KR100893486B1 - Electrode comprising organic/inorganic composite deposited by electrochemical deposition and their preparation method, electrochemical device comprising the above electrode - Google Patents

Abstract

The negative electrode active material layer is formed on one or both surfaces of the current collector, the negative electrode active material layer is (a) at least one (semi) metal selected from the group consisting of Si and Sn; And (b) an electrochemically polymerizable substituent, wherein the at least one substituent selected from the group consisting of vinyl group, aryl group, acrylate group, methacrylate group, cyclic lactone and cyclic carbonate is chemically bonded ), Wherein the polymerizable substituent is fixed in combination with a current collector, and the (semi) metal is mutually chemically bonded to another adjacent (semi) metal to provide a negative electrode and a method of manufacturing the same. The present invention also provides an electrochemical device having the electrode described above.

The present invention provides an electrochemically deposited electrode using a (quasi) metal-containing compound including an ionically bonded substituent and a polymerizable substituent as a precursor compound, thereby increasing the adhesive strength of the electrode and thereby exhibiting long life characteristics of the battery. Can be.

Electrochemical Vapor Deposition, Organic Material, Composite, Electrode Active Material, Electrochemical Device, Lithium Secondary Battery

Description

ELECTRODE COMPRISING ORGANIC / INORGANIC COMPOSITE DEPOSITED BY ELECTROCHEMICAL DEPOSITION AND THEIR PREPARATION METHOD, ELECTROCHEMICAL DEVICE COMPRISING THE ABOVE ELECTRODE}

The present invention significantly improves adhesion and lifespan by significantly inhibiting cracking and / or micronization of electrode active material particles and electrical separation of electrode active materials and current collectors due to large volume change of electrode active materials during charging and discharging of batteries. The present invention relates to an electrode having improved characteristics, a method of manufacturing the same, and an electrochemical device including the electrode.

Silicon, tin, copper, and the like are negative electrode materials for lithium secondary batteries, and can replace carbon materials. The theoretical capacity currently available for graphite materials is 372 mAh / g, while silicon has a very large theoretical capacity of 4000 mAh / g or more. However, the above-described negative electrode material exhibits poor lifespan characteristics. The main reason is a very large volume change of the electrode active material involved in charging and discharging.

In order to minimize the volume change of the electrode active materials involved in charging and discharging, various attempts have been made, and among them, the method of controlling the particle size of these materials has been found to be the most effective. That is, a battery using nanoparticles of several tens of nm or less as a negative electrode shows relatively good performance. As a method of manufacturing such nanoparticles, methods such as a high energy ball milling method and a laser depositione have been proposed. However, these methods have a problem in that the process is complicated and the manufacturing cost is increased, and the surface of the prepared nanoparticles is easily changed to oxide.

On the other hand, electrochemical deposition (electrodeposition) is a method that can easily prepare nanoparticles. Lithium secondary batteries using Sn as a negative electrode manufactured by the current electrochemical deposition method has already been published a number of studies, while the electrochemical deposition of Si is relatively poor. As an example of this research, an attempt has recently been made to synthesize amorphous Si using SiCl ₄ as a precursor and to apply it to semiconductor device fabrication, and Si is deposited on a carbon material using Si (OEt) ₄ as a precursor to form a negative electrode for a lithium ion secondary battery. There was an attempt to use it.

However, when using the Sn or Si prepared as a negative electrode for a lithium ion secondary battery, it did not show a significant improvement compared to the characteristics of the negative electrode manufactured by a method such as conventional high energy ball milling method or laser deposition. In other words, as the charge and discharge progresses, the electrode active material particles are cracked, resulting in micronization of the particles or electrical separation at the deposition surface between the electrode active material and the current collector. There was a problem of deterioration.

