Art
[1]This application is all the information and claims the benefit of priority based on 2017.08.11 character Korea Patent Application No. 10-2017-0102252, described in the literature of the Korea patent application is included as part of this specification.
[2]It relates to a method of pre lithiated to form an inorganic composite layer, the present invention provides a lithium metal in the negative electrode in that, specifically, the steps before assembling the lithium secondary battery in accordance with the method of the secondary battery negative electrode lithiated before.
BACKGROUND
[3]The price of energy due to the depletion of fossil fuels is rising, while the amplified interest in environmental pollution becomes an indispensable factor for the demand for eco-friendly alternative energy sources, the future life and, in particular, technology development for mobile devices the demand for secondary batteries as an energy source is rapidly increasing as the demand increases.
[4]
[5]Typically in the form face of the battery in the high and the demand for prismatic secondary batteries or pouch type secondary batteries with a thin thickness can be applied to products such as a mobile phone, the material surface at high energy density, discharge voltage, the lithium ion battery of the output stability, the demand is high for a lithium secondary battery such as a lithium ion polymer battery.
[6]
[7]In general, secondary batteries are home coating the entire active materials to the surface of the configuration on the positive and negative electrodes, and then by interposing the separator therebetween made of an electrode assembly, a cylindrical or prismatic metal can, or inside the pouch-shaped case of the aluminum laminate sheet of attached, either primarily or impregnated with a liquid electrolyte injected into the electrode assembly, or is manufactured using a solid electrolyte.
[8]
[9]A cathode active material of a lithium secondary battery has been various forms of carbon-based materials, including the insertion and desorption of lithium available artificial graphite, natural graphite, and hard carbon is applied. Graphite such as natural graphite or artificial graphite of the carbon-based material is lowered to the discharge voltage of lithium compared to the 0.1V, a battery using graphite as a negative electrode active material exhibits a high discharge voltage of 3.6V, the advantage in the energy density of the lithium cell surface provided, and also the most widely used because it ensures a long life of the lithium secondary battery with excellent reversibility.
[10]
[11]
However, there is a case of fabricating an electrode plate of graphite as the active material, a polar plate capacity density becomes low in a low energy density per unit volume of the side plates a problem. In addition, a high discharge voltage tends to occur a side reaction with the graphite and the organic electrolyte solution, there is a risk of fire or explosion due to erroneous operation and the excessive charging of the battery.
[12]
[13]
In order to solve this problem, a negative active material of the oxide being recently developed. The metal-based active material such as Si, Sn has been proposed as a material capable of represents a high-capacity replacement for the lithium metal. Among them, Si has received attention due to low prices and high capacity (4200mAh / g).
[14]
[15]
However, in the case of using a silicon-based negative active material is a major problem arises initial irreversible capacity. In the charging and discharging reaction of the lithium secondary battery, and has a lithium insertion in the cathode discharge from the anode during charging and discharging when there are desorbed from the negative electrode dolahganeunde back to the anode, in the case of a silicon-based negative active severe a change in volume and the surface side reactions during the initial charge a large amount of lithium inserted into the negative electrode not to go back to the positive electrode, and thus there arises a problem of enlarging the initial irreversible capacity. The larger the initial irreversible capacity, there arises a problem that the battery capacity decreases rapidly with cycle.
[16]
[17]
The method for pre lithiated silicon oxide negative electrode including a silicon-based negative active material in order to solve the problem as described above is known. I lithiated method, and a method for pre lithiated a method for producing the electrode and the negative electrode was lithium by a physicochemical method for the negative electrode active material Chemistry electrochemically known.
[18]
[19]
Conventional physical and chemical methods have a problem that had to due to environmental factors that must be carried out at high temperatures pose a risk of fire and explosion, the production cost increases existing electrochemical method can not uniformly control the initial irreversible capacity there was.
[20]
[21]
US Patent Publication No. 2015-0357628 discloses a negative electrode active material in order to improve the efficiency of the electrode with a high specific capacitance, a mixture of ceramic particles in the molten lithium lithium but is disclosed for coating a negative electrode of a ceramic extrusion technology, lithium due to the high reactivity of the metal must be performed for the entire process under inert gas atmosphere, there was a difficult process disadvantage.
[22]
[23]
Therefore, the technology for a method of improving the initial irreversibility, and improves the safety of the battery is necessary to pre lithiated in a manner relatively easy for the negative electrode having a high capacity.
