silver surface, the alloy is aluminum - can be used for cadmium alloy, In addition, sintered carbon, a surface-treated with a conductive material, a non-conductive polymer, or a conductive polymer such as the can also be used. In total typically the negative electrode collector is applied to the copper foil. [45] [46] The lithium metal plate can be adjusted according to the electrode width to the electrode shape to facilitate manufacture. The thickness of the lithium metal plate may be from 30 to 500 ㎛. [47] [48] Polymer protective layer [49] The polymer protective layer of the invention serves to prevent the formation of a passivation layer by a non-uniform relative to lower the reactivity of the lithium metal prevents the lithium metal layer is directly exposed to the electrolyte. Therefore, the polymer protective layer is preferably formed of a stable material in the cell in the environment while having the ion conductivity. In the polymer protective layer according to the invention include preferably fluorine-containing polymers, as well as be within the amount of water the carbon-based protective layer reduces the absorption of external moisture is inhibited, there is no possibility of side reactions occur due to moisture, a stable lithium fluoride (LiF) a solid electrolyte interface formed on the carbon-based protective layer with a film formed: by preventing the loss of (solid electrolyte interface SEI) layer it is possible to improve performance and reliable performance of the expression cell. [50] [51] The fluorine-containing polymer constituting the polymer protective layer according to the present invention, for example, polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP: Polyvinylidene fluoride-Hexafluoropropylene copolymer), tetrafluoroethylene (PTFE: Polytetrafluoroethylene) , polyvinylidene fluoride (PVDF: polyvinylidene fluoride), tetrafluoroethylene-hexafluoropropylene copolymer (TFE-HFP: tetrafluoroethylene-hexafluoropropylene copolymer), and mixtures thereof, composites, or it may be any one selected from copolymer have. [52] [53] The polymer protective layer may be formed on one or both surfaces of the lithium metal, preferably should be formed, including the surface facing the electrolyte. Method of forming the polymer protective layer is not particularly limited in the present invention may be formed by performing a variety of coating methods known in the art. For example, spin-coating (Spin coating), the doctor blade (Doctor blade) coating, DIP (Dip) coating, gravure (Gravure) coating, slit die (Slit die) coating, screen (Screen), but a method such as a coating limited to no. [54] [55] The thickness of the polymer protective layer is formed so as to be 0.1 to 20 ㎛, preferably from 5 to 15 ㎛, more preferably 8 to 12 ㎛. If the thickness of the polymer protective layer is less than 0.1 ㎛ difficult to achieve sufficient protection of the lithium metal plate ion conductivity and the electron conductivity is low, and results in the battery capacity is decreased, on the contrary results in the same dimensions compared to the energy density decreases if it exceeds 20 ㎛ It is. [56] [57] According to an exemplary embodiment of the present application, the ionic conductivity of the polymer protective layer is 10 -6 S / cm or more, for example 10 -4 to 10 -3 may be less than S / cm. When the ion conductivity of the polymer protective layer is within the range, can be made to the lithium electrode smooth ion transmission, it is possible to further improve the performance of the battery. [58] [59] According to the present invention, the polymer protective layer may comprise an organic sulfur compound. The organic sulfur compound may be a monomer or polymer form containing a thiol group, is preferable because the monomer and the organic sulfur compound containing more thiol groups. [60] [61] Examples of the organic sulfur compound is 2, 5-mercapto-1,3,4-thiadiazole dimmer, bis (2-mercapto-ethyl) ether, N, N'- dimethyl -N, N'- dimmer mercaptomethyl ethylene-diamine, N, N, N ', N'- tetra-mercapto-ethylenediamine, polyethyleneimine derivatives, 2,4,6-trimmer Cobb tote Ria sol, N, N'- dimmer mercapto-piperazine, 2, 4-mercapto toffee limiter Dean, 1,2-ethane dithiol, bis (2-mercapto-ethyl) sulfide or can be used in combination of two or more compounds thereof. The 2,5 dimmer mercapto-1,3,4-thiadiazole of formula (I) are preferred to in double. [62] [63] The organic sulfur compound is preferably one containing a thiol group in the terminal groups, organic sulfur compound having a thiol group is such it is possible to form a lithium-metal complex is advantageous and easy to coat. In addition, it is possible to suppress dendrite formation to ensure electronegativity of the large I and the large amount S or N times the lithium ions are easy to uniformly deposited (deposition) onto the surface of the lithium metal during charging to the lithium