The present invention constitutes a cathode through the above-described electrochemical vapor deposition, but is a precursor compound of the electrochemical vapor deposition, and includes an electrochemically polymerizable organic substituent and an ion-bonding substituent at the same time, and may occlude / desorb lithium. The use of a compound containing a (qua) metal solved the above-mentioned problems and found that the improvement of the life characteristics of the negative electrode was achieved by suppressing the volume expansion of the electrode active material and increasing the bonding force between the electrode active material and the current collector. Due to

Accordingly, an object of the present invention is to provide an electrode, a method of manufacturing the same, and an electrochemical device including the electrode, which increases adhesion of the deposition surface between the electrode active material and the current collector and provides improved life characteristics as described above.

The negative electrode active material layer is formed on one or both surfaces of the current collector, the negative electrode active material layer is (a) at least one (semi) metal selected from the group consisting of Si and Sn; And (b) an electrochemically polymerizable substituent, wherein the at least one substituent selected from the group consisting of vinyl group, aryl group, acrylate group, methacrylate group, cyclic lactone and cyclic carbonate is chemically bonded And a polymerizable substituent is fixed in combination with a current collector, and the (quasi) metal is mutually chemically bonded to another neighboring (quasi) metal, and a method of manufacturing the same. It provides an electrochemical device, preferably a lithium secondary battery.

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In the present invention, by providing an electrode that is electrochemically deposited, it is possible to provide long life characteristics of the battery by preventing the deterioration of the electrode due to the volume change of the electrode active material during charging and discharging, increasing the deposition surface with the current collector.

Hereinafter, the present invention will be described in detail.

In the present invention, an electrode, preferably a cathode, is formed of an electrode active material, which can replace a conventional carbon material, such as Si, Sn, or a mixture thereof, by using an electrochemical vapor deposition method, and those largely involved in charging and discharging. In order to suppress the volume change and increase the adhesion between the electrode active material and the current collector, the above-mentioned (quasi) metal-containing compound having a specific substituent is used as a precursor compound.

There are two specific substituents included in the (quasi) metal-containing compound, the first being an ionic bond substituent, and the second being an electrochemically polymerizable substituent. These substituents dissolve in a solvent and then act differently from each other. For example, the ionic bonding substituent portion of the precursor compound is dissociated into an anion after dissolving in a solvent, while the remaining portion of the precursor compound, such as a polymerizable substituent (organic matter) ) And (qua) metal parts capable of occluding and releasing lithium are dissociated into cations in the form of hybrids connected through chemical bonds. When a constant current is applied after immersing an electrically conductive substrate (eg, a current collector) in such a solution, the cations or anions move toward electrodes having different charges due to electrostatic attraction, resulting in positive The hybrid portion deposits an electrode active material layer containing the aforementioned components on the cathode.

The electrode formed by the electrochemical deposition of a complex portion of a cationically polymerizable substituent and a (quasi) metal capable of occluding and releasing lithium can achieve the following effects.

The conventional negative electrode including the above-described materials such as Si, Sn, Cu, Bi, and the binder simply existed in a state in which the negative electrode material and the binder are physically mixed, and thus cannot suppress a large volume change of the negative electrode active material accompanying charging and discharging. In addition, crack generation and micronization of the electrode active material particles due to the volume change could not be basically solved.

In contrast, in the present invention, when depositing a complex portion of the above-mentioned polymerizable substituent and a (semi) metal capable of occluding and releasing lithium on a current collector, it is already chemically bonded to the (semi) metal that can be used as an electrode active material. Organic matter (polymerizable substituents) may form an electrode through physical or chemical bond formation with the current collector. Therefore, the problem of electrode deterioration can be solved by relieving the stress caused by the volume expansion of the (metal) involved in charging and discharging by the organic material connected through the metal bond and the chemical bond, and the electrode active material layer and the current collector. Electrical separation at the deposition surface is also significantly reduced, which can lead to longer battery life.

The electrode active material formed on the current collector according to the present invention includes a hybrid in which one or more (quasi) metals and organics selected from the group consisting of Si and Sn are chemically bonded to each other. The bond then includes all conventional chemical bonds known in the art, such as intramolecular bonds.

The (quasi) metal capable of occluding and releasing lithium in the electrode active material is not limited to the aforementioned components, such as Si, Sn, or a mixed component thereof, and may further include conventional electrode active material components known in the art. It may include.

