KR100790852B1 - Anode, method of preparing the same, and lithium battery containing the anode - Google Patents

Abstract

An anode for a lithium battery is provided to inhibit swelling of a lithium battery, and to impart improved charge/discharge capacity, capacity maintenance and capacity per unit volume to a lithium battery. An anode comprises a composite anode active material comprising a core containing a metal capable of forming an alloy with lithium, a conductive agent, a binder and an organosilicon compound, wherein coating layers formed on the core and the conductive agent comprises the organosilicon compound, and the core and the conductive agent having the coating layers are bound to each other by the binder. The coating layers have a dual layer structure including a first coating layer individually formed on the core and the conductive agent, and a second coating layer formed on the first coating layer, wherein the first coating layer comprises the organosilicon compound and the second coating layer comprises the binder.

Description

Anode, method of preparing the same, and a lithium battery employing the same {Anode, method of preparing the same, and lithium battery containing the anode}

1 is a graph showing the results of charge and discharge experiments of the first set of lithium batteries of Examples 4 to 6 and Comparative Example 2. FIG.

2 is a graph showing the results of charge and discharge experiments of the second set of lithium batteries of Examples 4 to 6 and Comparative Example 2. FIG.

The present invention relates to a negative electrode, a method for manufacturing the same, and a lithium battery employing the same. More particularly, a negative electrode including a core and a conductive material coated with an organic silicon compound, a method for manufacturing the same, and a charge / discharge efficiency and a charge / discharge including the same The present invention relates to a lithium battery with improved capacity.

Nonaqueous electrolyte secondary batteries using lithium compounds as negative electrodes have high voltage and high energy density and have been the subject of many studies. Among them, lithium metal has been the subject of much research in the early days when lithium was attracting attention as a negative electrode material due to its rich battery capacity. However, when lithium metal is used as a negative electrode, a large amount of dendritic lithium precipitates on the lithium surface during charging, which may reduce charge and discharge efficiency, cause short circuits with the positive electrode, and may cause heat or shock due to instability or high reactivity of lithium itself. It is sensitive to the danger of explosion and has been an obstacle to commercialization. The carbon-based negative electrode solves the problem of the conventional lithium metal. The carbon-based negative electrode is a so-called rocking-chair method in which a lithium ion present in an electrolyte solution does not use lithium metal and performs a redox reaction while intercalating and discharging between crystal surfaces of a carbon electrode during charging and discharging. The carbon-based negative electrode contributed to the popularization of lithium batteries by solving various problems of lithium metal. However, as various portable devices have become smaller, lighter, and higher in performance, higher capacity of lithium secondary batteries has emerged as an important problem. Lithium batteries using carbon-based negative electrodes have inherently low battery capacity due to the porous structure of carbon. For example, even in the case of the most crystalline graphite, the theoretical capacity is about 372 mAh / g in the composition of LiC6. This is only about 10% of the theoretical capacity of lithium metal at 3860mAh / g. Therefore, despite the existing problems of the metal negative electrode, a study to improve the capacity of the battery by introducing a metal such as lithium to the negative electrode is being actively attempted.

Alloys such as lithium, lithium-aluminum, lithium-lead, lithium-tin, and lithium-silicon are known to achieve greater capacitance than carbon-based materials. However, the use of such alloys or metals alone has a problem due to precipitation of dendritic lithium, so that research has been conducted in a direction to avoid problems such as short circuits while increasing electric capacity by appropriately mixing them with carbon-based materials.

The problem in this case is that the volume expansion ratio of the carbonaceous material and the metal material at the time of redox reduction is different, and the metal material reacts with the electrolyte solution. In the negative electrode material, lithium ions enter the negative electrode during charging. In this case, the volume of the entire negative electrode expands to have a more compact structure. Then, when discharged, lithium escapes back to the ionic state and the volume of the negative electrode material decreases. At this time, since the expansion rate of the carbon-based material and the metal material is different, when they contract again, empty spaces are left, and even a space is generated, resulting in an electrically disconnected portion, which causes electrons to not move smoothly, thereby degrading battery efficiency. In addition, during the charging and discharging process, the metal material reacts with the electrolyte to reduce the life of the electrolyte and consequently to reduce the life and efficiency of the battery. Various conventional techniques have been proposed to solve the problems caused by the use of the composite material. It became.