ion. [64] [65] And the polymer protective layer preferably includes an organic sulfur compound with 20 to 50% by weight. Not the amount of the organic sulfur compound can be sufficiently obtained if the coating effect less than 20% by weight, and if it exceeds 50% by weight, the content of the polymer material is decreased relatively, which is not sufficient to obtain the desired effect. [66] [67] The carbon-based protective layer [68] The carbon-based protective layer according to the invention is absorbed, for example, by forming a lithium intercalation material reacts with DEN not involved in charging and discharging the inert lithium or lithium on the negative electrode Dendrite. As a result, the internal short circuit of the battery is prevented thereby improving the cycle life characteristics when charging and discharging. [69] [70] After agglomeration by the lithium dendrites water absorbent material in contact with each other conductive network is formed, so that the first charge to the conductive network before charging is done on the negative electrode in accordance with will be written. After absorption of dendrite can be reduced and result in a lowering of the cycle characteristic of the battery. Accordingly, the lithium dendrite absorbing material is preferably distributed uniformly. [71] [72] Carbon-based material contained in the carbon-based protective layer is that kind of limitation but, may include artificial graphite, natural graphite, low crystalline carbon-based and at least one member selected from the group consisting of, preferably uses a low-crystalline carbon-based. [73] [74] The shape of the carbonaceous material contained in the carbon-based protective layer is not particularly limited such as a spherical, plate-like, fibrous, or amorphous. [75] [76] Wherein the carbon-based, based on the content of the carbon-based protective layer the total weight of the amorphous carbon-based material contained in the protective layer preferably comprises 50 to 80% by weight. The content of the specific surface area becomes smaller and becomes much less than 50% by weight if the amorphous carbon-based content of lithium ion intercalation / deintercalation is not easy, and if it exceeds 80% by weight, there is the problem of amorphous carbon content break too much down the overall capacity Because. [77] [78] Particle size of the carbon-based material contained in the carbon-based protective layer is preferably not in particular limited range of 0.01 to 20 ㎛. If it exceeds 20 ㎛ there is a problem that the uniformity of the electrode surface is lowered and adhesion strength is lowered, to particle size is maintained at preferably 0.01 to 20 ㎛ range of less than 0.01 ㎛ by agglomeration occurs it is possible to form a conductive network. [79] [80] The carbon-based material to attach to the polymeric protective layer, the carbon-based protective layer may further comprise a further binder. Such binders include for example, polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose by Woods (CMC), starch, hydroxypropylcellulose, as in the woods, playing cellulose cellulose, polyvinylpyrrolidone, tetrafluoroethylene ethylene, polyethylene, polypropylene, ethylene-can be used butadiene rubber, fluoro rubber and various copolymers thereof, such as-propylene-diene polymer (EPDM), sulfonated -EPDM, styrene. [81] [82] In order to uniformly coating the carbon-based material and a binder in the polymer protective layer, it is possible by using a predetermined solvent to prepare a slurry. At this time, a usable solvents may be mentioned dimethyl cell width side (Dimethyl sulfoxide, DMSO), an alcohol, N- methylpyrrolidone (NMP), acetone or water. [83] [84] The thickness of the carbon-based protective layer according to the invention is formed so as to be preferably to 2 to 20 ㎛, 10 to 15 ㎛ to more preferred. If the thickness of the carbon-based protective layer is less than 2 ㎛ if there is a possibility that the thickness of the carbon layer may not properly play a role of the protective layer is too thin, on the contrary exceeding 20 ㎛ the thickness of the negative electrode thickening lowering the energy density problem there is. [85] [86] A method of applying a slurry containing the prepared carbonaceous materials in the polymer protective layer may be selected from known methods in view of the characteristics of the material, or be a new proper way. For example, it may be desirable to uniformly disperse was partitioned for forming a negative active material layer composition on the current collector using a doctor blade (Doctor blade) and the like. In some cases, it is also possible to use a method of executing the allocation and distribution process in one process. In addition, it is also possible to use a method such as die casting (Die casting), comma coating (Comma coating), screen printing (Screen printing). [87] [88] The lithium secondary