In addition, the organic material in the electrode active material may include an electrochemically polymerizable substituent, non-limiting examples of such a polymerizable substituent, vinyl group, aryl group, acrylate group, methacrylate group, cyclic lactone, Cyclic carbonates or mixtures of one or more thereof. Other conventional polymerizable substituents known in the art are also applicable.

When the organic material is polymerized in this manner, as described above, not only can the stress due to the volume expansion of the (qua) metal be reduced, but also the electrical separation in the deposition surface of the electrode active material layer and the current collector can be reduced. .

The electrode active material of the present invention composed of the (semi) metal and the organic material described above is not a simple combination or mixed form of the organic material and the inorganic material (eg, (semi) metal), but represents a form in which they are bonded to each other. Therefore, as described above, the volume change of the (quasi) metal generated during charging and discharging of the battery can be suppressed by organic chemically bonded to each other, that is, a polymerizable substituent. In particular, the organic material already chemically bonded to the (quasi) metal may include (a) a current collector in the final electrode; And / or (b) form one or more physical or chemical bonds with other organics. Physical bonds here include conventional intermolecular bonds known in the art, such as hydrogen bonds, van der Waals bonds and the like.

The electrode active material composed of the complex of the above-described organic material and (quasi) metal may further include components common to those in the art, such as additive components, in addition to the above components.

The electrode according to the present invention may be in a form in which the above-described electrode active material layer is laminated on an electrically conductive substrate, for example, a current collector, and in particular, the current collector and the (quasi) metal which is an electrode active material component and a hybrid of an organic material are bonded to each other. It is appropriate to be stacked in a stacked state. Preferably, the current collector and the organic material are interconnected through physical or chemical bonds, and the (quasi) metal is fixed through chemical bonds with the organic material (see FIG. 1), and the organic material is polymerized under appropriate conditions. It can also exist as a polymer form through reaction. At this time, since the fraction of the polymer in the electrode is maintained below a certain level compared to the electrode active material, the movement of lithium ions is hardly caused by the polymer.

The physical or chemical bonds described above are not particularly limited, and for example, the bond between the organic material and the metal component may be a coordination bond and a covalent bond or a hydrogen bond with a polar group present on the metal surface. Bonding between organic materials may be covalent bonding by polymerization.

The current collector on which the electrode active material layer is formed is not particularly limited as long as it is made of a conductive material, and non-limiting examples include copper, nickel, stainless steel, tungsten or tantalum. It may also be in the form of a mesh or foil. Double copper metal foil is preferable, and one or both surfaces thereof may be roughened or surface treated.

The electrode according to the present invention can be prepared according to electrochemical deposition (electrodeposition) known in the art, one embodiment thereof includes (a) an electrochemically polymerizable substituent and an ion-bonding substituent and occludes lithium and Preparing a solution by dissociating a compound containing a material selected from Si and Sn as a (qua) metal which can be released into a solvent; (b) immersing an energizable positive substrate in the solution and spaced apart from each other at predetermined intervals, and then applying a predetermined voltage to electrochemically deposit a complex of a polymerizable substituent and a (quasi) metal; And (c) drying the electrochemically deposited negative electrode or current collector.

In this case, as the method for laminating the electrode active material, electrolytic plating, electroless plating, or electrophoretic deposition may be performed.

First, an electrolyte is prepared by dissolving a (quasi) metal-containing precursor compound containing 1) an electrochemically polymerizable substituent and an ionic bond substituent and capable of occluding and releasing lithium in a solvent.

As the (quasi) metal-containing precursor compound including the electrochemically polymerizable substituent and the ion-bonding substituent, an ion-bonding compound including each of the aforementioned metals (eg, Si, Sn, etc.) or a combination thereof may be used. Can be used. In this case, the polymerizable substituent is the same as described above, and the ionic bond substituent is an anionic substituent known in the art capable of bonding with a (semi) metal, such as a halogen group or a salt containing the (semi) metal component described above. As a substituent which can be ionized, there is no special limitation.