Japanese Patent Laid-Open No. 1994-318454 proposes a negative electrode comprising a mixture of scaly metal or alloy powder, scaly carbon powder, and a binder. In the present invention, the metal or alloy powder is stacked in parallel to the surface of the electrode, so that current is poorly collected in the electrode due to repeated charge and discharge cycles by applying a uniform pressure to the entire electrode against expansion and contraction of the electrode during battery operation. Is the concept of suppressing. However, even with such a flat powder, it is difficult to solve the above problems caused by the charging and discharging by simple mixing alone. As a result, the stress caused by the expansion and contraction of the metal is generated and the disconnection of the electron transfer path is severe, resulting in an increase in the number of charge and discharge cycles. There is a disadvantage that the battery capacity is greatly reduced.

Japanese Patent Laid-Open No. 1997-249407 proposes a negative electrode containing graphite particles and metal fine particles capable of forming an alloy with lithium. A method of producing a graphite composite in which a raw material powder composed of graphite particles and metal particles is prepared and the powder is pulverized to disperse high-crystalline graphite particles and metal particles. The use of metal fine particles is different from the conventional one, but it is a simple assembly method, and in this case, it is difficult to avoid the problem that the bonding with graphite particles due to the expansion of the metal particles is broken.

Therefore, there is still a need for the development of a negative electrode, which solves these problems of conventional negative electrode materials and shows better charge and discharge characteristics by maintaining high binding force between the negative electrode materials despite charge and discharge.

The first technical problem to be achieved by the present invention is to provide a negative electrode comprising a composite negative electrode active material comprising a core and a conductive material coated with an organic silicon compound.

The second technical problem to be achieved by the present invention is to provide a lithium battery including the negative electrode in which the volume change is suppressed and the charge / discharge capacity, the capacity retention rate, and the capacity per unit volume (mAh / cc) are improved. The problem is to provide a method for producing the negative electrode.

The present invention to achieve the first technical problem,

A core comprising a metal alloyable with lithium; Conductive material; bookbinder; And an organic silicon compound, wherein each of the coating layers formed on the core and the conductive material includes an organic silicon compound, and the core and the conductive material on which the coating layer is formed are bonded to each other by a binder;

It provides a negative electrode comprising a.

In addition, the present invention provides a lithium battery employing the negative electrode in order to achieve the second technical problem.

In addition, the present invention to achieve the third technical problem,

Preparing a slurry by mixing a core, a conductive material, a binder, an organosilicon compound, and a solvent including a metal alloyable with lithium; And it provides a negative electrode manufacturing method comprising the step of drying the slurry.

The negative electrode according to the present invention additionally includes an organosilicon compound, unlike the negative electrode including the conventional metal core, which is bound only by a binder, thereby increasing the high binding force between the negative electrode materials despite the volume change caused by the high expansion rate of the metal active material during charge and discharge. It can maintain and suppress the volume change of a metal active material. In addition, the lithium battery including the negative electrode has excellent charge and discharge characteristics.

Hereinafter, the present invention will be described in more detail.

The negative electrode of the present invention includes a core comprising a metal alloyable with lithium; Conductive material; bookbinder; And a composite anode active material including an organic silicon compound, wherein the coating layers formed on the core and the conductive material each include a silicon compound, and the core and the conductive material on which the coating layer is formed are bound to each other by a binder.

The organic silicon compound in the cathode means an organic compound containing a silicon atom. The organosilicon compound is a compound containing both inorganic and organic properties. Therefore, by coating the surface of the inorganic material such as the core and the conductive material with an organic silicon compound, it is possible to further improve the binding strength of the binder and the inorganic material and to better absorb the volume change of the metal core. As a result, it is possible to maintain a high binding force between the cathode materials despite repeated volume changes of the metal core.

In the cathode, the coating layer may be a composite coating layer in which a binder and a silicon compound are mixed with each other. Such a composite coating layer may be difficult to distinguish the binder and the silicone compound are mixed with each other in the manufacturing step. However, the structure of the composite coating is not necessarily limited thereto. The coating layer may have a multilayer structure consisting of a first coating layer made of silicon and a second coating layer made of a binder formed on the first coating layer, or may have a multilayer structure consisting of three or more coating layers.

In addition, a coating layer formed on each of the core and the conductive material may cover the core and the conductive material. That is, the coating layer may be present in a form surrounding the entire surface of the core and the conductive material.

The core is preferably a composite of graphite, a metal alloyable with lithium. The composite can be prepared, for example, by premixing metal and graphite and then grinding with a high energy mill.

