Method for forming lithium metal and inorganic material composite thin film and method for pre-lithiation of negative electrode for lithium secondary battery by using same

Abstract

A method for pre-lithiation of a negative electrode and a negative electrode formed by the method, the method including forming a mixture of inorganic material powder and molten lithium, forming a lithium metal-inorganic material composite ribbon, rolling the ribbon into a film and bonding the lithium metal-inorganic material composite film on a surface of a negative electrode to form a lithium metal-inorganic material composite layer on the surface of the negative electrode. This method reduces the deterioration of lithium during application of a mixture slurry and a negative electrode for a secondary battery, manufactured by the method for pre-lithiation, has improved initial irreversibility, and a secondary battery manufactured using such a negative electrode has excellent charging and discharging efficiency.

Claims

1. A method for pre-lithiating a negative electrode, the method comprising: adding an inorganic powder to molten lithium to form a mixture; extruding the mixture and cooling the mixture to prepare a lithium metal-inorganic composite ribbon having a thickness of 100 μm to 200 μm; rolling the lithium metal-inorganic composite ribbon to produce a lithium metal-inorganic composite film; and bonding the lithium metal-inorganic composite film on a surface of the negative electrode to form a lithium metal-inorganic composite layer on the surface of the negative electrode.

2. The method of claim 1, wherein a thickness of the lithium metal-inorganic composite layer is 1 μm to 50 μm.

3. The method of claim 1, wherein the inorganic powder comprises at least one selected from the group consisting of alumina (Al.sub.2O.sub.3), titanium dioxide (TiO.sub.2), zirconium dioxide (ZrO.sub.2), silicon dioxide (SiO.sub.2), tin oxide (SnO.sub.2), cerium oxide (CeO.sub.2), magnesium oxide (MgO), calcium oxide (CaO), and yttria (Y.sub.2O.sub.3).

4. The method of claim 1, wherein a mixing ratio of the molten lithium and the inorganic powder is 70 to 85% by volume of the molten lithium and 15 to 30% by volume of the inorganic powder.

5. The method of claim 1, further comprising mixing a binder with the molten lithium or the mixture of the molten lithium and inorganic powder.

6. The method of claim 1, wherein the lithium metal-inorganic composite layer does not remain in a metallic form of lithium after an initial activation charge.

7. The method of claim 1, wherein the inorganic powder has a particle diameter of 0.1 μm to 10 μm.

8. The method of claim 1, wherein the negative electrode comprises silicon oxide.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram of a manufacturing process schematically showing first to third steps of the present invention.

(2) FIG. 2 is a schematic diagram of a manufacturing process showing a fourth step of the present invention.

(3) FIG. 3 is a diagram showing a lithium metal-inorganic composite layer formed on an electrode by the fourth step of the present invention and pre-lithiation.

(4) FIG. 4 is a diagram showing an inorganic layer remaining after lithium is absorbed into an electrode from the lithium metal-inorganic composite layer by pre-lithiation of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(5) Hereinafter, the present invention will be described in detail. The present invention is not limited by the following examples and experimental examples. The embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

(6) The pre-lithiation of a negative electrode for a secondary battery according to the present invention includes: a first step of adding an inorganic powder to molten lithium to form a mixture; a second step of extruding the mixture and cooling the mixture to prepare a lithium metal-inorganic composite ribbon having a thickness of 100 to 200 μm; a third step of rolling the lithium metal-inorganic composite ribbon to produce a lithium metal-inorganic composite thin film; and a fourth step of depositing the lithium metal-inorganic composite thin film on a surface of the negative electrode to form a lithium metal-inorganic composite layer.

(7) The negative electrode material of the lithium ion battery has a disadvantage that the initial irreversibility is large. In particular, the negative electrode of the Si-based material has a large volume change and surface side reaction, so that a large amount of lithium used during charging cannot be re-discharged at the time of discharging. In order to improve this initial irreversibility, if pre-lithiation is performed before the fabrication of the battery assembly, the side reaction occurs during the first charging in advance. Therefore, when the battery assembly is actually formed and charged/discharged, the first cycle is performed with the reduced irreversibility, thereby reducing the initial irreversibility.

(8) In the present invention, as shown in FIG. 1, the lithium metal-inorganic composite layer is formed on the surface of SiO or a graphite electrode containing SiO having a large initial irreversibility, and the lithium metal part in the lithium metal-inorganic composite layer is used for pre-lithiation to reduce the initial irreversibility, and the inorganic material remaining after the pre-lithiation helps improve the safety of the negative electrode.

