KR20060118962A - Electrode including si material layer and lithium battery employing the same - Google Patents

Abstract

Provided is an electrode including a silicon-containing material layer, which prevents oxidation of an electrode collector to lower resistance and increases adhesive force between the electrode collector and an electrode active material to improve ohmic contact and a lifetime. The electrode comprises an electrode collector, a silicon-containing material layer, and an electrode active material layer. The silicon-containing material layer includes a material represented by the following formula (I). In the formula, each of R1, R2, R3 is independently a hydrogen atom, a halogen atom, a hydroxyl group, an amine group, -SH, a C1-20 alkyl group, a C3-20 cycloalkyl group, a C2-20 alkenyl group, a C1-20 alkoxy group, a C6-30 aryl group, a C6-30 aryloxy group, or a C1-20 alkylcarbonyl group, X is -NH-, -O-, -SO3-, a C1-20 alkylene group, a C2-20 alkenylene group, a silanylene group, a C6-30 arylene group, a peptyl group, a carbonylene group, or a C1-20 oxyalkylene group, and A represents a hydrogen atom, a halogen atom, -SH, an amino group, a C2-15 heterocycloalkyl group, a C2-20 alkenyl group, a C1-10 silanyl group, or a C6-20 aryl group.

Description

Electrode including Si-containing material layer and lithium battery employing the same {Electrode including Si material layer and lithium battery employing the same}

1 is a perspective view of an electrode assembly having an electrode according to an embodiment of the present invention.

2A to 2C are cross-sectional views of electrodes according to an embodiment of the present invention.

3 is a partially enlarged cross-sectional view of a conventional electrode.

4 is an explanatory view of the reaction between the Si-containing material layer and the electrode current collector in the electrode surface according to an embodiment of the present invention.

5 is a plan view showing a test specimen for the adhesion of the electrode according to the present invention.

6 is an explanatory view showing a test method for the adhesion of the electrode according to the present invention.

<Short description of drawing symbols>

100 electrode assembly 110, 120, 200, 300, 400, 500: electrode

115, 125: Electrode tab 130, 140: Separator

200, 300, 400, 500: electrode

210, 310, 410, 510: electrode collector 220, 320, 420: Si-containing material layer

230, 330, 430, 530: electrode active material layer

The present invention relates to an electrode including a Si-containing material layer and a lithium battery employing the same, and more particularly, by applying a Si-containing material to the electrode current collector to increase the adhesion between the electrode current collector and the electrode active material layer of the electrode active material By preventing desorption and preventing oxidation of the electrode current collector, ionization of the electrode current collector is prevented, thereby maintaining adhesion between the electrode current collector and the electrode active material layer, and improving ohmic contact, and by using a Schottky barrier ( The present invention relates to an electrode capable of reducing shottkey-barrier) and a lithium battery employing the same.

Recently, compact and lightweight electric / electronic devices such as mobile phones and notebook computers have been actively developed and produced. The portable electric / electronic device includes a battery pack that can be operated without a separate power source. The battery pack includes at least one battery, and recently, a rechargeable battery that can be charged and discharged is considered in consideration of economic aspects. I adopt it. Representative secondary batteries include lithium secondary batteries such as nickel-cadmium (Ni-Cd) batteries, nickel-hydrogen (Ni-H) batteries, lithium (Li) batteries, and lithium ion (Li ion) batteries.

In particular, the lithium secondary battery is a battery that can be recharged using lithium occlusion and release reactions, and is easy to miniaturize and large in capacity. The operating voltage is three times higher than that of a nickel-cadmium battery or a nickel-hydrogen battery, and the energy per unit weight is increased. In terms of high density, many were initially studied. However, when lithium metal is used as the negative electrode, a large amount of dendritic lithium precipitates on the surface of the lithium during charging, which may lower the charge and discharge efficiency, cause short circuits with the positive electrode, and also cause instability of lithium itself, that is, high reactivity.

In order to solve this problem, researches on using carbon materials for the negative electrode have been made. A cathode of this kind is disclosed, for example, in Japanese Patent Laid-Open No. 5-299073, Japanese Patent Laid-Open No. 2-121258, and Japanese Patent Laid-Open No. 7-335623. However, this study has a problem that the expansion and contraction due to charge and discharge is less than the case of the lithium or lithium alloy, but the capacity is lowered and the initial charge and discharge efficiency is lower than when using lithium or the like.

Accordingly, researches to improve the capacity of batteries by introducing metals such as lithium to the negative electrode have been actively attempted. However, when using alloys or metals alone, carbon-based compounds are considered in consideration of problems due to precipitation of dendritic lithium and rapid volume changes. Research has been conducted in a direction to avoid problems such as short circuits while increasing the capacitance by properly mixing with the material. In such a composite material, Japanese Patent Laid-Open Publication No. 199-286763 discloses a negative electrode material obtained by mixing a carbon-based material and a metal material of a similar size, then coating the mixture with an organic compound and firing the same. In 6-349482, by adding a metal as a conductive agent to carbon used in a negative electrode or a positive electrode active material, the contact resistance between the active materials is reduced, or the contact resistance between the current collector and the active material is lowered, and a rapid capacity reduction is achieved even at high rate discharge. A method that can be suppressed is disclosed.

However, in the structure in which the electrode active material is in direct contact with the electrode current collector, a difference occurs in concentration of electron density due to a difference between an electrode active material and a portion in contact with the electrode current collector and a portion not in contact with the electrode current collector. In this case, ionization of the electrode current collector proceeds, thereby increasing battery resistance due to metal oxidation and making ionization easy even at low voltage. In addition, there is a problem in that a portion of the electric power line is not concentrated, the ions of the electrode current collector is precipitated as a metal to cause a dendrite phenomenon.

Accordingly, there is a need to improve resistance due to ionization of the electrode current collector, decrease in ohmic contact, decrease in lifespan capacity, and the like, and increase adhesion.