Further, the metal capable of alloying with lithium is not particularly limited as long as it is a metal capable of forming an alloy with lithium, but Si, Sn, Al, Ge, Pb, Bi, Sb, and the like are preferred, and Si is most preferred.

Examples of the conductive material used for the negative electrode include carbon black and graphite fine particles, but are not limited thereto.

The organosilicon compound is preferably a silane compound, a siloxane compound, a silanol compound, or the like. More specific details of the organosilicon compound will be described in the method of manufacturing a negative electrode according to an embodiment of the present invention.

In addition, the present invention provides a lithium battery employing the negative electrode in order to achieve the second technical problem.

The lithium battery of the present invention is characterized by being manufactured including the above negative electrode. The lithium battery of the present invention can be produced as follows.

First, a cathode active material composition is prepared by mixing a cathode active material, a conductive material, a binder, and a solvent. The positive electrode active material composition is directly coated on a metal current collector and dried to prepare a positive electrode plate. It is also possible to produce the positive electrode plate by casting the positive electrode active material composition on a separate support, and then laminating the film obtained by peeling from the support onto a metal current collector.

The positive electrode active material may be any lithium-containing metal oxide, as long as it is commonly used in the art, for example, LiCoO ₂ , LiMn _x O _2x , LiNi _x-1 Mn _x O _2x (x = 1, 2), Li _1-xy Co _x Mn _y O ₂ (0 ≦ x ≦ 0.5, 0 ≦ y ≦ 0.5) and the like, and more specifically, LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ , V ₂ O ₅ And redox compounds such as TiS, MoS, and the like. Carbon black is used as the conductive material, and vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF) and poly Acrylonitrile, polymethylmethacrylate, polytetrafluoroethylene and mixtures thereof, and styrene butadiene rubber-based polymers are used, and N-methylpyrrolidone, acetone, water and the like are used as the solvent. At this time, the content of the positive electrode active material, the conductive material, the binder, and the solvent is at a level commonly used in lithium batteries.

As the separator, any one commonly used in lithium batteries can be used. In particular, it is preferable that it is low resistance with respect to the ion migration of electrolyte, and is excellent in electrolyte-moisture capability. More specifically, the material selected from glass fiber, polyester, teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and combinations thereof may be nonwoven or woven. In more detail, a lithium ion battery uses a rollable separator made of a material such as polyethylene or polypropylene, and a lithium ion polymer battery uses a separator having excellent organic electrolyte impregnation ability. It can be manufactured according to the method.

That is, a separator composition is prepared by mixing a polymer resin, a filler, and a solvent, and the separator composition is directly coated and dried on an electrode to form a separator film, or the separator composition is cast and dried on a support, and then the support The separator film peeled off can be laminated on the electrode and formed.

The polymer resin is not particularly limited, and any material used for the binder of the electrode plate may be used. For example, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and mixtures thereof can be used.

Examples of the electrolyte include propylene carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, and dioxo Column, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate LiPF ₆ , LiBF ₄ in a solvent such as methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diethylene glycol or dimethyl ether, or a mixed solvent thereof. , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , LiN (C _x F _{2x + 1} SO2) (C _y F _{2y + 1} SO ₂ ) (where x and y are natural waters), one or more electrolytes consisting of lithium salts such as LiCl and LiI or a mixture of two or more thereof are dissolved A separator is disposed between the positive electrode plate and the negative electrode plate as described above to form a battery structure. The battery structure is wound or folded, placed in a cylindrical battery case or a square battery case, and then the organic electrolyte solution of the present invention is injected to complete a lithium ion battery.

In addition, after stacking the battery structure in a bi-cell structure, it is impregnated in an organic electrolyte, and the resultant is placed in a pouch and sealed to complete a lithium ion polymer battery.

In addition, the present invention provides a method of manufacturing a negative electrode in order to achieve the third technical problem.

In general, the negative electrode may be formed by molding a negative electrode mixture material including the core and the binder into a predetermined shape, or may be manufactured by applying the negative electrode mixture material to a current collector such as copper foil.

More specifically, a negative electrode material composition is prepared and coated directly on a copper foil current collector, or the porous negative electrode active material film cast on a separate support and peeled from the support is laminated on the copper foil current collector to obtain a negative electrode plate. In addition, the negative electrode of this invention is not limited to the form enumerated above, The form other than the enumerated form is possible.