The (quasi) metal-containing compound including the electrochemically polymerizable substituent and the ionic bond substituent may be represented by the following Chemical Formulas 1 to 3, but is not limited thereto.

MR _n (I)

Where

M is at least one (quasi) metal selected from the group consisting of Si and Sn;

n is an integer of 2 or 4, where n is 4 (R _n = R ₁ R ₂ R ₃ R ₄ ) when M is Si, and n is 2 (R _n = R ₁ R ₂ ) when M is Sn Or 4 (R _n = R ₁ R ₂ R ₃ R ₄ );

R _n are each independently a homologous or hetero substituent, and each hydrogen, hydroxy group (-OH), nitrile group (-CN), C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ hydroxyalkyl ( hydroxyalkyl group, C ₂ ~ C ₁₂ alkenyl group, C ₁ ~ C ₁₂ alkoxy group, C ₆ ~ C ₁₈ aryl group, C ₇ ~ C ₁₈ benzyl group ,

At least one of R _n is a substituent ionic bond with M, and at least another one of R _n is an electrochemically polymerizable substituent.

At this time, a non-limiting example of the substituent which is ion-bonded with M is a halogen group, etc. A non-limiting example of the polymerizable substituent is vinyl, aryl, acrylate, methacrylate group, cyclic lactone, cyclic carbonate or Combinations;

Non-limiting examples of the compound represented by the formula (1) is trichloro vinyl silane (trichloro vinyl silane), dichloro divinyl silane (dichloro divinyl silane), chloro trichlorovinyl silane (chloro trichlorovinyl silane), chloro dimethyl vinyl silane (chloro dimethyl vinyl silane), where M = Si; Chloro vinyl tin, trichloro vinyl tin, dichloro divinyl tin, chloro trivinyl tin (where M = Sn), and the like. In particular, when the metalloid compound is Si, it may be a compound including a Si-Si bond as shown in Formula 2 or a Si-O-Si or Si-S-Si bond as shown in Formula 3. In addition, these compounds may have a chain and cyclic structure.

R ₁ R ₂ R ₃ Si- (SiR _{2n +5} R _{2n +6} ) _n -SiR ₄ R ₅ R ₆ (Ⅱ)

R ₁ R ₂ R ₃ Si- (X _{n +1} -SiR _{2n +5} R _{2n +6} ) _n -SiR ₄ R ₅ R ₆ (Ⅲ)

Where

R ₁ to R _{2n + 6} each independently represent a homogeneous or hetero substituent, and a hydrogen, a hydroxy group (-OH), a nitrile group (-CN), a C ₁ to C ₁₂ alkyl group, and C ₁ to C ₁₂ Hydroxyalkyl group, C ₂ ~ C ₁₂ alkenyl group, C ₁ ~ C ₁₂ alkoxy group, C ₆ ~ C ₁₈ aryl group, C ₇ ~ C ₁₈ benzyl ( benzyl) group;

_Wherein at least one of R ₁ to R _{2n + 6} is a substituent ionically bonded to X, and at least another one of R ₁ to R _{2n + 6} is an electrochemically polymerizable substituent;

X is oxygen or sulfur atom,

n is an integer between 0 and 10.

In Chemical Formulas 2 and 3, the substituent that is ion-bonded is a halogen group, and the electrochemically polymerizable substituent may be selected from vinyl, aryl, acrylate, methacrylate groups, cyclic lactones, cyclic lactones, and cyclic carbonates. .

Non-limiting examples of the compound represented by Formula 2 include tetrachloro divinyl disilane, dichloro tetravinyl disilane, dichloro dimethyl divinyl disilane, and the like. have. In addition, non-limiting examples of the compound represented by the formula (3) is tetrachloro divinyl disiloxane, dichloro tetravinyl disiloxane, dichloro dimethyl divinyl disiloxane , 2,4,6,8-tetrachloro-2,4,6,8-tetravinyl cyclosiloxane (2,4,6,8-tetrachloro-2,4,6,8-tetravinylcyclotetrasiloxane).