[24]
Detailed Description of the Invention
SUMMARY
[25]
The present invention has been conceived to solve the problems of the prior art, in the former lithiated to improve the initial irreversibility of the negative electrode having a high capacity, and to provide a method which more work processes is easy simple and the handling of lithium metal there are those aimed at.
[26]
Further object of the present invention is also to provide a lithiated prior method of improving the safety of the secondary battery.
Problem solving means
[27]
The present invention was dispersed into a lithium metal powder, inorganic powder and a binder in a solvent to prepare a mixed solution; And lithium metal in the negative electrode using the above-mentioned mixed solution-I is lithiated method of a secondary battery negative electrode, comprising the step of forming the inorganic compound layer.
[28]
According to the preferred embodiment of the present invention, the thickness of the composite layer is from 0.5 to 20㎛.
[29]
According to an appropriate embodiment of the invention, the inorganic powder is alumina (Al 2 O 3 ), titanium dioxide (TiO 2 ), zirconium dioxide (ZrO 2 ), silicon dioxide (Si0 2 ), tin oxide (Sn0 2 ), oxide cerium (Ce0 2 ), magnesium oxide (MgO), calcium oxide (CaO) and yttria (Y oxide 2 O 3 may be alone or in combination of two or more selected from a).
[30]
According to an appropriate embodiment of the invention, the lithium metal powder 20 to 40 parts by weight of the inorganic powder is 50 to 80 parts by weight, the binder is placed in a solvent of 1 to 10 parts by weight.
[31]
According to an appropriate embodiment of the invention, the lithium metal-method for forming the inorganic compound layer, it is one method selected from coating, spraying, lamination.
[32]
According to the preferred embodiment of the present invention, the particle size of the lithium metal powder is 5 ~ 50㎛.
[33]
According to the preferred embodiment of the present invention, the particle size of the inorganic powder is 0.1 to 10㎛.
[34]
According to an appropriate embodiment of the invention, the lithium metal-inorganic compound layer is not activated after the initial charge, the remaining lithium metal in the form.
[35]
According to an appropriate embodiment of the invention, the cathode may comprise silicon oxide.
[36]
In another aspect, the present invention provides a negative electrode of a secondary battery manufactured by applying the pre lithiated way, the secondary battery including the cathode.
Effects of the Invention
[37]
The present invention provides a method for pre lithiated a high negative electrode capacity by a simple process, and a negative electrode of a secondary battery manufactured by the former lithiated method provided by the invention have an initial irreversible improved properties, such secondary battery, a secondary battery manufactured using the negative electrode has a high charge-discharge efficiency.
[38]
In addition, the lithium metal of the present invention an inorganic compound layer is introduced into the cathode, as inserted into the anode active material layer of lithium by the former lithiated is a mineral left in the residue in the multiple layer safety of the battery to protect the cathode surface the effect of improving.
Brief Description of the Drawings
[39]
1 is a lithium metal of the present invention is a view showing the aspect of applying the inorganic material to the cathode mixture.
[40]
2 is formed on a lithium metal negative electrode-lithium is occluded by the negative electrode composite layer from the inorganic substance is a view showing the sun around the lithiated.
[41]
3 is a view showing the inorganic material layer is coated by cathode before lithiated method of the present invention.
Best Mode for Carrying Out the Invention
[42]
Hereinafter, the present invention in detail. The present invention is not limited by the following Examples and Experimental Examples. Examples according to the present invention can be modified in many different forms and the scope of the invention is not to be construed as limited to the embodiments set forth herein. Embodiments of the present invention are provided to more fully illustrate the present invention the technician skilled in the art.
[43]
[44]
I lithiated cathode of a secondary battery according to the present invention is to prepare a mixed solution was dispersed into a lithium metal powder, inorganic powder and a binder in a solvent; And a lithium metal anode using the mixed solution - a step of forming an inorganic compound layer.
[45]
Cathode material initial irreversibility of the lithium ion battery has a major drawback. In particular, the former lithiated (pre-lithiation) before making a cell assembly for a cathode of Si system is severe a change in volume and the surface side reactions there is let come out again during the discharge a large amount of lithium used in charge, to improve such an initial irreversible when there.Aye embodiment undergoes a side reaction generated when the first pre-charge. Therefore, when actually making a cell assembly subjected to charge / discharge the first cycle is to be conducted in a non-reversible reduction conditions as those which will be the initial irreversible decrease.