(9) In particular, the manufacturing process of a conventional technology of coating a slurry generated by mixing molten lithium with an inorganic material with a negative electrode is difficult due to the high reactivity of lithium metal and there is a possibility that the lithium metal may be deteriorated during the application. However, according to the present invention, since a lithium metal-inorganic composite ribbon is made, the ribbon is rolled to form a thin film, and the thin film is bonded with the negative electrode, there is an advantage that time for lithium to be exposed to the air can be minimized.

(10) The first step of the present invention is to add an inorganic powder to molten lithium to form a mixture. At this time, the melting temperature of lithium is 180° C. to 400° C., and more preferably 190° C. to 250° C. If the melting temperature of lithium exceeds the upper limit value, lithium becomes too highly reactive, and if the melting temperature of lithium is lower than the lower limit value, lithium is not liquidized.

(11) According to a preferred embodiment of the present invention, the inorganic powder may be one or more selected from the group consisting of alumina (Al.sub.2O.sub.3), titanium dioxide (TiO.sub.2), zirconium dioxide (ZrO.sub.2), silicon dioxide (SiO.sub.2), tin oxide (SnO.sub.2), cerium oxide (CeO.sub.2), magnesium oxide (MgO) calcium oxide (CaO) and yttria (Y.sub.2O.sub.3). Among them, alumina is most preferable. According to a preferred embodiment of the present invention, the particle diameter of the inorganic powder is 0.1 to 10 μm, more preferably 0.3 to 5 μm, and most preferably 0.5 to 1 μm. If the particle size of the inorganic powder exceeds 10 μm, it may not be dispersed well in the molten lithium, which is not preferable.

(12) According to a preferred embodiment of the present invention, the proportion of the inorganic powder injected into the molten lithium is 70 to 85% by volume of lithium and 15 to 30% by volume of the inorganic substance. When the mixing ratio is satisfied, an effect of improving the safety of the pre-lithiation and the negative electrode is exhibited.

(13) According to a preferred embodiment of the present invention, by further adding a binder to the molten lithium solution in addition to the inorganic powder, it is possible to prevent the lithium metal-inorganic composite layer from being separated from the negative electrode. As the binder, commonly used binders such as PVDF and SBR based binders may be used. Also, polyacrylic acid (PAA), carboxymethyl cellulose (CMC), and polyimide binders may be used.

(14) The preferable content of the binder to be charged into the molten lithium is 1 to 10 parts by weight relative to 100 parts by weight of the inorganic powder to be added together. If it is less than 1 part by weight, the lithium metal-inorganic composite layer may be separated from the negative electrode, and if it exceeds 10 parts by weight, it is not preferable from the viewpoint of pre-lithiation.

(15) In the second step of the present invention, the mixture is extruded and then cooled to produce a lithium metal-inorganic composite ribbon. The mixture can be extruded by a known method. After extrusion, the mixture is cooled to room temperature to form a lithium metal-inorganic composite ribbon having a thickness of 100 to 200 μm. The thickness of the lithium metal-inorganic composite ribbon can be adjusted according to the purpose. If the thickness of the lithium metal-inorganic composite ribbon is less than 100 μm, it is difficult to produce a lithium metal-inorganic composite ribbon by an extrusion method. When the thickness is more than 200 μm, there is a disadvantage in that the energy and manufacturing time are increased during the rolling process for thinning the lithium metal-inorganic composite ribbon made by extrusion.

(16) The third step of the present invention is to make the lithium metal-inorganic composite thin film by rolling the lithium metal-inorganic composite ribbon. The method of rolling the lithium metal-inorganic composite ribbon is generally a method of rolling a metal in the form of a thin film.

(17) According to a preferred embodiment of the present invention, the thickness of the lithium metal-inorganic composite thin film after the rolling is 1 to 50 μm. The thickness is more preferably 1 to 30 μm, and most preferably 5 to 10 μm. When the thickness of the lithium metal-inorganic composite thin film is in the range of 1 to 50 μm, the lithium metal-inorganic composite layer exhibits the effect of improving the safety of the pre-lithiation and the battery.