One aspect of the method for manufacturing a negative electrode according to the present invention comprises the steps of preparing a slurry by mixing a core, a conductive material, a binder, an organosilicon compound and a solvent comprising a metal alloyable with lithium; And drying the slurry.

The preparing of the slurry may include preparing a first slurry by mixing a core, a conductive material, an organic silicon compound, and a solvent including a metal capable of alloying with lithium; And mixing the binder with the first slurry to prepare a second slurry, but is not limited thereto.

That is, it is also possible to prepare a slurry by simultaneously mixing the core, the conductive material, the binder, the organosilicon compound and the solvent containing a metal capable of alloying with lithium. In the case of mixing at the same time, since there is a silicon compound on the surface of the current collector, there is an advantage in that the binding force between the negative electrode material and the copper foil current collector is improved.

And, the core containing the metal alloyable with lithium used in the production method is preferably a composite of lithium alloyable metal and graphite. The metal capable of alloying with lithium is preferably Si, Sn, Al, Ge, Pb, Bi, Sb and the like, with Si being most preferred.

The organosilicon compound used in the production method is preferably a silane compound, a siloxane compound, a silanol compound, and the like, and more specifically, the silane compound may be represented by the following Chemical Formula 1.

<Formula 1>

Si (R ₁ ) (R ₂ ) (R ₃ ) (R ₄ )

Wherein R ₁ is a C _1-5 alkylamine group or C _2-5 alkenyl group, and R ₂ , R ₃ and R ₄ are independently of each other hydrogen, halogen, hydroxy group, substituted or unsubstituted C _1-5 alkoxy group, a substituted or unsubstituted C _1-5 acyloxy group and a substituted or unsubstituted one functional group chosen from the group consisting of unsubstituted C _1-5 acyl.

Among them, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (2-ethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxyoxytri Ethoxysilane, γ-amipropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ -Aminopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, β- (3, 4 epoxycyclohexyl) ethyl triethoxy silane, (gamma)-glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propyl triethoxysilane, (gamma)-mercaptopropyl trimethoxysilane, (gamma)-mercaptopropyl trie Oxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltrimethoxysilane, methyl Trieoxy silane, phenyl trimethoxysilane, phenyl triethoxysilane, etc. are more preferable.

In addition, the siloxane compound is preferably a high molecular compound consisting of a repeating unit of the formula (2).

<Formula 2>

-[Si (R ₅ ) (R ₆ ) -O] _n-

Wherein R ₅ and R ₆ are independently selected from the group consisting of a substituted or unsubstituted C _1-5 alkyl group, a substituted or unsubstituted C _1-5 alkenyl group and a substituted or unsubstituted C _1-5 alkoxy group N is an integer of 10 to 10,000, and the molecular weight of the compound is from 100 to 700,000.

Among these, polydimethylsiloxane, polyaminosiloxane, polyammoniumsiloxane, polymethylphenylsiloxane, polyhydrogensiloxane, etc. of a weight average molecular weight (Mw = 30000) are especially preferable.

Substituents of the alkylamine group, acyl group, acyloxy group, alkyl group, alkenyl group and alkoxy group substituted in the silane and siloxane compound are a group consisting of halogen, hydroxy group, C _1-5 alkyl group and C _1-5 alkoxy group At least one selected from.

The content of the organosilicon compound is preferably 0.0002 to 2% by weight based on the total solids of the core, the conductive material and the binder. If it is less than 0.0002% by weight, there is a problem in that the binding force is lowered due to the lack of a chemically bondable substance, and in the case of more than 2% by weight, it is difficult to uniformly make the slurry.

The content of the organosilicon compound is based on the dry matter, and the amount of the solution containing the organosilicon compound used in the actual slurry production may be appropriately controlled within the content range of the dry matter.

Drying the slurry in the negative electrode manufacturing method is preferably performed at a temperature of 80 ℃ to 300 ℃. If the temperature is less than 80 ° C., there is a problem in that solvents such as water and NMP, which are used for slurry production, cannot be removed. If the temperature is higher than 300 ° C., the binder is pyrolyzed.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and does not limit the scope of the present invention only by these.

Example 1

Core manufacturing (composite of metal and graphite)

1 g of silicon fine particles (Noah, 20 to 60 nm in diameter) and 2 g of graphite (MCMB2528, Osaka Gas) having a diameter of less than 100 nm were mixed for 1 hour using a mechanical stirrer. The mixture was then ground for 60 minutes using a high energy mechanical mill (SPEX CertiPrep, 8000M) to prepare a composite core.