battery [89] The lithium secondary battery according to the present invention can be produced through a known technique that is normally carried out for a supplier party other than the structure and properties of the above-described negative electrode remaining configuration, and will be described in detail below. [90] [91] A positive electrode according to the invention may be film-forming compositions comprising a positive electrode active material, conductive material and a binder on a positive electrode collector to be prepared in the form of a positive electrode. [92] [93] The positive electrode active material is LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , Li (Ni a Co b Mn c ) O 2 (0 [141] The positive electrode was used for LCO. The cathode is coated with PVDF-HFP polymer protective layer on the surface of Li metal and having a thickness of 150㎛ to a thickness of 8 ~ 12㎛, and particles in the polymer protective layer size (D 50 ) of about 5㎛ electrical / ionic conductivity is excellent a carbon-based protective layer of hard carbon material (amorphous hard carbon, Carbotron using Kureha Corporation-P) was used after coating with a thickness of 10 ~ 15㎛. After interposing the polyolefin separator between the positive electrode and the negative electrode, ethylene carbonate (EC), diethyl carbonate (DEC) 50: in a mixed solvent of 50 volume of 1M LiPF 6 to the injection of the molten electrolyte coin-type half-cell It was prepared. [142] [143] [144] Except for Li metal on the 150㎛ thickness was used to form the negative electrode non-coating the polymer protective layer and the carbon-based protective layer was prepared a coin-type half-cell in the same manner as in Example 1. [145] [146] [147] The PVDF-HFP polymer protective layer only on the surface of Li metal 150㎛ thickness was prepared a coin-type half-cell in the same manner as in Example 1 except for using the cathode coated with 8 ~ 12㎛ thickness. [148] [149] [150] Without the Li metal on the polymer protective layer thickness 150㎛ particle size (D 50 ) of about 5㎛ electrical / ionic conductivity is excellent hard carbon material (amorphous hard carbon, Carbotron using Kureha Corporation-P) of the carbon-based protective layer It was prepared a coin-type half-cell in the same manner as in example 1 except for using a cathode coated with a thickness of 10 ~ 15㎛. [151] [152] [153] Example 1 and the coin-type half-cell in the same manner as in Example 1 except for using the PTFE instead of PVDF-HFP polymer as a protective layer was prepared in the. [154] [155] [156] Example 1 and the coin-type half-cell in the same manner as in Example 1 except for using the PVDF-HFP instead of the PVA polymer in the protective layer was prepared in the. [157] [158] [159] Example 1 instead of the LCO in the positive electrode, except that the Li metal in 150㎛ thickness was prepared a coin-type half-cell in the same manner as in Example 1. [160] [161] [162] Comparison was prepared a coin-type half-cell in the same manner as in Example 3 except for using the same negative electrode as in Example 1. [163] [164] [165] Except for using the same negative electrode as in Comparative Example 2 was prepared a coin-type half-cell in the same manner as in Example 3. [166] [167] [168] Comparison was prepared a coin-type half-cell in the same manner as in Example 3 except for using the same negative electrode as in Example 3. [169] [170] [171] It was carried out, except for using the same negative electrode as in Example 2 to prepare a coin-type half-cell in the same manner as in Example 3. [172] [173] [174] Comparison was prepared a coin-type half-cell in the same manner as in Example 3 except for using the same negative electrode as in Example 4. [175] [176] the electrochemical charge / discharge capacity, life characteristics and capacity efficiency measurements [177] Example 1 and comparative charge / discharge capacity of Examples 1 to 3, the service life (Cycle) by measuring the characteristics, efficiency and capacity. The results are shown in Figures 2a and 3a. According to Figures 2a and 3a, it can be found in Example 1. The Comparative Examples 1 to 3 that the cycle is excellent in charge / discharge capacity and the capacity efficiency in progress compared. [178] Further, the second embodiment and the charge / discharge capacity of Comparative Example 4, the life (Cycle) by measuring the characteristics, efficiency and capacity. The results are shown in Figure 2b and 3b. According to Fig. 2b and 3b, Example 2, this can be confirmed that Comparative Example 4 is excellent in the cycle charging / discharging capacity and the capacity efficiency in progress compared. [179] [180] the electrochemical charge / discharge voltage Behavior Measurement [181] Example 3 and Comparative Example 5 to measure the voltage occurring at the charging / discharging process of 7 the results are shown in Figure 4a. Referring