Additives that enhance strength and conductivity may be additionally used in the electrolyte, and this additive serves to help ensure particle size and uniformity of a desired coating layer. Examples of additives include coumarin, thiourea, saccharin, boric acid, and the like. The additive is preferably used after applying the heat to the electrolyte solution after the above-mentioned (quasi) metal precursor compound is sufficiently dissolved, in order to ensure uniformity of the electrolyte solution.

2) electrochemical deposition using the prepared electrolyte solution. For example, a current collector (conductable substrate) to be deposited is used as a cathode, and an insoluble substrate is used as an anode, and these electrodes are separated from each other to face each other, and then immersed in the prepared plating solution, and current or voltage It is applied to precipitate a composite layer of (quasi) metal bonded to the above-mentioned polymerizable substituent on the electrode or the current collector.

The present invention can vary the plating time, current density and other variables depending on the thickness of the coating layer desired.

The cathode or the current collector is preferably subjected to a conventional pretreatment step before the electrochemical deposition step in order to remove the surface contamination and the oxide film and to facilitate the deposition of the surface.

When such a process is performed, an electrode active material layer composed of a polymerizable substituent and a (quasi) metal complex is formed on the surface of the current collector, which is a cathode.

After the above step through the usual drying process in the art, the production of an electrode including a composite of the organic material of the present invention and (quasi) metal as an electrode active material can be completed. At this time, the step of heat treatment after the drying step may be added.

The electrode manufactured as described above is preferably a negative electrode, but is not limited thereto.

The present invention provides an electrochemical device comprising an anode, a cathode, a separator, and an electrolyte, wherein the anode, the cathode, or the positive electrode includes an electrode active material as described above or an electrode manufactured by the above method. to provide.

The electrochemical device of the present invention includes all devices that undergo an electrochemical reaction, and specific examples thereof include all kinds of primary, secondary cells, fuel cells, solar cells, or capacitors. In particular, a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery or a lithium ion polymer secondary battery among the secondary batteries is preferable.

The electrochemical device may be manufactured according to a conventional method known in the art, for example, may be manufactured by injecting an electrolyte after assembling a separator between the positive electrode and the negative electrode.

In this case, the electrode, which is used in combination with the electrode on which the electrode active material layer is formed by electrochemical deposition, preferably the anode is prepared in the form of the electrode active material bound to the electrode current collector according to conventional methods known in the art. For example, an electrode slurry including a positive electrode active material or a negative electrode active material may be prepared by coating and drying a current collector on a current collector. In this case, a small amount of a conductive agent and / or a binder may be optionally added.

Non-limiting examples of the positive electrode active material may be used a conventional positive electrode active material that can be used for the positive electrode of the conventional electrochemical device, in particular by lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium iron oxide or a combination thereof Lithium intercalation materials such as a composite oxide to be formed are preferred. Non-limiting examples of the negative electrode active material may be a conventional negative electrode active material that can be used in the negative electrode of the conventional electrochemical device, in particular lithium metal or lithium alloy, carbon, petroleum coke, activated carbon, Lithium adsorbents such as graphite, metal oxides or other carbons are preferred.

Using the electrolyte salts is A ⁺ B ^- A salt of the structure, such as, A ⁺ is Li ^+, Na ^+, K ⁺ comprises an alkaline metal cation or an ion composed of a combination thereof, such as, and B ^- is PF ₆ ^-, BF _{^{4 -, Cl -, Br -}} , I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C (CF 2 SO 2) 3 ^- is a salt containing an anion ion or a combination thereof, such as. In particular, lithium salt is preferable.

As the electrolyte solution, an organic solvent for a battery commonly used in the art, such as cyclic carbonate and / or linear carbonate, may be used. Non-limiting examples of the cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), gamma butyrolactone (GBL), and the like. Non-limiting examples of linear carbonates include diethyl carbonate (DEC) and dimethyl carbonate ( DMC), ethylmethyl carbonate (EMC), methyl propyl carbonate (MPC), or mixtures thereof.