Therefore, the present invention is designed to solve the problems of the prior art, the first technical problem to be achieved by the present invention is to prevent the oxidation of the electrode current collector to lower the resistance of the electrode, while the adhesion between the electrode current collector and the electrode active material It is to provide an electrode that can increase the ohmic contact to increase the Schottky-barrier.

A second object of the present invention is to provide an electrode that can improve the liquid-liquidity by removing the OH group on the electrode to smooth the contact angle between the electrode active material and the electrolyte to increase the moisture content of the electrolyte.

A third object of the present invention is to provide a lithium battery employing the above improved electrode.

In order to achieve the above object of the present invention, the present invention

Electrode current collectors;

An electrode active material layer; And

Provided is an electrode comprising a Si containing material layer comprising a compound of formula (I):

(I)

(I)

Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted amine group, -SH, a substituted or unsubstituted C1-20 alkyl group, substituted or unsubstituted A cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or Unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylcarbonyl group having 1 to 20 carbon atoms,

X is -NR- (where R is a possible substituent such as hydrogen, alkyl group), -O-, -SO _3- , substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, substituted or unsubstituted carbon atoms 2 to 20 Alkenylene group, substituted or unsubstituted silanylene group, substituted or unsubstituted arylene group having 6 to 30 carbon atoms, substituted or unsubstituted peptyl group, substituted or unsubstituted carbonylene group, substituted or unsubstituted carbon number 1-20 oxy alkylene group, heteroalkylene group,

A is a hydrogen atom, a halogen atom, -SH, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocycloalkyl group having 2 to 15 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted carbon atom The silanyl group of 1-10, a substituted or unsubstituted C6-C20 aryl group is shown.

According to one embodiment of the present invention, the compound of formula II is preferable as the compound of formula I.

(II)

(II)

Wherein R ₁ , R ₂ , R ₃ and X are as defined above.

According to another embodiment of the present invention, the compound of formula III is preferable as the compound of formula I.

(III)

(III)

Wherein R ₁ , R ₂ , R ₃ are as defined above, R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted amine group, a substituted or unsubstituted Thiol group, substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C1-C20 alkenyl group, substituted or unsubstituted C1-C20 An alkoxy group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylcarbonyl group having 1 to 20 carbon atoms,

X ₁ is —O—, —NH—, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms to be.

According to another embodiment of the present invention, the compound of formula IV is preferable as the compound of formula I.

(IV)

(IV)

Wherein R ₁ to R ₆ are as defined above.

According to another embodiment of the present invention, the compound of formula (V) is preferred as the compound of formula (I).

(V)

(V)

Wherein R ₁ to R ₆ are as defined above, and R ₇ and R ₈ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted amine group, a substituted or unsubstituted thiol group, a substituted or unsubstituted A substituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkenyl group, a substituted or unsubstituted C1-C20 alkoxy group, substituted or An unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and a substituted or unsubstituted alkyl carbonyl group having 1 to 20 carbon atoms.

According to another embodiment of the present invention, the compound of formula VI is preferable as the compound of formula I.

(VI)

(VI)

Wherein R ₁ , R ₂ and R ₃ are as defined above, R ₉ and R ₁₀ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted amine group, a substituted or unsubstituted thiol group, Substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C3-C20 cycloalkyl group, substituted or unsubstituted C1-C20 alkenyl group, substituted or unsubstituted C1-C20 alkoxy group , A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl carbonyl group having 1 to 20 carbon atoms,

X ₂ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

The present invention to solve the above technical problem

An electrode current collector, laminated on at least one surface of the electrode current collector in order of an Si-containing material layer and an electrode active material layer;

An electrode current collector, laminated on at least one surface of the electrode current collector in order of an electrode active material layer and a Si-containing material layer; or

An electrode current collector and an electrode stacked on at least one surface of the electrode current collector in order of a Si-containing material layer, an electrode active material layer, and a Si-containing material layer are provided.

The present invention to solve the above technical problem

In a lithium battery comprising a negative electrode, a positive electrode and an electrolyte, a lithium battery including at least one or more of the above-described electrodes is provided.

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

An electrode including the Si-containing material layer according to the present invention is characterized in that it comprises a Si-containing material layer on at least one side of the electrode current collector.

In one embodiment according to the invention is characterized in that it comprises a Si-containing material layer on the electrode active material.

In one embodiment according to the invention is characterized in that it comprises a Si-containing material layer on at least one side of the electrode current collector and the electrode active material.

In this case, when the Si-containing material layer is applied to the surface of the electrode current collector, the Si of the Si-containing material layer reacts with the OH groups on the surface of the electrode current collector to prevent oxidation of the electrode current collector to ensure lifetime, while improving ohmic contact. It serves to increase the adhesion between the electrode active material and the electrode current collector. In addition, when the Si-containing material is applied on the electrode active material layer, the Si of the Si-containing material layer reacts with OH on the negative electrode to remove OH groups, thereby reducing the contact angle between the electrolyte and the negative electrode active material, thereby increasing the moisture content of the electrolyte, thereby improving the liquid-liquidity. .

The alkyl group, which is a substituent used in the compound of the present invention, includes straight or branched monovalent alkyl groups having 1 to 20 carbon atoms, and preferably includes straight or branched monovalent alkyl groups having 1 to 15 carbon atoms. The term is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, n-nonyl, n-dodecyl, tridecyl, pentadecyl, n- Illustrated by functional groups such as pentyl and their straight or chained analogs. More preferred alkyl groups are lower alkyl groups having 1 to 6 carbon atoms, and even more preferred alkyl groups are lower alkyl groups having 1 to 3 carbon atoms.