[46]
As shown in the present invention 1, the lithium metal-inorganic material composite layer and the initial irreversible is formed on the surface of a graphite electrode comprising a larger SiO or SiO, Li-In metal-inorganic compound layer of lithium metal part is reduced initial irreversible the former being used as a lithiated uses having, mineral that is to be left before and after lithiated is characterized in that to help improve the safety of a cathode.
[47]
[48]
According to an appropriate embodiment of the invention, the lithium-metal-layer thickness of the inorganic compound is 0.5 to 20㎛. And more preferably from 3 to 1 to 8㎛ it decided 10㎛, most preferred. The effect is exhibited in enhancement of the safety around the lithiated and the battery when the thickness of the inorganic layer compound be 0.5 to 20㎛ - lithium metal.
[49]
[50]
According to an appropriate embodiment of the invention, the inorganic powder is alumina (Al 2 O 3 ), titanium dioxide (TiO 2 ), zirconium dioxide (ZrO 2 ), silicon dioxide (Si0 2 ), tin oxide (Sn0 2 ), oxide cerium (Ce0 2 ), magnesium oxide (MgO), calcium oxide (CaO) and yttria (Y oxide 2 O 3 may be alone or in combination of two or more selected from a).
[51]
According to an appropriate embodiment of the invention, the lithium metal powder 20 to 40 parts by weight of the inorganic powder is 50 to 80 parts by weight, the binder is placed in a solvent of 1 to 10 parts by weight. Li metal - when the composition of the mineral mixture is il above range, there is the effect to all lithiated and safety improvement in the negative electrode.
[52]
The binder I is typically bonded to be used as may be used, and PVDF, a SBR-based binder typically. Also it may be used PAA (Poly acrylic acid) series, CMC (Carboxymethyl cellulose) based, polyimide (Polyimide) binder. If the content of the binder is less than 1 part by weight, the lithium metal of the present invention and the possibility of the inorganic compound layer to be readily desorbed from the negative electrode, is not preferable in all lithiated side if more than 10 parts by weight.
[53]
According to the preferred embodiment of the present invention, the particle size of the lithium metal powder is 5 ~ 50㎛.
[54]
According to an appropriate embodiment of the invention, the particle size of the inorganic powder is 0.1 to 10 ㎛, more preferably 0.1 to 5 ㎛, and most preferably 0.5 to 1㎛. If the particle diameter of the inorganic powder exceeds 10㎛ is not preferable because it may not be well dispersed in the solvent.
[55]
[56]
Kinds of the solvent as long as the lithium metal and the inorganic powder to be uniformly dispersed in the solvent is not particularly limited, and can be specifically exemplified the hexene (Hexane), benzene (benzene), toluene (toluene), and xylene (xylene), etc. . According to an embodiment of the present invention was used as n- hexane.
[57]
The solid content concentration of the lithium metal and the inorganic powder, the volume ratio of 50 to 70wt% and a solid content compared to the solvent is, a solid content of 55 to 65 vol%, a solvent of 35 to 45vol%. Solid content of the case is less than 50wt%, the lithium-metal-low amount of loading upon coating the inorganic substance powder mixed slurry on the electrode can be a problem with the final target thickness is lowered, if it exceeds 70wt%, the solid concentration is too high, the electrode phase there is less uniformity when applied problems.
[58]
[59]
According to an appropriate embodiment of the invention, the lithium metal-method for forming the inorganic compound layer, it is one method selected from coating, spraying, lamination. Lithium metal powder, to an inorganic powder and a binder dispersed into a solvent, a lithium metal-to form an inorganic composite layer, applying a solution of the inorganic compound in the negative electrode, or spraying, or using the release film of lithium metal. Using the release film of lithium metal - a method of forming the inorganic compound layer, wherein the lithium metal on the release film of the polymer material - after coating an inorganic compound solution, and laminating the coated release film on the negative electrode, detaching the release films how it can to.
[60]
According to an appropriate embodiment of the invention, the lithium metal-inorganic compound layer is not activated after the initial charge, the remaining lithium metal in the form.
[61]
[62]
On the other hand, the present invention has the characteristic that even in providing a secondary battery including the negative electrode produced in the same manner as described above.
[63]
[64]
A secondary battery according to the present invention is composed by two separate electrodes of different polarities are stacked in a separate state to the separator housing a formed electrode assembly, the electrode assembly is a cathode including a positive electrode, a negative electrode active material comprising a positive electrode active material , and it is composed of a separator.
