KR20170083413A - Silicon based copolymer, electrolyte composition comprising the same and lithium secondary battery using the same - Google Patents

Abstract

The present invention relates to a silicone-based copolymer graft-copolymerized with a functional group exhibiting high ionic conductivity and a functional group exhibiting high ionic conductivity, and an electrolyte composition comprising the same, and a lithium secondary battery using the silicone-based linear polymer.

Description

TECHNICAL FIELD [0001] The present invention relates to a silicone-based copolymer, an electrolyte composition containing the same, and a lithium secondary battery using the same. BACKGROUND ART [0002]

The present invention relates to a silicone-based copolymer graft-copolymerized with a functional group exhibiting high ionic conductivity and a functional group exhibiting high ionic conductivity, and an electrolyte composition comprising the same, and a lithium secondary battery using the silicone-based linear polymer.

As the field of small-sized high-tech devices develops, the demand for lithium secondary batteries used as energy sources is rapidly increasing. The lithium secondary battery has a higher energy density per unit weight than conventional secondary batteries such as lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries and nickel-zinc batteries so that the lithium secondary batteries operate at a high driving voltage, have a long cycle life, It is widely commercialized.

Also, as interest in environmental problems has increased recently, studies on electric vehicles (EV) and hybrid electric vehicles (HEV) that can replace fossil fuel-based vehicles have been actively conducted. Although a nickel-hydrogen metal (Ni-MH) secondary battery is mainly used as a power source for electric vehicles (EV) and hybrid electric vehicles (HEV), the use of a lithium secondary battery showing high energy density, discharge voltage, Research is also underway.

Generally, a lithium secondary battery includes a lithium ion battery including a liquid electrolyte, depending on the type of electrolyte; A lithium ion polymer battery comprising an electrolyte in the form of a gel; And a lithium polymer battery including a solid electrolyte.

Conventionally, an ion conductive organic electrolyte in which a salt is dissolved in a non-aqueous organic solvent is used as an electrolyte for an electrochemical device using an electrochemical reaction. Korean Patent Laid-Open Publication No. 1997-069220 discloses a lithium ion- A lithium ion secondary battery comprising a nonaqueous electrolyte solution is disclosed. However, when a liquid electrolyte is used, the electrode material is degenerated and the possibility of volatilization of the organic solvent is high. In addition, there is a problem in stability due to the ambient temperature and the combustion due to the temperature rise of the battery itself. There is a fear of leakage, and it may be difficult to realize various types of electrochemical devices using the same. Accordingly, in order to overcome the stability problem of the liquid electrolyte, an electrolyte in gel or solid form has been proposed. The stability of an electrochemical device is improved by the order of liquid <gel <solid compared to the type of electrolyte applied, but the performance of an electrochemical device is known to decrease in the order of liquid> gel> solid. Since the performance of the electrochemical device using the solid electrolyte is deteriorated, it is difficult to commercialize batteries including the solid electrolyte. On the other hand, the gel type electrolyte has a lower ionic conductivity than the liquid electrolyte, is liable to leak, and has poor mechanical properties.

Currently, polyethylene oxide (PEO) polymer electrolytes among solid electrolytes are known to have the highest commercial potential. However, when a polyethylene oxide (PEO) based polymer electrolyte is used, the ion conductivity is relatively high at 10 ^-4 S / cm at a high temperature of 60 ° C or higher, but the ionic conductivity is lowered to 10 ^-8 S / cm at room temperature. This problem is caused by the fact that the polyethylene oxide (PEO) based polymer shows high crystallinity at room temperature. In general, the movement of ions in the electrolyte is caused by the segmental motion of the polymer, and the movement of such ions is limited when crystals are formed. Therefore, much research has been conducted to develop a solid electrolyte having a high ionic conductivity and excellent mechanical properties at a relatively low temperature and a room temperature by suppressing the crystallinity of the polymer electrolyte.

Korean Patent Publication No. 1997-069220

In order to solve the above-mentioned problems, the present invention aims to provide a silicone copolymer having excellent ion conductivity and mechanical properties, an electrolyte composition containing the same, and a lithium secondary battery using the same.

In order to achieve the above object, the present invention provides a silicone-based copolymer represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₈ are the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heteroaryl group having 5 to 40 nuclear atoms Lt; / RTI &gt;

m and n are each independently an integer of 1 or more,

X is a single bond or an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 40 carbon atoms, And a heteroarylene group having 5 to 40 nuclear atoms, provided that when X is plural, they are the same as or different from each other,

A is _{-O- (CH 2 CH 2 O)} i-CH 3, - (CH 2) 3 O- (CH 2 CH 2 O) i-CH 3, -OSi (CH 3) 2 - (CH 2) 3 _{O- (CH 2 CH 2 O)} i-CH 3, -OSi (CH 3) 2 -OSi (CH 3) 2 - (CH 2) 3 O- (CH 2 CH 2 O) i-CH 3, -O _{- (CH 2 CH 2 CH 2} O) i-CH 3, - (CH 2) 3 O- (CH 2 CH 2 CH 2 O) i-CH 3, -OSi (CH 3) 2 - (CH 2) 3 _{O- (CH 2 CH 2 CH 2} O) i-CH 3, -OSi (CH 3) 2 -OSi (CH 3) 2 - (CH 2) 3 O- (CH 2 CH 2 CH 2 O) i-CH _{3, -O- (CH 2 CH 2} O) i- (CH 2 CH 2 CH 2 O) j-CH 3, -OSi (CH 3) 2 -OSi (CH 3) 2 -OSi (CH 3) 2 - (CH ₂ ) ₃ O- (CH ₂ CH ₂ O) i-CH ₃ , provided that when A is plural, they are the same as or different from each other, and i and j are each independently 2 - Lt; / RTI &gt;