Alkenyl group represents a C2-C30 linear or branched aliphatic hydrocarbon group containing a carbon-carbon double bond here. Preferred alkenyl groups have 2 to 15 carbon atoms in the chain, more preferably 2 to 6 carbon atoms in the chain. Branched refers to one or more lower alkyl or lower alkenyl groups attached to the alkenyl chain. Such alkenyl groups may be unsubstituted or may be independently substituted by one or more substituents including halogen atoms, carboxy, hydroxy, formyl and the like. Examples thereof include ethenyl, n-2-propenyl, carboxyethenyl, carboxypropenyl and the like.

Wherein the alkoxy group represents an —OR group, wherein R is “C ₁ -C ₁₂ -alkyl”, or “aryl”, or “heteroaryl”, or “C ₁ -C ₁₂ -alkyl aryl” or “C ₁ -C ₁₂ -Alkyl heteroaryl ". Preferred alkoxy groups are lower alkoxy groups having 1 to 6 carbon atoms, more preferably lower alkoxy groups having 1 to 3 carbon atoms. For example methoxy, ethoxy, propoxy, butoxy and t-butoxy. The alkoxy group may be further substituted with one or more halo atoms such as fluoro, chloro or bromo to provide a haloalkoxy group. More preferred are lower haloalkoxy groups having from 1 to 3 carbon atoms. Examples include fluoromethoxy, chloromethoxy, trifluoromethoxy, trifluoroethoxy, fluoroethoxy and the like.

The aryl group here represents an unsaturated, aromatic carbocyclic group having 6 to 30 carbon atoms having a single ring (for example phenyl) or multiple condensed ring (for example naphthyl). The aryl group may have 1 to 3 substituents such as hydroxy, halo, haloalkyl, nitro, cyano, alkoxy and lower alkylamino. Aryl groups include aromatic radicals such as phenyl, naphthyl, tetrahydronaphthyl, indane and biphenyl, preferred aryls are aromatic radicals having 6 to 9 carbon atoms, examples include phenyl and the like.

Herein, the aryloxy group means aryl-O-, and the definition of aryl in the aryloxy group is as described above.

Wherein the alkylcarbonyl group represents a -COOR group, where R is "C ₁ -C ₁₂ -alkyl", or "aryl", or "heteroaryl", or "C ₁ -C ₁₂ -alkyl aryl" or "C ₁ -C ₁₂ -alkyl heteroaryl ". Preferred carbonyl groups are lower alkylcarbonyls having 1 to 3 carbon atoms, examples include methylcarbonyl, t-butylcarbonyl and the like.

Wherein the alkylene group is represented by the formula -C _n H _2n-, where n is an integer from 0 to 20. The alkylene group may be linear or branched, and preferably includes a straight or branched monovalent alkylene group having 1 to 15 carbon atoms. The term is methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-hexylene, n-octylene, n-nonylene, n-dodecylene, tride Illustrated by functional groups such as styrene, pentadecylene, n-pentylene and their straight or chained analogs. More preferred alkylene groups are lower alkylene groups having 1 to 6 carbon atoms, and even more preferred alkylene groups are lower alkylene groups having 1 to 3 carbon atoms.

Wherein the alkenylene group is represented by the formula -C _n H _2n-2- (n is an integer from 2 to 20).

Wherein the arylene group is a substituent including an aromatic ring and may include an arylalkyl or arylalkenyl group. Benzene ring, naphthalene ring, anthracene ring and the like can be used as the aromatic ring.

Wherein the silanylene group is a substituent containing 1 to 6 atoms, preferably 1 to 4 atoms, particularly preferably 1 to 3 atoms, and containing at least one silicon atom in the formula -SiR _2- ; Atoms can contain 0-2 oxygen atoms, 0-2 nitrogen atoms, and 0-4 carbon atoms. Silicon and carbon atoms may be unsubstituted or substituted with the same or different halogen, alkyl silanyl or silaalkyl groups. Examples include dialkylsilazaneylene [-R ₂ SiNH-], peptidylsilanylene [-CO-NH-SiR _2- ], trihaloalkyloxysilanylene [-CX ₃ RO-SiR _2- ], tetraalkyl Disilanilene [-SiR ₂ -SiR _2- ], dialkylsiloxy (dialkyl) silanylene [-R ₂ SiO ₂ -SiR _2- ]. Here, the heteroalkylene group means a straight or branched alkylene having 1 to 3 carbon atoms containing 1 to 3 hetero atoms selected from N, O, or S, and the remaining atoms are C, preferably 1 to 15 carbon atoms. Lower heteroalkylene, more preferably 1-6 lower heteroalkylene. Examples include ethylaminopropylene, aminopropylene and the like.

Here, it means a monocyclic or bicyclic alkyl having 3 to 10 ring atoms containing 1 to 3 heteroatoms selected from a heterocyclo alkyl group N, O, or S, and the remaining ring atoms are C. Lower heterocycloalkyl having 1 to 6 carbon atoms is preferred. Examples include oxy cyclopropyl, oxy cyclobutyl and the like.

According to an embodiment of the present invention, the Si-containing material includes the compound of Table 1 below.

A X R ₁ R ₂ R ₃ Cl -(CH ₂ ) _3- -OCH ₃ -OCH ₃ -OCH ₃ H ₂ N- -(CH ₂ ) _3- -OC ₂ H ₅ -OC ₂ H ₅ -OC ₂ H ₅ HS- -(CH ₂ ) _3- -OCH ₃ -OCH ₃ -OCH ₃ H- -CH _2- -OCH ₃ -OCH ₃ -OCH ₃ H- -CH _2- -OCH ₃ -OCH ₃ -CH ₃ H- -CH _2- -OC2H5 -OC ₂ H ₅ -OC ₂ H ₅ H- -CH _2- -OCH ₃ -CH ₃ -CH ₃ (CH ₃ ) _2- -(CH ₂ ) _2- -OCH ₃ -OCH ₃ -OCH ₃ H-