[65]
[66]
Specifically, the positive electrode is, for example, be prepared by drying after applying the mixture of the positive electrode active material, conductive material and a binder on a positive electrode collector, as necessary, a filler may be further added to the mixture.
[67]
[68]
The positive electrode active material according to the present invention lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ) the compound substituted by a layered compound or one or more transition metals, and the like; Formula Li 1 + x Mn 2-x O4 (wherein, x is from 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2, lithium manganese oxide (LiMnO of 2 ); the lithium copper oxide (Li 2 CuO 2 ) ; LiV 3 O 8 , LiFe 3 O 4 , V 2 O 5 , Cu 2 V 2 O 7 including the vanadium oxide; Formula LiNi 1-x M x O 2 (where, M = Co, Mn, Al , Cu, Fe, Mg, B or Ga, and, x = 0.01 ~ 0.3 Im) Ni-site type lithium nickel oxide (lithiated nickel expressed in oxide); Formula LiMn 2-x M x O 2 (where, M = Co, Ni, Fe , Cr, and Zn, or Ta, x = 0.01 ~ 0.1 Im) or Li 2 Mn 3 MO 8 (where, M = Fe, Co, Ni, lithium manganese composite oxides represented by Cu or Zn); LiMn lithium portion of the formula is substituted by an alkaline earth metal ion 2 O 4 ; disulfide compounds; Fe 2 (MoO 4 ) 3Or it may be mixed with the compound containing as a main component a lithium adsorbent material (lithiumintercalation material), such as composite oxides formed by combination thereof.
[69]
[70]
The cathode current collector is generally fabricated to have a thickness of 3 to 500 ㎛. The cathode current collector, if it has suitable conductivity without causing chemical changes in the fabricated battery is not particularly limited, for example, the surface of stainless steel, aluminum, nickel, titanium, sintered carbon, or aluminum or stainless steel on carbon, nickel, titanium and the like may be used as a surface treatment or the like. Current collector may increase the adhesive strength of the positive electrode active material to form fine irregularities on the surface thereof, films, sheets, foils, nets, porous structures, foams and non-woven fabrics and so on can take various forms.
[71]
[72]
The conductive material is commonly added in the mixture including the cathode active material to the total weight of 1 to 50% by weight. This conductive material so long as it has suitable conductivity without causing chemical changes in the fabricated battery is not particularly limited, for example, graphite such as natural graphite or artificial graphite; Carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, carbon black and thermal black; Conductive fibers such as carbon fibers and metallic fibers; Metal such as carbon fluoride, aluminum, nickel powder, powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive oxides such as titanium oxide; Poly is a conductive material such as phenylene derivative may be used.
[73]
[74]
The binder is a component assisting in binding to the total binding and the home, such as the active material and the conductive material is commonly added in the total mixture weight, includes the cathode active material of 1 to 50% by weight. Examples of the binder include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose by Woods (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinyl pyrrolidone, ethylene, polyethylene tetrafluoroethylene , polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene beuti butylene rubber, fluoro rubber and various copolymers and the like.
[75]
[76]
Up pingye polymer of the filler and so on are optionally used as a component of suppressing the expansion of the positive electrode, if the standing fibrous materials without causing chemical changes in the fabricated battery, nor particularly limited, for example, polyethylene and polypropylene; And fibrous materials such as glass fiber and carbon fiber.
[77]
[78]
Further, the cathode is fabricated by applying and drying a negative electrode material on a negative electrode current collector and, if necessary, may be further included to the same components described above.
[79]
[80]
The anode current collector is generally fabricated to have a thickness of 3 to 500 ㎛. The anode current collector, so long as it has suitable conductivity without causing chemical changes in the fabricated battery is not particularly limited, for example, of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel surface to be surface-treated with carbon, nickel, titanium or silver, and aluminum-cadmium alloys. Also Similar to the cathode current collector, to form fine irregularities on the surface may enhance the bonding strength between the negative electrode active material, films, sheets, foils, nets, porous structures, foams and non-woven fabrics or the like can be used in various forms.
[81]
Negative electrode active material of the present invention, it is possible to use a material which reversibly inserts / release lithium ions such as silicon (Si) or tin. With this material, it is that of the composite anode active material including the organization, an alloy, a compound, a solid solution and a silicon-containing material or a tin-containing material which would also exert the effects of the present invention are possible. A silicon containing material, Si, SiO x (0.5
[103]
As the negative electrode active material by the addition of SiO 92% by weight of Denka black (Denka Black, a conductive agent) and 3% SBR (binder) 3.5% by weight, and CMC (thickener) 1.5% by weight in water to prepare a negative electrode mixture slurry.