(18) Conventionally, it has been difficult to apply a slurry of a lithium metal-inorganic compound to a negative electrode. However, the present invention is featured in forming a lithium metal-inorganic composite thin film by the second and third steps and bonding the film to the negative electrode to thereby form a lithium metal-inorganic composite layer on the negative electrode in a relatively easy manner.

(19) In the fourth step of the present invention, the lithium metal-inorganic composite thin film is deposited on the surface of a negative electrode to form a lithium metal-inorganic composite layer. The lithium metal-inorganic composite thin film is placed on a negative electrode, and then laminated by applying heat and pressure.

(20) According to a preferred embodiment of the present invention, the lithium metal-inorganic composite layer does not remain in the metallic form of lithium after the initial activation charge.

(21) The present invention also provides a secondary battery including a negative electrode manufactured by the above-described method.

(22) The secondary battery according to the present invention includes an electrode assembly in which two electrodes of different polarities are stacked in a state separated from each other by a separator. The electrode assembly includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and a separator.

(23) Specifically, the positive electrode, for example, may be prepared by applying a mixture of a positive electrode active material, a conductive material and a binder on a positive electrode current collector, followed by drying. If necessary, a filler may be further added to the mixture.

(24) The positive electrode active material according to the present invention may be mixed with a compound, which uses a lithium intercalation material as its main component, such as a layered compound such as lithium cobalt oxide (LiCoO.sub.2), lithium nickel oxide (LiNiO.sub.2), or a compound substituted with one or more transition metals; lithium manganese oxides such as Li.sub.1+xMn.sub.2−xO.sub.4 (herein, x is between 0 and 33), LiMnO.sub.3. LiMn.sub.2O.sub.3, and LiMnO.sub.2; lithium copper oxide (Li.sub.2CuO.sub.2); vanadium oxides such as LiV.sub.3O.sub.8, LiFe.sub.3O.sub.4, V.sub.2O.sub.5, and Cu.sub.2V.sub.2O.sub.7; lithium nickel oxide expressed by LiNi.sub.1−xM.sub.xO.sub.2 (herein. M=Co, Mn, Al, Cu, Fe, Mg, B or Ga, and x=0.01 to 0.3); lithium manganese composite oxide expressed by LiMn.sub.2−xM.sub.xO.sub.2 (herein, M=Co, Ni, Fe, Cr, Zn or Ta , x=0.01 to 0.1) or Li.sub.2Mn.sub.3MO.sub.8 (herein, M=Fe, Co, Ni, Cu or Zn); LiMn.sub.2O.sub.4 in which a part of Li in the formula is substituted with an alkaline earth metal ion; disulfide compound; and Fe.sub.2(MoO.sub.4).sub.3 or a compound oxide formed by combination thereof.

(25) The positive electrode collector generally has a thickness of 3 to 500 micrometers. The positive electrode current collector is not particularly limited as long as it has high conductivity without causing a chemical change in the battery. Examples of the positive electrode current collector include stainless steel, aluminum, nickel, titanium, sintered carbon or aluminum or stainless steel of which the surface has been treated with carbon, nickel, titanium, silver, or the like. The current collector may have fine irregularities on the surface thereof to increase the adhesion of the positive electrode active material, and various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric are possible.

(26) The conductive material is usually added in an amount of 1 to 50% by weight based on the total weight of the mixture including the positive electrode active material. Such a conductive material is not particularly limited as long as it has electrical conductivity without causing a chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; carbon black such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; conductive fibers such as carbon fiber and metal fiber; metal powders such as carbon fluoride, aluminum and nickel powder; conductive whiskey such as zinc oxide and potassium titanate; conductive oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives and the like.

(27) The binder is added in an amount of 1 to 50% by weight, on the basis of the total weight of the mixture containing the positive electrode active material, as a component that assists in bonding between the active material and the conductive material and bonding to the current collector. Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.

(28) The filler is optionally used as a component for inhibiting expansion of a positive electrode, and is not particularly limited as long as it is a fibrous material without causing a chemical change in the battery. Examples of the filler include olefin polymers such as polyethylene and polypropylene; fibrous materials such as glass fibers and carbon fibers.

(29) Further, the negative electrode may be formed by coating a negative electrode material on a negative electrode collector and drying the negative electrode active material. The negative electrode may further include the above-described components.

(30) The negative electrode current collector is generally made to a thickness of 3 to 500 micrometers. The negative electrode current collector is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and examples thereof include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel of which the surface has been treated with carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like. In addition, like the positive electrode current collector, fine unevenness can be formed on the surface to enhance the bonding force of the negative electrode active material, and it can be used in various forms such as a film, a sheet, a foil, a net a porous body, a foam, and a nonwoven fabric.