Cathode manufacturing

7.5 g of the composite core powder prepared above, 1.5 g of graphite powder, 0.5 g of aminopropyltriethoxysilane, and N-methylpyrrolidone (NMP) were mixed to prepare a first slurry. Subsequently, 1 g of polyvinylidene fluoride (PVDF, 5 wt%) was mixed with the first slurry, and a second slurry was prepared using a mechanical stirrer.

The second slurry was applied to a thickness of about 200 μm over a copper (Cu) current collector using a doctor blade and dried at room temperature. Thereafter, the resultant was dried again at 130 ° C. in a vacuum atmosphere to prepare a negative electrode plate.

Example 2

A negative electrode plate was manufactured in the same manner as in Example 1, except that vinyltrimethoxysilane was used instead of aminopropyltriethoxysilane.

Example 3

A negative electrode plate was manufactured in the same manner as in Example 1, except that polydimethylsiloxane (Mw = 30000) was used instead of aminopropyltriethoxysilane.

Comparative Example 1

A negative electrode plate was manufactured in the same manner as in Example 1, except that only the polyvinylidene fluoride binder was used without adding aminopropyltriethoxysilane.

Lithium battery manufacturers

Example 4

Example 1 The negative electrode plate prepared as a lithium metal counter electrode, a solution in which a PTFE separator and 1.3 M LiPF ₆ dissolved in EC (ethylene carbonate) + DEC (diethyl carbonate) (3: 7 volume ratio) Two coin cells of the 2016 standard were prepared using as an electrolyte.

Example  5 to 6 and Comparative example  2

Two coin cells were prepared in the same manner except that the negative plates prepared in Examples 2 to 3 and Comparative Example 1 were used instead of the negative electrode plates prepared in Example 1, respectively.

Charge / discharge experiment

The coin cells prepared in each of the above Examples 4 to 6 and Comparative Example 2 were prepared by dividing the first and second sets into a constant current until a constant current was reached at 0.001 V with respect to the Li electrode at a current of 100 mA per gram of the active material. Filling was performed. After the charging was completed, the cell went through a rest period of about 10 minutes, and then discharged by constant current discharge until the voltage reached 1.5 V at a current of 100 mA per 1 g of the active material. From this, capacity retention rate, density, and unit volume capacity were calculated. Capacity retention, density, and unit volume capacity are represented by the following Equations 1 to 3, respectively.

<Equation 1>

Capacity retention rate (%) = discharge capacity in 30 ^th cycle / discharge capacity in 1 ^st cycle x 100

The discharge capacity and capacity retention rate were respectively measured according to the number of cycles.

<Equation 2>

Density (g / cc) = weight of active material at electrode / (electrode area x electrode thickness)

<Equation 3>

Capacity per unit volume (mAh / cc) = Capacity [mAh / g] × Density [g / cc] × (active material + conductive material)

Charging and discharging test results of the first and second sets of coin cells of Examples 4 to 6 and Comparative Example 2 are shown in Tables 1 to 2 and FIGS. 1 to 2, respectively.

Battery (first set) 1st cycle discharge capacity (mAh / g) 30th cycle discharge capacity (mAh / g) Capacity retention rate (%) Comparative Example 2 1018 330 32 Example 4 1062 698 65 Example 5 1079 787 72 Example 6 1111 622 55

Battery (second set) 1st cycle discharge capacity (mAh / cc) 30th cycle discharge capacity (mAh / cc) Density (g / cc) Capacity retention rate (%) Comparative Example 2 999 359 1.09 35 Example 4 1252 823 1.31 65 Example 5 1292 943 1.33 72 Example 6 1250 700 1.25 55

As shown in Tables 1 and 2 and FIGS. 1 and 2, the capacity retention rate in the 30 ^th cycle was about 2 times that of the comparative example. This result indicates that the battery life can be improved by about two times. This remarkable difference is considered to be because, in the case of the embodiments, the organosilicon compound improves the binding force between the negative electrode materials to suppress the occurrence of cracking between the negative electrode materials despite the change in the volume of the metal core during charging and discharging.

In addition, since the embodiments have a higher density than the comparative example, the capacity per unit volume may be increased to implement a battery having a small volume but a high capacity.

Therefore, the lithium battery according to the present invention can provide a high discharge capacity and improved battery life at the same time by overcoming the low capacity retention rate of the conventional lithium battery including a metal core as an active material.