[104]
On a surface of a copper collector, and coating the negative electrode mixture slurry, which was dried and rolled to prepare a negative electrode was punched into a predetermined size.
[105]
[106]

[107]
-Al lithium metal on the negative electrode surface SiO 2 O 3 to form a composite layer of lithium metal powder (particle size: 5 ~ 50㎛) 30% by weight, Al 2 O 3 powder (particle diameter: 0.5 ~ 1) ㎛ 66% by weight and 4% by weight of a binder to prepare a slurry by dispersing into the n- hexane solution. The mixing ratio of the solvent and the solid content was set at 35vol% solvents, solid 65vol%. Al - the slurry prepared as above, the lithium metal has a mean thickness of the coating on the electrode surface and dried SiO 5㎛ 2 O 3 to form a composite layer.
[108]
[109]

[110]
Relative (counter) was used as the lithium metal foil (150μm) to the electrode, as the anode and then through a polyolefin separator between the counter electrode, ethylene carbonate (EC), ethyl methyl carbonate in a volume ratio (DEC) 50:50 1M lithium phosphate hexafluoride (LiPF in a mixed solvent of 6 to inject a) is dissolved in the electrolytic solution was prepared a coin-type half cell.
[111]
[112]
Example 2
[113]
Al 2 O 3 , except that the magnesium oxide (MgO) was prepared in place of a battery in the same manner as in Example 1.
[114]
[115]
Example 3
[116]
Al 2 O 3 in place of zirconium dioxide (ZrO 2 , except that a) to prepare a cell in the same manner as in Example 1.
[117]
[118]
Example 4
[119]
It was prepared in a cell in the same manner as in Example 1 except for adjusting the thickness of the inorganic layer compound in 3㎛ - lithium metal.
[120]
[121]
Example 5
[122]
It was prepared in a cell in the same manner as in Example 1 except for adjusting the thickness of the inorganic layer compound in 8㎛ - lithium metal.
[123]
[124]
Example 6
[125]
Lithium metal powder and the Al 2 O 3 was prepared in a cell in the same manner as in Example 1 except that the weight ratio of the powder was changed to 20:76.
[126]
[127]
Example 7
[128]
Lithium metal powder and the Al 2 O 3 was prepared in a cell in the same manner as in Example 1 except that the weight ratio of the powder was changed to 35:61.
[129]
[130]
Comparative Example 1
[131]
Cathode in the embodiment with an average thickness of lithium metal 5㎛ -Al 2 O 3 was produced by the cell in Example 1 and the same method except for using SiO electrode are not yet processed instead of SiO electrode composite layer is formed.
[132]
[133]
Comparative Example 2
[134]
Insert the powder in the form of MgO in molten lithium which was prepared by extrusion Example 1 of the same cell as in Example 1 except that SiO was coated on the negative electrode surface. Wherein the weight ratio of lithium and MgO is 8: 2, and the coating thickness was 20㎛.
[135]
[136]
Comparative Example 3
[137]
It was prepared in a cell in the same manner as in Example 1 except for adjusting the thickness of the inorganic layer compound in 30㎛ - lithium metal.
[138]
[139]
Experimental Example 1 The first cycle charge-discharge reversibility test
[140]
Examples and compared using a coin-type half-cell for electrochemical charge discharger prepared in Examples were tested for charge-discharge reversibility. The first cycle charging 0.005V (vs. Li / Li + voltage) voltage 0.1C-rate 1.5V (vs. Li / Li +) at a current density of charged and dropped by applying an electric current at a current density, during the discharge of up to It was carried out to discharge. At this time, the charge capacity and the discharge capacity was measured, by calculating the rate (discharge capacity / charge capacity of 100 *) are shown in Table 1 below.
[141]
[142]
Experimental Example 2. The calorimeter test
[143]
Calorimetry tests (differential scanning calorimetry) issued a scrape the Examples and Comparative Examples after the dolls nose half cell one cycle charge and discharge as described above, gave a cathode was activated by the charged up to 0.005V at the second cycle to. In this way the addition of the electrolyte solution in a charged cathode 0.1ml 13mg powder obtained was loaded into the DSC equipment (mettle Toledo). Thus heating the loaded sample at a heating rate of 10 ℃ / min, and by measuring the amount of heat The results are shown in Table 1.