(31) As the negative electrode active material of the present invention, a material capable of reversibly adsorbing/discharging lithium ions such as silicon (Si) and tin may be used. As long as such a material is used, it is possible to exhibit the effects of the present invention in any of composite, alloy, compound, solid solution and composite negative electrode active material including silicon-containing material and tin-containing material. As the silicon-containing material, Si, SiO.sub.x (0.5<x<2.0) or an alloy, a compound or a solid solution which is generated by substituting part of Si or Si contained in SiO.sub.x with at least one element selected from the group consisting of B, Mg, Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Nb, Ta, V, W, Zn, C, N, and Sn may be used.

(32) These materials may constitute a negative electrode active material alone or may constitute a negative electrode active material by a plurality of kinds of materials. Examples of constituting the negative electrode active material by the plural kinds of materials include a compound containing Si, oxygen and nitrogen, a composite of a plurality of compounds containing Si and oxygen and having different composition ratios of Si and oxygen, and the like. Among these, SiO.sub.x (0.5<x<2.0) is preferable because the discharge capacity density is large and the expansion ratio at the time of filling is smaller than that of Si.

(33) The silicon oxide negative electrode is a negative electrode which uses silicon and oxides thereof as main materials in order to increase the capacity density of the negative electrode which uses the existing carbon material such as graphite. It has a theoretical capacity density of 4200 mAh/g, which is much higher than the theoretical capacity density of carbon material of 372 mAh/g, which can be suitably used as a negative electrode for a secondary battery. However, since the silicon oxide negative electrode is inferior in the stability of the form, the initial irreversible capacity is large, and there is a risk that the electrode capacity is reduced or the cell balance is collapsed, and thus a pre-lithiation process as in the present invention is required.

(34) It is possible to use a commonly known polyolefin separator or a composite separator in which an organic and inorganic composite layer is formed on the olefin based material, as a separator for insulating the electrodes between the positive electrode and the negative electrode, and the present invention is not limited to these examples.

(35) The electrolyte injected into the secondary battery is a lithium salt-containing non-aqueous electrolyte, which is composed of a nonaqueous electrolyte and lithium. As the non-aqueous electrolyte, a non-aqueous electrolyte, a solid electrolyte, an inorganic solid electrolyte and the like are used.

(36) Examples of the non-aqueous electrolyte include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylenecarbonate, dimethyl carbonate, diethyl carbonate, gamma-Butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, methyl pyrophosphate, ethyl propionate, etc.

(37) Examples of the organic solid electrolyte include a polymer electrolyte such as a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, an agitation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, a polymer including an ionic dissociation group, and the like.

(38) Examples of the inorganic solid electrolyte include nitrides, halides, and sulfates of Li such as Li.sub.3N, LiI, LisNI.sub.2, Li.sub.3N—LiI—LiOH, LiSiO.sub.4, LiSiO.sub.4—LiI—LiOH, Li.sub.2SiS.sub.3, Li.sub.4SiO.sub.4, Li.sub.4SiO.sub.4—LiI—LiOH, and Li.sub.3PO.sub.4—Li.sub.2S—SiS.sub.2.

(39) The lithium salt is a substance that is soluble in the non-aqueous electrolyte. The examples of the lithium salt include LiCl, LiBr, LiI, LiClO.sub.4, LiBF.sub.4, LiB.sub.10Cl.sub.10, LiPF.sub.6, LiCF.sub.3SO.sub.3, LiCF.sub.3CO.sub.2, LiAsF.sub.6, LiSbF.sub.6, LiAlCl.sub.4, CH.sub.3SO.sub.3Li, CF.sub.3SO.sub.3Li, (CF.sub.3SO.sub.2).sub.2NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium 4-phenylborate, imide and the like.

(40) For the purpose of improving charge/discharge characteristics, flame retardancy, etc., pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexaphosphoric triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, aluminum trichloride, etc. may be added to the non-aqueous electrolyte. In some cases, a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further added to impart nonflammability, or a carbon dioxide gas may be further added to improve high temperature storage characteristics.

(41) Hereinafter, the present invention will be described in more detail through examples below. However, the following Examples and Experimental Examples are provided for illustrating the present invention, and the scope of the present invention is not limited by these Examples and Experimental Examples.