The separator may use a porous separator that serves to block internal short circuit of the positive electrode and impregnate the electrolyte, and non-limiting examples thereof include a polypropylene-based, polyethylene-based, and polyolefin-based porous separator.

The external shape of the electrochemical device, preferably the lithium secondary battery, manufactured by the method presented in the present invention is not particularly limited, but may be a cylindrical, coin-shaped, square or pouch type of can.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1

1-1. Electrode manufacturing

Pt plate electrodes (1 cm ² ) were used as working electrodes, and Pt line electrodes were used as counter electrodes. 0.1 M trichlorovinyl silane (TCVS) was added to a propylene carbonate (PC) solution containing 0.5 M LiClO ₄ , and a Si-organic complex was electrochemically deposited on a Pt plate electrode by flowing a reduction current of 2 mA for 30 minutes. . The deposition was carried out in a glove box in an argon (Ar) atmosphere having a moisture and oxygen concentration of 10 ppm or less.

1-2. Secondary battery manufacturing

A battery was manufactured using the electrode prepared in Example 1-1 as a cathode and a Li metal as a cathode. In this case, EC / EMC (1/2) in which 1 M LiPF ₆ was dissolved was used, and a porous polyolefin-based separator was used.

Example 2

Except for adding 0.05 M TCVS and 0.05 M tetrachlorosilane (SiCl ₄ ) instead of 0.1 M TCVS, the same method as in Example 1 was carried out to form an electrode on which a Si-organic composite was deposited and a secondary battery having the electrode. Prepared.

Example 3

The electrode and the electrode on which the Si-organic composite was deposited in the same manner as in Example 1, except that 0.05 M TCVS and 0.05 M hexachlorodisiloxane (Cl ₃ Si-O-SiCl ₃ ) were added instead of 0.1 M TCVS. A secondary battery having a was prepared.

Example 4

Except that the flow of 0.5 mA reduction current for 120 minutes, the same method as in Example 1 was carried out to prepare an electrode on which the Si-organic composite was deposited and a secondary battery having the electrode.

Comparative Example 1

Except for using 0.1 M SiCl ₄ instead of 0.1 M TCVS, the same method as in Example 1 was carried out to prepare an electrode on which the Si-organic composite was deposited and a secondary battery having the electrode.

Comparative Example 2

A Si thin film was deposited on a platinum foil using RF magnetron sputtering, and a secondary battery was manufactured using an electrode on which the Si thin film was deposited.

Experimental Example 1. Evaluation of Battery Performance

The cells of Examples 1 to 3 including the electrodes on which the Si-organic complexes were formed were used, and the batteries of Comparative Examples 1 and 2 including the electrodes composed of silicon components were used as a control thereof.

In order to evaluate the life characteristics of the batteries, each battery was charged and discharged with a 1 mA current, the results are shown in Table 1.

As shown in Table 1 below, the batteries of Examples 1 to 3 having Si-organic composite electrodes showed significantly improved life characteristics compared to those of Comparative Examples 1 and 2 using Si single electrodes. This was confirmed that the organic material connected with the metal, which is a metalloid, through a Si-bond, alleviates the stress caused by the volume expansion of Si accompanying charge and discharge, thereby minimizing the degradation of the electrode and the deterioration of the battery life.

Discharge capacity once (Ah / g) 30 times discharge capacity (Ah / g) Example 1 2.66 2.44 Example 2 2.81 2.65 Example 3 2.75 2.32 Comparative Example 1 2.96 1.32 Comparative Example 2 2.89 0.78

1 is a schematic diagram of an electrode produced by the electrochemical vapor deposition according to the present invention.