-OCH ₃ -OCH ₃ -OCH ₃ H- -CH _2- -Cl -Cl -Cl H- -CH _2- -Cl -Cl -CH ₃ H- -CH _2- -Cl CH ₃ -CH ₃ H- -CH ₂ CH _2- -Cl -CH2CH3 -CH ₂ CH ₃ H- -CH _2- -Cl t-butyl- CH ₃ H- -CH = CH- -OCH ₃ -OCH3 -OCH ₃ H- -CH = CH- -OCOCH ₃ -OCOCH ₃ -OCOCH ₃ H2N- -CH ₂ NH (CH ₂ ) _3- -OCH ₃ -OCH ₃ -OCH ₃ H2N- -(CH ₂ ) ₂ NH (CH ₂ ) _3- -CH ₃ -OCH ₃ -OCH ₃

NH (CH ₂ ) _3- -OCH ₃ -OCH ₃ -OCH ₃

-CH ₂ O (CH ₂ ) _3- -OCH ₃ -OCH ₃ -OCH ₃

-CH ₂ O (CH ₂ ) _3- -CH ₃ -OCH ₃ -OCH ₃ CH ₂ = CCH _3- -COO- (CH ₂ ) _3- -OCH ₃ -OCH ₃ -OCH ₃ CH ₂ = CCH _3- -COO- (CH ₂ ) _3- -CH ₃ -OCH ₃ -OCH ₃ CF _3- -OSO _2- -CH ₃ -CH ₃ -CH ₃ (CH ₃ ) ₃ Si- -NH- -CH ₃ -CH ₃ -CH ₃ H ₂ N- -CONH (CH ₂ ) _3- -OC ₂ H ₅ -OC ₂ H ₅ -OC ₂ H ₅ (CH ₃ ) ₃ SiNH- -CONH- -CH ₃ -CH ₃ -CH ₃ (CH ₃ ) ₃ SiNH- CCF ₃ O- -CH ₃ -CH ₃ -CH ₃ Cl (i-Pr) ₂ Si- -O- -i-Pr -i-Pr -Cl

According to one embodiment of the present invention, the Si-containing material is preferably hexamethyl disilazane (HMDS).

According to an embodiment of the present invention, the thickness of the Si-containing material coating layer is 0.005 μm to 1 μm, preferably 0.01 μm to 0.05 μm.

In the present invention, the electrode current collector may be made of a metal used in a typical lithium battery, for example, aluminum metal or copper metal.

In the present invention, the electrode active material is an electrode active material used in a conventional lithium battery, for example, lithium oxide such as LiCoO ₂ , LiMn ₂ O ₄ , LiNiO ₂ , LiMnO ₂ is used as the cathode active material, and as the cathode active material Natural graphite, artificial graphite or mixtures thereof, or Si, Sn, tin oxide, composite tin alloys, transition metal oxides, lithium metal nitrides or lithium metal oxides and the like are used.

Hereinafter, an electrode according to an exemplary embodiment of the present invention will be described with reference to the accompanying drawings.

1 shows a perspective view of an electrode assembly having an electrode according to the invention. 2A to 2C show cross-sectional views of an electrode according to an embodiment of the present invention. 3 is a partially enlarged cross-sectional view of a conventional electrode. 4 is an explanatory view of the reaction on the electrode surface according to the present invention.

The electrode assembly 100 to which the electrode according to the present invention is applied includes a positive electrode 110 having a positive electrode active material layer formed in a predetermined region of the positive electrode current collector, a negative electrode 120 having a negative electrode active material layer formed in a predetermined region of the negative electrode current collector, Separators 130 and 140 which are positioned between the anode electrode 110 and the cathode electrode 120 to prevent the short circuit of the anode electrode 110 and the cathode electrode 120 and allow only lithium ions to move are jelly. It is wound and formed in roll shape.

At this time, a Si-containing material layer is applied to at least one surface of the electrode current collector of the positive electrode 110 and the negative electrode 120 to increase the adhesion between the positive electrode active material layer or the negative electrode active material layer and the electrode current collector, It prevents oxidation of the whole and prevents detachment of electrode active material. In addition, after coating and rolling the electrode active material, the Si-containing material layer is coated on the electrode active material layer to remove OH groups on the electrode, thereby reducing the contact angle between the electrolyte and the electrode active material, thereby increasing the moisture content of the electrolyte and improving the liquid-liquidity of the battery. It becomes possible.

At this time, the coating of the Si-containing material layer on the cathode electrode is effective in terms of cost.

The positive electrode current collector of the positive electrode plate 110 is made of aluminum (Al), the negative electrode current collector of the negative electrode plate 120 is made of copper (Cu) material, the separator 130 is generally polyethylene (PE) or polypropylene ( PP), but the above material is not limited in the present invention. In addition, the positive electrode tab 110 is generally made of aluminum (Al) and is bonded to the positive electrode tab 115 having a predetermined length protruded upward. The cathode electrode 120 is generally made of nickel (Ni) and is bonded to the negative electrode tab 125 with a predetermined length protruding downward, but is not limited to the above material in the present invention.

2A to 2C are cross-sectional views of electrodes according to an embodiment of the present invention.

Referring to FIG. 2A, an electrode 200 according to an exemplary embodiment of the present invention includes an electrode current collector 210, a Si-containing material layer 220, and an electrode active material layer 230.