Example 1

(42) <Preparation Method of Lithium Metal-Al.sub.2O.sub.3 Composite Thin Film>

(43) Lithium ingots were sufficiently melted at a temperature of 180 degrees Celsius or more to prepare molten lithium, and then Al.sub.2O.sub.3 powder having a particle size of 0.5 to 1.0 μm was added and stirred to prepare a mixture. At this time, the ratio of the molten lithium and μm was adjusted to 75 volume % of lithium and 25 volume % of Al.sub.2O.sub.3 in a volume ratio. The prepared molten lithium-Al.sub.2O.sub.3 mixture was extruded from a frame having a gap of 100 μm and cooled to room temperature to prepare a lithium metal-Al.sub.2O.sub.3 ribbon having a thickness of 100 μm. The lithium metal-Al.sub.2O.sub.3 ribbon was rolled to a thickness of 5 μm to prepare a lithium metal-Al.sub.2O.sub.3 thin film.

(44) <Preparation of Negative Electrode>

(45) As a negative electrode active material, 92 wt % of SiO, 3 wt % of Denka Black (conductive material), 3.5 wt % of SBR (binder) and 1.5 wt % of CMC (thickener) were added to water, to thereby prepare a negative electrode mixture slurry.

(46) The negative electrode mixture slurry was coated on one side of the copper collector, dried and rolled, and then punched to a predetermined size to produce a negative electrode.

(47) <Formation of Lithium Metal-Al.sub.2O.sub.3Composite Film on the Surface of Negative Electrode>

(48) A lithium metal-Al.sub.2O.sub.3 composite thin film having a thickness of 5 μm prepared above was formed on the surface of the SiO negative electrode by a lamination method to prepare an electrode.

(49) <Preparation of Lithium Secondary Battery>

(50) A lithium metal foil (150 μm) was used as a counter electrode, and a polyolefin separator was interposed between the negative electrode and the counter electrode. Then an electrolytic solution in which 1 M lithium hexafluorophosphate (LiPF 6) was dissolved was injected into a solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (DEC) were mixed at a volume ratio of 50:50, to prepare a coin type half-cell.

Example 2

(51) A battery was prepared in the same manner as in Example 1, except that the thickness of the lithium metal-Al.sub.2O.sub.3 ribbon was changed to 150 μm and the thickness of the lithium metal-Al.sub.2O.sub.3 thin film was changed to 5 μm.

Example 3

(52) A battery was prepared in the same manner as in Example 1, except that the thickness of the lithium metal-Al.sub.2O.sub.3 ribbon was changed to 200 μm and the thickness of the lithium metal-Al.sub.2O.sub.3 thin film was changed to 10 μm.

Example 4

(53) A battery was prepared in the same manner as in Example 1, except that the SBR-based binder (6 parts by weight based on 100 parts by weight of Al.sub.2O.sub.3) was added to the molten lithium together with the Al.sub.2O.sub.3 powder.

Example 5

(54) A battery was prepared in the same manner as in Example 1, except that the polyacrylic acid (PAA)-based binder (8 parts by weight based on 100 parts by weight of Al.sub.2O.sub.3) was added to the molten lithium together with the Al.sub.2O.sub.3 powder.

Example 6

(55) A battery was prepared in the same manner as in Example 1, except that the ratio of lithium to Al.sub.2O.sub.3 was adjusted to 78% by volume of lithium and 22% by volume of Al.sub.2O.sub.3.

Comparative Example 1

(56) The battery was prepared in the same manner as in Example 1, except that an untreated SiO electrode was used in place of the SiO electrode on which the lithium metal-Al.sub.2O.sub.3 composite layer having an average thickness of 5 μm in the above example is formed as the negative electrode.

Comparative Example 2

(57) Powdered MgO was added to the molten lithium and they were mixed (weight ratio of lithium and MgO particles was 8:2). In the argon protective gas environment, the molten lithium mixed with the MgO was transferred to an extrusion coater so that the mixed molten lithium was coated on the surface of the SiO negative electrode of Example 1 to a thickness of 5 μm, and then cooled at room temperature. Thereafter, a battery was prepared in the same manner as in Example 1.

Comparative Example 3

(58) A battery was prepared in the same manner as in Comparative Example 2, except that Al.sub.2O.sub.3 particles were mixed with molten lithium instead of MgO in Comparative Example 2.