Claims (15)

In the negative electrode, the negative electrode active material layer is formed on one side or both sides of the current collector, The anode active material layer (a) at least one (quasi) metal selected from the group consisting of Si and Sn; And (b) an electrochemically polymerizable substituent, wherein at least one substituent selected from the group consisting of vinyl groups, aryl groups, acrylate groups, methacrylate groups, cyclic lactones and cyclic carbonates is chemically bonded Including; The polymerizable substituent is fixed in combination with the current collector, The (quasi) metal is a negative electrode, characterized in that the mutual chemical bonding with the adjacent (qua) metal. delete delete delete The method of claim 1, wherein the negative electrode active material layer is formed by electrochemical deposition (electrodeposition) using a (quasi) metal-containing compound containing an electrochemically polymerizable substituent and an ionic bond substituent as a precursor compound (precursor) Cathode characterized by. The negative electrode according to claim 5, wherein the (quasi) metal-containing compound including the electrochemically polymerizable substituent and the ionic bond substituent is represented by the following Chemical Formula 1. [Formula 1] MR _n (I) Where M is at least one (quasi) metal selected from the group consisting of Si and Sn; n is an integer of 2 or 4, where n is 4 when M is Si and n is 2 or 4 when M is Sn; R _n are each independently a homologous or hetero substituent, and each hydrogen, hydroxy group (-OH), nitrile group (-CN), C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ hydroxyalkyl ( hydroxyalkyl group, C ₂ ~ C ₁₂ alkenyl group, C ₁ ~ C ₁₂ alkoxy group, C ₆ ~ C ₁₈ aryl group, C ₇ ~ C ₁₈ benzyl group In this case, at least one of R _n is a halogen group as a substituent ionic bond with M, at least another one of R _n is an electrochemically polymerizable substituent, vinyl, aryl, acrylate, methacrylate group, cyclic lactone And a substituent selected from the group consisting of cyclic carbonates. The negative electrode of claim 5, wherein the (quasi) metal-containing compound including the electrochemically polymerizable substituent and the ionic bond substituent is represented by the following Chemical Formula 2 or Chemical Formula: [Formula 2] R ₁ R ₂ R ₃ Si- (SiR _{2n + 5} R _{2n + 6} ) _n -SiR ₄ R ₅ R ₆ (II) [Formula 3] R ₁ R ₂ R ₃ Si- (X _{n + 1} -SiR _{2n + 5} R _{2n + 6} ) _n -SiR ₄ R ₅ R ₆ (III) Where R ₁ to R _{2n + 6} each independently represent a homogeneous or hetero substituent, and a hydrogen, a hydroxy group (-OH), a nitrile group (-CN), a C ₁ to C ₁₂ alkyl group, and C ₁ to C ₁₂ Hydroxyalkyl group, C ₂ ~ C ₁₂ alkenyl group, C ₁ ~ C ₁₂ alkoxy group, C ₆ ~ C ₁₈ aryl group, C ₇ ~ C ₁₈ benzyl ( benzyl) group; In this case, at least one of R ₁ to R _{2n + 6} is a halogen group as an ion-bonding substituent, and at least another one of R ₁ to R _{2n + 6} is an electrochemically polymerizable substituent, and includes vinyl, aryl, acrylate, and meta. A substituent selected from the group consisting of an acrylate group, a cyclic lactone and a cyclic carbonate; X is oxygen or sulfur atom, n is an integer between 0 and 10. delete delete delete An electrochemical device comprising an anode, a cathode, a separator, and an electrolyte, wherein the cathode is the cathode according to any one of claims 1 and 5 to 7. The electrochemical device of claim 11, wherein the electrochemical device is a lithium secondary battery. (a) A solution is prepared by dissociating a compound containing an electrochemically polymerizable substituent and an ionic bond substituent and containing a substance selected from Si and Sn as a (qua) metal capable of occluding and releasing lithium in a solvent. Making; (b) immersing an energizable positive substrate in the solution and spaced apart from each other at predetermined intervals, and then applying a predetermined voltage to electrochemically deposit a complex of a polymerizable substituent and a (quasi) metal; And (c) drying the electrochemically deposited negative electrode or current collector Including the manufacturing method of the negative electrode according to claim 1. delete The method of claim 13, wherein the solution of step (b) is added with at least one additive selected from the group consisting of coumarin, thiourea, saccharin and boric acid.

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