to Figure 4a, it can be confirmed that Example 3 performed the comparative examples 5-7 to over-voltage is decreased significantly compared. [182] Example 4 and compared by measuring the voltage occurring in the charging / discharging process of Example 8 is shown in Figure 4b the results. According to Fig. 4b, Example 4 is can be seen that Comparative Example 8, the voltage is decreased significantly compared. [183] [184] After the electrochemical charging / discharging, make dendrite morphology [185] It was confirmed in Example 3 and Comparative Examples 5 ~ 7 SEM measurements, dendrite morphology (Dendrite morphology) to break down the cell after the charge / discharge process of the results are shown in Figure 5-8. Example 3 of the dendrite is, the current density distribution is uniform is the reduction of lithium laminated (Deposition) is the porosity (Porous) form, as identified in Figure 5 it can be confirmed that a flat (Broad). On the other hand, Comparative Example 5-7 is confirmed to be such, that the current density distribution while not been uniform current SOLiD in one non-uniform shape, which is the lithium is reduced lamination and is vertically as identified in Figure 6-8 have. [186] Reference Numerals [187] 100. lithium metal [188] 200. The polymer protective layer [189] 300. The carbon-based protective layer Claims [Claim 1] Lithium metal; Polymer protection layer formed on at least one surface of the lithium electrode layer; And the carbon-based protective layer formed on the polymer protective layer; The lithium secondary battery anode double protective layer is formed comprising a. [Claim 2] The method of claim 1, wherein the polymer protective layer is a negative electrode for a lithium secondary battery, characterized in that formed by a fluorine-containing polymer. [Claim 3] Ethylene, tetrafluoroethylene: - according to claim 1, wherein the polymer protective layer is a polyvinylidene fluoride hexafluoropropylene copolymer (Polyvinylidene fluoride-Hexafluoropropylene copolymer PVDF-HFP) (PTFE: Polytetrafluoroethylene), polyvinylidene fluoride (PVDF: Polyvinylidene fluoride), tetrafluoroethylene-hexafluoropropylene copolymer (TFE-HFP: tetrafluoroethylene-hexafluoropropylene copolymer) and a lithium secondary battery negative electrode comprising the at least one selected from a combination of the two. [Claim 4] The method of claim 1, wherein the lithium secondary battery anode, characterized in that the thickness of the polymer protective layer is from 0.1 to 50 ㎛. [Claim 5] The method of claim 1, wherein the carbon-based protective layer of artificial graphite, natural graphite, low crystalline carbon-based and a lithium secondary characterized in that it comprises at least one member selected from the group consisting of a carbon-based material battery anode. [Claim 6] The method of claim 1, wherein the negative electrode a carbon-based protective layer is a lithium secondary battery comprising the carbon-based materials to 50 to 80% by weight. [Claim 7] The method of claim 1, wherein the lithium secondary battery anode, characterized in that the carbon-based protective layer comprises a carbon-based material particle size is 0.01 to 20 ㎛. [Claim 8] The method of claim 1, wherein the negative electrode for a lithium secondary battery, characterized in that the thickness of the carbon-based protective layer is from 2 to 20 ㎛. [Claim 9] Any one of claims 1 to 8, the lithium secondary battery comprising a negative electrode of any one of claims. [Claim 10] Lithium metal; Polymer protection layer formed on at least one surface of the lithium electrode layer; And the carbon-based protective layer formed on the polymer protective layer; A, the polymer protective layer is a lithium secondary battery negative electrode having a double protective layer comprising the organic sulfur compounds, including but. [Claim 11] 11. The method of claim 10, wherein the organic sulfur compound is a lithium secondary battery negative electrode, characterized in that the monomer or polymer form containing a thiol group. [Claim 12] Claim 10 wherein the organic sulfur compound is 2, 5-mercapto-1,3,4-thiadiazole dimmer, bis (2-mercapto-ethyl) ether, N, N'- dimethyl -N, N ' - dimmer mercapto ethylene-diamine, N, N, N ', N'- tetra-mercapto-ethylenediamine, polyethyleneimine derivatives, 2,4,6-trimmer Cobb tote Ria sol, N, N'- dimmer mercapto-piperazine , 2,4-mercapto toffee limiter Dean, 1,2-ethane dithiol, and bis (2-mercapto-ethyl) for a lithium secondary battery negative electrode, characterized in that at least one compound selected from the group consisting of sulfide. [Claim 13] The method of claim 10, wherein the cathode of the polymer protective layer is a lithium secondary battery comprising the organic sulfur compound to 20 to 50% by weight. [Claim 14] Claim 10 to 13 lithium secondary battery comprising the cathode of any one of claims.