The electrode current collector 210 is formed of a thin metal film, and a Si-containing material layer is coated on at least one surface thereof. Referring to FIG. 3, according to the related art, when the Si-containing material layer is applied to the electrode current collector 510, adhesion between the electrode current collector 510 and the electrode active material layer 530 is not good, so that the electrode active material layer and A portion 540 which is not in contact with the electrode current collector (gluing point: 520) is formed between the electrode current collectors, so that the electric line of force that is in contact with the electrode active material layer may flow in a straight line as shown in B. Likewise, the electric field lines are split and flow to the bonding point. Therefore, at the point of adhesion, electron density is concentrated and ionization of the electrode current collector proceeds. If ionization of the electrode current collector is continued, as the contact portion is destroyed by the elution reaction of the metal, the adhesion between the electrode active material layer and the electrode current collector decreases and the ohmic contact also deteriorates, which causes a decrease in the lifespan capacity. In addition, metal ions are precipitated (dendrite) in a portion where electric force lines do not flow. The reaction proceeds at that point because the battery has 3.5V at the beginning of battery production from the configuration of the active material. That is, metal dendrite may occur over time at the initial aging time after battery assembly, which may cause OCV defects. In addition, since metal ions are movable, there is a possibility that dendrites are formed on the anode. However, according to the present invention, referring to FIG. 4, when the Si-containing material layer is applied to the electrode current collector, the Si-containing material layer (HMDS: hexamethyl disilazane) is applied onto the electrode current collector 210, whereby oxygen in air or moisture is applied. The metal current collector is formed by forming a thioether (-Si-O-) bond while simultaneously removing the OH group on the electrode current collector by dehydrogenation between the OH group and the Si-containing material, which remain in the metal thin film by reacting with the electrode current collector. By increasing the adhesion of the electrode active material and evenly across the entire adhesion can be prevented to concentrate the current. For this reason, oxidation of a metal current collector can be prevented, an increase of battery resistance can be prevented, and ionization by a voltage rise can be prevented. On the other hand, by improving ohmic contact, the Schottky-barrier is lowered. Therefore, the resistance of the negative electrode is reduced by about 40%, the battery has a resistance reduction effect of about 20% compared to the Si-containing material layer untreated battery. In addition, the adhesion between the electrode current collector and the electrode active material layer was improved, so that there was no peeling and the strength was improved. Therefore, when the electrode according to the present invention is used, it is possible to manufacture a battery having improved resistance and lifespan.

2B is a cross-sectional view of an electrode according to another embodiment of the present invention.

The electrode 300 of the lithium battery according to the present invention includes an electrode current collector 310, an electrode active material layer 320, and a Si-containing material layer 330.

The electrode current collector 310 and the electrode active material layer 320 are formed in the same manner as described above, and the Si-containing material layer 330 is formed on the electrode active material layer. Referring to FIG. 4, by coating a Si-containing material layer (HMDS) on the electrode active material layer 320, oxygen of air or moisture reacts with the electrode current collector and Si of the Si-containing material is dehydrogenated. By reacting to remove the OH groups on the electrode current collector, the contact angle between the electrode active material layer and the electrolyte is reduced to increase the moisture content of the electrolyte, thereby improving the liquid-liquidity.

The thickness of the Si-containing material and the Si-containing material layer is as described above.

2C is a cross-sectional view of an electrode according to another embodiment of the present invention. The electrode 400 according to the present invention includes an electrode current collector 410, an electrode active material 430, and a Si-containing material layer 420. The electrode current collector 410 and the electrode active material layer 430 are formed in the same manner as described above, the Si-containing material layer 420 on the surface of the electrode current collector 410 and the surface of the electrode active material layer 430, respectively Each is applied. As a result, as described above, the adhesion between the electrode current collector 410 and the electrode active material layer 430 is increased, thereby preventing oxidation of the electrode current collector, preventing desorption of the electrode active material, thereby improving lifetime characteristics, and increasing the electrode active material. As the contact angle between the layer and the electrolyte is reduced, the liquidity is improved. Thus seen The lithium battery having an electrode according to the invention has excellent life characteristics, low battery resistance, high capacity, and excellent safety, such as short resistance and heat resistance.

In addition, the lithium battery employing the electrode according to the present invention can be manufactured 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 cathode active material composition is directly coated and dried on an electrode current collector to prepare a cathode. It is also possible to produce the positive electrode by casting the positive electrode active material composition on a separate support, and then laminating the film obtained by peeling from the support on an electrode current collector.

The positive electrode active material is a lithium-containing metal oxide, any one commonly used in the art can be used, for example, LiCoO ₂ , LiMn _X O _2X , LiNi _1-X MnXO _2X (x = 1, 2), Ni _{1 -XY} Co _X MnO ₂ , and the like, and more specifically, compounds capable of redoxing lithium, such as LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ , V ₂ O ₅ , TiS, and MoS.

Carbon black is used as the conductive material, and vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene and mixtures thereof , Styrene butadiene rubber-based polymer is used, N-methylpyrrolidone, acetone, water and the like is used as the solvent. At this time, the content of the positive electrode active material, the conductive material, the binder and the solvent is a level commonly used in lithium batteries.

As the separator, any one used in a lithium battery can be used. In particular, it is preferable that it is low resistance to the ion migration of electrolyte, and is excellent in electrolyte-moisture capability. In more detail, glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) or a material selected from these may be non-woven or woven fabric.

Any electrolyte can be used as long as it is used in a lithium battery. For example, propylene carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butylene carbonate, benzonitrile acetonitrile, tetrahydrofuran, 2 -Methyltetrahydrofuran, -butyrolactone, dioxolane, 4-methyldioxolane, N, N-dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, 1,2-dimethoxyethane, sulf Porane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diethylene glycol or dimethyl ether LiPF ₆ , LiBF ₄ , LiSbF, LiAsF ₆ , LiClO ₄ , Li CF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , LiSbF ₆ , LiAlO ₄ , LiAlCl ₄ , LiN (CxF _{2x + 1} SO ₂ ) (CyF _{2y + 1} SO ₂ ) x, y can be used by dissolving one kind or a mixture of two or more kinds of electrolytes composed of lithium salts such as natural water), LiCl, LiI and the like.

According to the present invention, a separator is disposed between an anode plate and a cathode plate including a Si-containing material layer on at least one side to form a battery assembly. The battery assembly is wound or folded, placed in a cylindrical battery case or a square battery case, and then injected with electrolyte to complete a lithium battery.

 Next, the method of manufacturing an electrode according to the present invention comprises the steps of applying the Si-containing material to the electrode collector at 0.005㎛ ~ 1㎛, coating, drying, and applying the electrode active material prepared by the above method on the Si-containing material layer Squeezing.