Comparative Example 4

(59) A battery was prepared in the same manner as in Comparative Example 2, except that the coating thickness was adjusted to 10 μm in Comparative Example 2.

Comparative Example 5

(60) A battery was prepared in the same manner as in Comparative Example 3, except that the coating thickness was adjusted to 10 μm in Comparative Example 3.

Comparative Example 6

(61) A battery was prepared in the same manner as in Comparative Example 2, except that an argon protective gas atmosphere was not formed at the coating in Comparative Example 2.

Comparative Example 7

(62) A battery was prepared in the same manner as in Comparative Example 3, except that an argon protective gas atmosphere was not formed at the coating in Comparative Example 3.

Experimental Example 1 First Cycle Charge/Discharge Reversibility Test

(63) The coin-type half-cell produced in the above Examples and Comparative Examples was subjected to the charge-discharge reversibility test using an electrochemical charging/discharging device. During the first cycle charge, the current was applied at a current density of 0.1 C-rate up to a voltage of 0.005V (vs. Li/Li+) and discharged at the same current density up to a voltage of 1.5V (vs. Li/Li+). At this time, the charging capacity and the discharging capacity were measured, and the ratio (discharging capacity/charging capacity*100) was calculated and shown in Table 1.

Experimental Example 2 Calorimetric Test

(64) In order to perform the differential scanning calorimetry, the coin-type half-cells of Examples and Comparative Examples were charged and discharged for 1 cycle as described above, and charged to 0.005 V in the second cycle to activate the negative electrode, 0.1 ml of electrolyte was added to 13 mg of the thus-obtained charged negative electrode powder, and was then loaded to a DSC equipment (mettle Toledo). The thus-loaded sample was heated at a heating rate of 10° C./min. and the calorie was measured. The results are shown in Table 1.

(65) TABLE-US-00001 TABLE 1 First charge/discharge Main Calorific efficiency (%) Onset(° C.) peak(° C.) value (J/g) Example 1 95 120 296 2023 Example 2 93 120 297 2027 Example 3 92 120 296 2022 Example 4 91 121 298 2033 Example 5 90 122 298 2030 Example 6 94 120 296 2019 Comparative 73 97 261 4150 Example 1 Comparative 85 115 271 2950 Example 2 Comparative 87 120 280 2680 Example 3 Comparative 87 116 270 2900 Example 4 Comparative 88 120 280 2580 Example 5 Comparative 78 115 270 3380 Example 6 Comparative 79 120 280 3155 Example 7

(66) The first cycle charge/discharge reversibility of Example 1 was improved by 22% compared to Comparative Example 1. The reason why the reversibility of Example 1 was improved would be because the lithium metal of the lithium metal-inorganic composite layer formed on the surface of the SiO electrode reacted with SiO to cause a surface side reaction in advance and experienced volume change caused by charging, thereby making dead-lithium by volume expansion in advance. It is understood that the lithium metal consumed in the side reaction at the time of the first charge could be reduced by experiencing the side reaction in advance, and thus most of the lithium metal, which was inputted at the time of charging, was reversibly outputted.

(67) In addition, the onset temperature and the main peak temperature of Examples 1 to 6 were higher than those of Comparative Example 1, which means that the cell is maintained safely to a higher temperature. Further, the fact that Examples 1 to 6 are smaller in calorific values than Comparative Example 1 is interpreted to mean that it is safer at high temperature exposure. The reason why the SiO electrode in which the lithium metal-inorganic composite layer of this embodiment is introduced has a safer result is because the lithium metal in the lithium metal-inorganic composite layer disappeared after the pre-lithiation, and the remaining inorganic layer played a role as a protective layer for protecting the surface of SiO electrode.

(68) In the batteries of Comparative Examples 2 to 7, the lithium metal-inorganic composite layer was introduced into the negative electrode, but it was observed that the charge-discharge efficiency was poor as compared with the batteries of Examples 1 to 6. This is presumably because the lithium metal was exposed to the atmosphere during the application of the molten lithium-inorganic mixed solution to the SiO negative electrode, resulting in the degeneration of the lithium and the lack of pre-lithiation of the negative electrode.

DESCRIPTION OF SYMBOLS

(69) 10: molten lithium 20: inorganic powder 30: extruder 40: lithium metal-inorganic composite ribbon 50: roller 60: lithium metal-composite thin film 70: negative electrode 80: inorganic layer 90: pre-lithiated negative electrode