The negative electrode according to the present invention additionally includes an organosilicon compound, unlike the negative electrode including the conventional metal core, which is bound only by a binder, thereby increasing the high binding force between the negative electrode materials despite the volume change caused by the high expansion rate of the metal active material during charge and discharge. It can maintain and suppress the volume expansion of the active material. In addition, the lithium battery including the negative electrode has excellent charge and discharge characteristics.

Claims (16)

A core comprising a metal alloyable with lithium; Conductive material; bookbinder; And An organic silicon compound (organic silicon compound), each of the coating layer formed on the core and the conductive material comprises an organic silicon compound, the core and the conductive material on which the coating layer is formed is bound to each other by a binder, A first coating layer in which the coating layer is formed on the core and the conductive material, respectively; And  It has a multilayer structure comprising a; a second coating layer formed on the first coating layer, A composite anode active material in which the first coating layer includes an organic silicon compound and the second coating layer includes a binder; A cathode comprising a. The negative electrode of claim 1, wherein the coating layer is a composite coating layer in which a binder and an organic silicon compound are mixed with each other. The negative electrode according to claim 1, wherein the coating layer covers the core and the conductive material. A negative electrode according to claim 1, wherein said core is a composite of lithium, alloyable metal, and graphite. The negative electrode of claim 1, wherein the metal alloyable with lithium is at least one metal selected from the group consisting of Si, Sn, Al, Ge, Pb, Bi, and Sb. The negative electrode of claim 1, wherein the organosilicon compound is at least one compound selected from the group consisting of a silane compound, a siloxane compound, and a silanol compound. The lithium battery which employ | adopted the negative electrode in any one of Claims 1-6. Preparing a slurry by mixing a core, a conductive material, a binder, an organosilicon compound, and a solvent including a metal alloyable with lithium; And Drying the slurry; Preparing the slurry, Preparing a first slurry by mixing a core, a conductive material, an organosilicon compound, and a solvent including a metal alloyable with lithium; And Mixing a binder in the first slurry to prepare a second slurry, characterized in that consisting of. delete 10. The method of claim 8, wherein the core comprising lithium and the alloyable metal is a composite of lithium and the alloyable metal and graphite. The method of claim 8, wherein the organosilicon compound is at least one compound selected from the group consisting of a silane compound, a siloxane compound and a silanol compound. 12. The method of claim 11, wherein the silane compound is represented by the following formula (1): <Formula 1> Si (R ₁ ) (R ₂ ) (R ₃ ) (R ₄ ) Where R ₁ is a C _1-5 alkylamine group or C _2-5 alkenyl group, R ₂ , R ₃ and R ₄ independently of one another are hydrogen, a halogen, a hydroxy group, a substituted or unsubstituted C _1-5 alkoxy group, a substituted or unsubstituted C _1-5 acyloxy group and a substituted or unsubstituted C _{1 -5} is one functional group selected from the group consisting of acyl groups. The method of claim 11, wherein the silane compound is vinyl trimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (2-ethoxy) silane, γ-methacrylooxypropyltrimethoxysilane, γ-methacrylooxypropyltriethoxysilane, γ-amipropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyl trimethoxysilane, N- β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrime Oxysilane, β- (3,4 epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane , γ-mercaptopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltrimeth Sisilran, methyltrimethoxysilane, the cathode manufacturing method, characterized in that at least one compound selected from the group consisting of the cock when the silane, phenyl trimethoxy silane and phenyltrimethoxysilane in methyltrimethoxysilane as silane. 12. The method of claim 11, wherein the siloxane compound is a high molecular compound consisting of a repeating unit represented by the following formula (2): <Formula 2> -[Si (R ₅ ) (R ₆ ) -O] _n- Where R ₅ and R ₆ are each independently a substituted or unsubstituted C _1-5 alkyl group, a substituted or unsubstituted C _{1 -} of one selected from the group consisting of a _{5-alkoxy-5-alkenyl} group and a substituted or unsubstituted C ₁ Is a functional group, N is an integer of 10 to 10,000, The molecular weight of the compound is 100 to 700,000. 12. The method of claim 11, wherein the siloxane compound is at least one compound selected from the group consisting of polydimethylsiloxane, polyaminosiloxane, polyammoniumsiloxane, polymethylphenylsiloxane and polyhydrogensiloxane. 9. The method of claim 8, wherein the drying of the slurry is carried out at a temperature of 80 to 300 ℃.

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