Another method of manufacturing an electrode according to the present invention comprises the steps of coating, drying and compressing the electrode active material prepared by the above-described method on the electrode current collector and coating and drying the Si-containing material on the electrode active material layer to form a coating film It includes a step.

Another method of manufacturing an electrode according to the present invention comprises the steps of coating and drying the Si-containing material on the electrode current collector to form a Si-containing material layer, coating, drying, compressing the electrode active material on the Si-containing material layer and And applying and drying the Si-containing material on the electrode active material layer. At this time, it is most preferable to vapor-deposit the Si-containing material.

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

Preparation of Cathode

Example 1

Hexamethyl disilazane (trade name OAP, manufactured by Tokyo Chemical Co., Ltd., trade name OAP) was formed to a thickness of 0.005 μm by vapor deposition on a 19 μm copper (Cu) current collector, and then 96 wt% graphite powder was used as a negative electrode active material and poly as a binder. 4 wt% of vinylidene fluoride (PVDF) and 100 ml of NMP (N-Methylpyrrolidone) were added and mixed well.Then, the negative electrode slurry prepared by kneading the ceramic ball for about 10 hours was applied on the HMDS layer. Placed in a 90 ° C. oven and dried for about 10 hours to allow NMP to evaporate completely. Thereafter, the negative electrode was roll pressed to prepare a negative electrode having a thickness of 120 μm.

Example 2

On a 19 μm copper (Cu) current collector, 96 wt% graphite-based powder as a negative electrode active material, 4 wt% polyvinylidene fluoride (PVDF) as a binder, and 100 ml of NMP were added and mixed well. The negative electrode slurry prepared by kneading was applied and then placed in an oven at about 90 ° C. and dried for about 10 hours to completely evaporate NMP. Thereafter, HMDS was formed on the electrode active material layer to a thickness of 0.005 μm by vapor deposition, and roll press was used to prepare a negative electrode having a thickness of 120 μm.

Example 3

HMDS was formed to a thickness of 0.005 mu m by vapor deposition on a 19 mu m copper (Cu) current collector. Then, 96 wt% graphite-based powder, 4 wt% polyvinylidene fluoride (PVDF) and 100 ml NMP (N-methylpyrrolidone) were added as a negative electrode active material, mixed well, and then the ceramic ball was added well for about 10 hours. Kneading to prepare a negative electrode slurry. The negative electrode slurry was applied onto an HMDS layer and placed in a 90 ° C. oven to dry for about 10 hours to allow NMP to evaporate completely. HMDS was again formed on the negative electrode active material layer to a thickness of 0.005 μm by vapor deposition and roll pressed to prepare a negative electrode having a thickness of 120 μm.

Example 4

It prepared in the same manner as in Example 1. However, the negative electrode was prepared with a thickness of HMDS of 0.05 μm.

Example 5

It prepared in the same manner as in Example 2. However, the negative electrode was prepared with a thickness of HMDS of 0.05 μm.

Example 6

It prepared in the same manner as in Example 3. However, the negative electrode was prepared with HMDS of 0.05 μm each.

Example 7

It prepared in the same manner as in Example 1. However, the negative electrode was manufactured with the thickness of HMDS as 1 μm.

Example 8

It prepared in the same manner as in Example 2. However, the negative electrode was manufactured with the thickness of HMDS as 1 μm.

Example 9

It prepared in the same manner as in Example 3. However, the negative electrode was manufactured with HMDS as 1 micrometer each.

Comparative Example 1

On a 19 μm copper (Cu) current collector, 96 wt% graphite-based powder, 4 wt% polyvinylidene fluoride (PVDF) as a binder, and 100 ml of NMP were added and mixed well. The negative electrode slurry prepared by kneading was applied and then placed in an oven at 90 ° C. and dried for about 10 hours to completely evaporate NMP. Thereafter, the negative electrode was roll pressed to prepare a negative electrode having a thickness of 120 μm.

Examples 10 to 18 and Comparative Example 2: Fabrication of Lithium Battery

The negative electrode prepared in Examples 1 to 9 and Comparative Example 1 was used as a counter electrode of lithium metal, and the PE separator and LiPF ₆ were EC (ethylene carbonate) + EMC (ethyl methyl carbonate) (3/7 vol%). An 18650 size, 2000 mAh cylindrical battery was prepared according to a conventional method using the solution formed so as to be 1.3 M dissolved in an electrolyte.

Experimental Study on Characteristics of Electrode Current Collector and Cathode by HMDS Treatment

The characteristics of the electrode current collector and the negative electrode according to the treatment of HMDS were tested in the following manner, and the results are shown in Table 2.

Discoloration experiment of electrode collector

After dissolving the electrode collector in an electrolyte solution formed by dissolving LiPF ₆ in EC (ethylene carbonate) + EMC (ethyl methyl carbonate) (3/7 vol%) to 1.3 M, discoloration of the electrode collector was observed after 24 hours. It was visually confirmed.

Adhesion test between electrode current collector and negative electrode active material

Referring to FIG. 5, electrodes prepared according to Examples 1 to 9 and Comparative Examples were cut out using a steel ruler having a width of 25.4 mm (= 1 inch) and a length of 100 mm. The software for driving the tester was run after the tensile tester and the PC were powered on. The protective film of the double-sided tape was peeled off, and the adhesive side of the double-sided tape was stuck to the test board so that it might correspond with a test board (glass plate). The substrate was slowly removed from the end of the sample that did not adhere to the test plate (the negative electrode active material adhered to the double-sided tape portion and the substrate portion fell). Each of the test glass plate and the substrate on which the negative electrode active material was attached was installed using a pedal in a tensile tester (see FIG. 6). Click the Run Tester button. The pulling rate was 100 mm / min and the drawing length was 50 mm.

Read measurements according to standard formats supported by the drive software, MAX, MIN, AVE. The average value was taken in the display.