[144]
[145]
TABLE 1
The first charge-and-discharge efficiency (%) Onset(℃) Main peak(℃) Heating value (J / g)
Example 1 88 115 292 1950
Example 2 87 116 313 1856
Example 3 89 118 350 1799
Example 4 82 115 292 1598
Example 5 97 115 292 2188
Example 6 81 115 292 1573
Example 7 88 114 290 1980
Comparative Example 1 73 97 261 4150
Comparative Example 2 108 (lithium precipitation) 97 242 8156
Comparative Example 3 125 (lithium precipitation) 96 250 8423

[146]
Examples 1 to 7 of the first cycle charge-discharge reversibility is improved by 15% than Comparative Example 1. This embodiment the reason reversible improvement in one of lithium metal was formed on the SiO electrode surface-aroused a pre-surface side reactions, the lithium metal of the inorganic hybrid layer by reaction with SiO, the volume expansion by having previously experienced a change in volume occurring during charge Dead- lithium by also determined by since jwotgi made in advance. By undergo such side reactions previously it could reduce the lithium is first charged in the actual consumption to the side reaction, so that the lithium metal containing charge is thought to have been most nearly reversibly out.
[147]
In the case of Examples 1-7 than Comparative Example was shown that the high temperature onset, main peak temperature, which is interpreted to mean that the cells are more securely held to the high temperature. In addition, it is also the amount of heat generated in Examples 1 to 7 is smaller than that of the comparative example is interpreted to mean that more safety during high-temperature exposure. This embodiment of the lithium metal-reason inorganic composite layer is shown for a safer result introduced SiO electrode is lithium metal-back the lithium metal in the inorganic compound layer disappeared after around lithiated, the remaining inorganic layer to the remainder of SiO electrode surface It is determined to have a role as a protective layer for protecting.
[148]
[149]
Reference Numerals
[150]
100: negative
[151]
200: lithium metal-inorganic mixed solution, the lithium metal-inorganic compound layer
[152]
210: Mineral powder
[153]
220: lithium metal powder
[154]
300: before a lithiated cathode
[155]
400: inorganic layer

Claims
[Claim 1]
It was dispersed into a lithium metal powder, inorganic powder and a binder in a solvent to prepare a mixed solution; Lithium by using the mixed solution in the negative electrode metal-I lithiated method of the secondary battery negative electrode, comprising the step of forming the inorganic compound layer.
[Claim 2]
According to claim 1, wherein said lithium-metal-I lithiated method of the secondary battery negative electrode according to the thickness of the inorganic compound layer it is characterized in that 0.5 to 20㎛.
[Claim 3]
The method of claim 1, wherein the inorganic powder is alumina (Al 2 O 3 ), titanium dioxide (TiO 2 ), zirconium dioxide (ZrO 2 ), silicon dioxide (Si0 2 ), tin oxide (Sn0 2 ), cerium oxide (Ce0 2 ), magnesium (MgO), calcium oxide (CaO) and yttria (Y oxide 2 O 3 ) around the lithiated cathode of a secondary battery of one kind or not less than two kinds selected from a method.
[Claim 4]
The method of claim 1, wherein the lithium metal powder 20 to 40 parts by weight of the inorganic powder is 50 to 80 parts by weight binder 1 to 10 parts by weight of the way around the lithium secondary battery negative electrode, characterized in that into the solvation.
[Claim 5]
According to claim 1, wherein said lithium-metal-method, coating, spraying, around the lithiated method of the secondary battery, the negative electrode, characterized in that one method selected from the group consisting of lamination for forming the inorganic compound layer.
[Claim 6]
The method of claim 1, wherein the particle size of the lithium metal powder before lithiated method of the secondary battery, the negative electrode, characterized in that 5 ~ 50㎛.
[Claim 7]
The method of claim 1, wherein the particle size of the inorganic powder before lithiated method of the secondary battery, the negative electrode, characterized in that 0.1 to 10㎛.
[Claim 8]
According to claim 1, wherein said lithium-metal-inorganic material composite layer around the lithiated method of the secondary battery, the negative electrode, characterized in that the initial activation since there are not left in the lithium form of the metal charge.
[Claim 9]
According to claim 1, wherein said cathode is lithiated former method of a secondary battery negative electrode comprising a silicon oxide.
[Claim 10]
The former method lithiated a secondary battery negative electrode prepared by applying according to any one of claims 1 to 9.
[Claim 11]
The secondary battery comprising a negative electrode prepared by applying a pre lithiated method according to any one of claims 1 to 9.