Electrolyte solution experiment

The negative electrode plates prepared in Examples 1 to 9 and Comparative Example 1 were immersed in an electrolyte solution in which LiPF ₆ was dissolved in EC (ethylene carbonate) + EMC (ethyl methyl carbonate) (3/7 vol%) to form 1.3 M, and then the electrolyte solution. All of these times were measured to be moistened.

TABLE 2

Discoloration  Adhesive force gforce / mm Electrolytic solution moisture time (min) Comparative Example 1 U 4.03 15 Example 1 radish 5.56 10 Example 2 radish 5.87 8 Example 3 radish 5.98 7 Example 4 radish 6.02 6 Example 5 radish 6.16 5 Example 6 radish 6.45 7 Example 7 radish 6.53 6 Example 8 radish 6.75 5

Performance Test of Battery by HMDS Treatment

In order to confirm the performance of the battery according to the HMDS treatment, resistance, discharge and life capacity, and safety evaluation were performed as follows, and the results are shown in Table 3.

Experiment of resistance, discharge and life capacity

The resistance is 100% of the AC impedance (impedence) of Comparative Example 2 measured the resistance of the battery of Examples 10-18 with a standard resistor and then expressed in% compared to Comparative Example 2, the discharge is cut off at 3C 3V off) The discharge capacity was measured and displayed as 100% of the capacity of Comparative Example 2. The lifespan capacity was 300 times after charging and discharging, and the lifespan capacity was indicated as 100% of the capacity of Comparative Example 2. The values are averaged after measuring the values of five batteries.

Safety evaluation

For safety evaluation, after 12 hours of overcharging at 2C / 12V, the steps were divided into 5 stages (L0: good, L1: leakage, L2: flash, L2: flame, L3: smoke, L4: fire, L5: burst) Evaluated. If 2-20 cells were tested, the number before L in the table indicates the number of cells tested.

Oven experiment

The battery was left in the chamber at 150 ° C. for 1 hour, and then the result was confirmed and displayed in the same manner as the overcharge experiment.

TABLE 3

resistance(%) 3C discharge (%) life span(%) 2C / 12V overcharge Oven Experiment (150?) Comparative Example 2 100 100 100 15L0, 5L5 15L0, 5L5 Example 10 96 115 105 17L0, 3L5 18L0, 2L4 Example 11 97 116 107 18L0, 2L3 17L0, 3L3 Example 12 95 120 110 19L0, 1L2 19L0, 1L2 Example 13 86 127 125 2L0 2L0 Example 14 87 126 124 2L0 2L0 Example 15 80 130 130 2L0 2L0 Example 16 87 121 115 19L0, 1L3 2L0 Example 17 88 120 120 2L0 2L0 Example 18 83 125 125 2L0 2L0

As shown in Table 2, when the electrode current collector and / or electrode active material layer was treated with Si-containing materials (HMDS in the experiment) of Examples 1 to 9 according to an embodiment of the present invention, represented by Comparative Example 2 Compared with the conventional electrodes, the adhesion between the electrode current collector and the electrode active material is increased, and it can be seen that oxidation is prevented because there is no discoloration of the electrode current collector, thus preventing ion dissolution of the electrode current collector metal. As a result of the decrease in the humidity of the electrolyte according to the treatment thickness of the HMDS, it was found that the OH group on the surface of the electrode was removed according to the present invention to decrease the contact angle between the electrolyte and the negative electrode active material, thereby increasing the humidity of the electrolyte. Therefore, the lithium battery employing the electrode according to the present invention showed an excellent life characteristics and liquid injection properties.

In addition, as shown in Table 3, when the present invention treated the electrode current collector and / or the electrode active material layer with the HMDS of Examples 10 to 18 according to one embodiment, compared with the conventional battery represented by Comparative Example 2, The resistance was lowered, while the discharge capacity and lifespan were increased, and the overcharge and oven experiments showed relatively high safety. Accordingly, the lithium battery according to the present invention provides a lithium battery having excellent life characteristics, low battery resistance, high capacity, and excellent safety, such as short resistance and heat resistance.

Electrode according to the present invention by applying a Si-containing material layer to the electrode current collector and / or the electrode active material layer, to prevent oxidation of the electrode current collector, lower the resistance, increase the adhesion between the electrode current collector and the electrode active material, ohmic contact And lifespan is increased, and the contact angle between the electrolyte and the electrode active material is reduced by removing OH groups on the surface of the electrode, thereby increasing the humidity of the electrolyte and thus improving the liquidity. Therefore, the lithium battery according to the present invention employing the same has excellent life characteristics, low battery resistance, high capacity, and excellent safety, such as short resistance and heat resistance.

Claims (21)

Electrode current collectors; Si containing material layer; And And an electrode active material layer. The method of claim 1, The Si-containing material layer And an electrode current collector, stacked on at least one surface of the electrode current collector in order of a Si-containing material layer and an electrode active material layer. The method of claim 1, The Si-containing material layer And an electrode current collector, laminated on at least one surface of the electrode current collector in order of an electrode active material layer and a Si-containing material layer. The method of claim 1, The Si-containing material layer And an electrode current collector, laminated on at least one surface of the electrode current collector in order of a Si-containing material layer, an electrode active material layer, and a Si-containing material layer. The method of claim 1, An electrode, wherein the Si-containing material layer comprises a material of general formula (I)

(I) Wherein R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amine group, -SH, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an alke having 2 to 20 carbon atoms. A silyl group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, X is -NH-, -O-, -SO _3- , an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, a silanylene group, an arylene group having 6 to 30 carbon atoms, a peptyl group and a carbonylene group , An oxyalkylene group having 1 to 20 carbon atoms, A represents a hydrogen atom, a halogen atom, -SH, an amino group, a heterocycloalkyl group having 2 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a silanyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms. The method of claim 5, R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amine group, -SH, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, An alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 9 carbon atoms, an aryloxy group having 6 to 9 carbon atoms, an alkylcarbonyl group having 1 to 3 carbon atoms, X is -NH-, -O-, -SO _3- , alkylene group having 1 to 6 carbon atoms, alkenylene group having 2 to 6 carbon atoms, silanylene group, arylene group having 6 to 9 carbon atoms, peptyl group, carbonyl A ethylene group and an oxyalkylene group having 1 to 6 carbon atoms, A represents a hydrogen atom, a halogen atom, -SH, an amino group, a heterocycloalkyl group of 2 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, a silanyl group of 1 to 6 carbon atoms, an aryl group of 6 to 9 carbon atoms The method of claim 5, Wherein said compound of formula I is a compound of formula II:

(II) Wherein R ₁ , R ₂ , R ₃ and X are as defined above. The method of claim 7, wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amine group, -SH, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, An alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 9 carbon atoms, an aryloxy group having 6 to 9 carbon atoms, an alkylcarbonyl group having 1 to 3 carbon atoms, X is -NH-, -O-, -SO _3- , alkylene group having 1 to 6 carbon atoms, alkenylene group having 2 to 6 carbon atoms, silanylene group, arylene group having 6 to 9 carbon atoms, peptyl group, carbonyl An ene group and an oxyalkylene group having 1 to 6 carbon atoms. The method of claim 5, Wherein said compound of formula I is a compound of formula III:

(III) Wherein R ₁ , R ₂ , R ₃ are as defined above, R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amine group, a thiol group, an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an alkylcarbonyl group having 1 to 20 carbon atoms. , X <1> is O-, -NH-, a C1-C20 alkylene group, a C2-C20 alkenylene group, and a C6-C30 arylene group. The method of claim 9, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amine group, -SH, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms. , An alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 9 carbon atoms, an aryloxy group having 6 to 9 carbon atoms, an alkylcarbonyl group having 1 to 3 carbon atoms, X ₁ is —NH—, —O—, —SO ₃ —, an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, a silanylene group, an arylene group having 6 to 9 carbon atoms, a peptyl group, and a carbon. A carbonyl group and an oxyalkylene group having 1 to 6 carbon atoms. The method of claim 5, Wherein said compound of formula I is a compound of formula IV:

(IV) Wherein R ₁ to R ₆ are as defined above. The method of claim 11, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amine group, -SH, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms. And an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 9 carbon atoms, an aryloxy group having 6 to 9 carbon atoms, and an alkylcarbonyl group having 1 to 3 carbon atoms. The method of claim 5, Wherein said compound of formula I is a compound of formula

(V) Wherein R ₁ to R ₆ are as defined above, and R ₇ and R ₈ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amine group, -SH, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl having 3 to 20 carbon atoms. An alkyl group, a C1-C20 alkenyl group, a C1-C20 alkoxy group, a C6-C30 aryl group, a C6-C30 aryloxy group, and a C1-C20 alkylcarbonyl group are shown. The method of claim 13, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ are hydrogen atom, halogen atom, hydroxy group, amine group, -SH, C1-6 alkyl group, C3-8 A cycloalkyl group, an alkenyl group of 2 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, an aryl group of 6 to 9 carbon atoms, an aryloxy group of 6 to 9 carbon atoms, and an alkylcarbonyl group of 1 to 3 carbon atoms . The method of claim 5, Wherein said compound of formula I is a compound of formula VI:

(VI) Wherein R ₁ , R ₂ and R ₃ are as defined above, and R ₉ and R ₁₀ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amine group, -SH, an alkyl group having 1 to 20 carbon atoms, and having 3 to 3 carbon atoms. A cycloalkyl group of 20, an alkenyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, an aryloxy group of 6 to 30 carbon atoms, and an alkylcarbonyl group of 1 to 20 carbon atoms, X <_2> is a C1-C20 alkylene group, a C2-C20 alkenylene group, and a C6-C30 arylene group. The method of claim 15, R ₁ , R ₂ , R ₃ , R ₉ , and R ₁₀ are a hydrogen atom, a halogen atom, a hydroxy group, an amine group, -SH, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a carbon atom having 2 to 6 carbon atoms. An alkenyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 9 carbon atoms, an aryloxy group having 6 to 9 carbon atoms, an alkylcarbonyl group having 1 to 3 carbon atoms, X ₂ is an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, and an arylene group having 6 to 9 carbon atoms. The method of claim 1, An electrode comprising at least one selected from the group consisting of materials of the following formula: Cl (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , HS (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₃ Si (OCH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , CH ₃ Si (OC ₂ H ₅ ) ₃ , (CH ₃ ) ₃ SiOCH ₃ , (CH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ,

, CH ₃ SiCl ₃ , (CH ₃ ) ₂ SiCl ₂ , (CH ₃ ) ₃ SiCl, (CH ₃ CH ₂ ) ₃ SiCl,

, CH ₂ = CHSi (OCH ₃ ) ₃ , CH ₂ = CHSi (OCOCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ ,

,

,

, CH ₂ = CCH ₃ COO (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ , CH ₂ = CCH ₃ COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CF ₃ OSO ₂ Si (CH ₃ ) ₃ , ( CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ , H ₂ NCONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , (CH ₃ ) ₃ SiNHCONHSi (CH ₃ ) ₃ , (CH ₃ ) ₃ SiNHCCF ₃ OSi (CH ₃ ) ₃ , Cl (i-Pr) ₂ SiO-i (i-Pr) ₂ Cl. According to claim 1, And wherein the Si-containing material layer comprises hexamethyl disalazane. The method according to any one of claims 1 to 18, And the thickness of the Si-containing material coating layer is 0.005㎛ ~ 1㎛. The method according to any one of claims 1 to 18, And the thickness of the Si-containing material coating layer is 0.01㎛ ~ 0.05㎛. In a lithium battery comprising a negative electrode, a positive electrode and an electrolyte solution, A lithium battery comprising at least one electrode according to any one of claims 1 to 20.

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