Y is a single bond or an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 40 carbon atoms, And a heteroarylene group having 5 to 40 nuclear atoms, provided that when Y is plural, they are the same as or different from each other,

B is at least one member selected from the group consisting of trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, tetra- Methyldiethoxysilane, ethyldimethoxysilane, ethyldiethoxysilane, propyldimethoxysilane, propyldiethoxysilane, isobutyldietethoxysilane, cyclohexyldimethoxysilane, phenyldimethoxy Silane, phenyldiethoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, allyldimethoxysilane, allyldiethoxysilane, dimethylmethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenyl Ethoxysilane, and when B is plural, they are the same or different from each other.

The present invention also provides an electrolyte composition comprising the silicone-based copolymer, the lithium salt and the curing accelerator.

The present invention also provides a positive electrode comprising: a positive electrode; cathode; And an electrolyte membrane existing between the anode and the cathode, the electrolyte membrane being formed of the electrolyte composition.

The silicone-based copolymer according to the present invention comprises an ester group (-COO-) and a silane group (-SiO-), and thus the ionic conductivity and mechanical properties (particularly, Mechanical strength) and a lithium secondary battery including such a solid electrolyte can be produced.

1 is a schematic diagram of a solid electrolyte according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention. Therefore, the configuration of the embodiment described in the present specification is merely the most preferred embodiment of the present invention, and does not represent all the technical ideas of the present invention, so that various equivalents and variations Examples should be understood.

1. Silicon-based copolymer

The silicone-based copolymer according to an embodiment of the present invention includes an ester group (-COO-) and a silane group (-SiO-), and is represented by the following formula (1).

R ₁ to R ₈ are the same or different from each other and each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 40 carbon atoms, a nucleus And a heteroaryl group having 5 to 40 atoms.

m and n are each independently an integer of 1 or more. In this case, m may preferably be an integer of 4 to 80, more preferably an integer of 20 to 40. The above n may preferably be an integer of 4 to 80, more preferably an integer of 2 to 20.

When m and n are each independently an integer of 2 or more, each of X, A, Y and B may be plural.

X is a single bond or an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 40 carbon atoms, And a heteroarylene group having 5 to 40 nuclear atoms, provided that when X is plural, they are the same as or different from each other.

A is _{-O- (CH 2 CH 2 O)} i-CH 3, - (CH 2) 3 O- (CH 2 CH 2 O) i-CH 3, -OSi (CH 3) 2 - (CH 2) 3 _{O- (CH 2 CH 2 O)} i-CH 3, -OSi (CH 3) 2 -OSi (CH 3) 2 - (CH 2) 3 O- (CH 2 CH 2 O) i-CH 3, -O _{- (CH 2 CH 2 CH 2} O) i-CH 3, - (CH 2) 3 O- (CH 2 CH 2 CH 2 O) i-CH 3, -OSi (CH 3) 2 - (CH 2) 3 _{O- (CH 2 CH 2 CH 2} O) i-CH 3, -OSi (CH 3) 2 -OSi (CH 3) 2 - (CH 2) 3 O- (CH 2 CH 2 CH 2 O) i-CH _{3, -O- (CH 2 CH 2} O) i- (CH 2 CH 2 CH 2 O) j-CH 3, -OSi (CH 3) 2 -OSi (CH 3) 2 -OSi (CH 3) 2 - (CH ₂ ) ₃ O- (CH ₂ CH ₂ O) i -CH ₃ , provided that when A is plural, they are the same as or different from each other.

Here, i and j are each independently an integer of 2 to 100, preferably an integer of 4 to 50. [

 Y is a single bond or an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 40 carbon atoms, And a heteroarylene group having 5 to 40 nuclear atoms, provided that when Y is plural, they are the same as or different from each other.

B is at least one member selected from the group consisting of trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, tetra- Methyldiethoxysilane, ethyldimethoxysilane, ethyldiethoxysilane, propyldimethoxysilane, propyldiethoxysilane, isobutyldietethoxysilane, cyclohexyldimethoxysilane, phenyldimethoxy Silane, phenyldiethoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, allyldimethoxysilane, allyldiethoxysilane, dimethylmethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenyl Ethoxysilane, and when B is plural, they are the same or different from each other.

The weight average molecular weight (MW) of the silicone polymer represented by the formula (1) is not particularly limited, but may be 500,000 or less. Particularly, when the silicone-based polymer has a weight-average molecular weight (MW) of 200 to 20,000, it can provide an effect of increasing ionic conductivity while greatly improving mechanical properties (particularly, mechanical strength) when applied to a solid electrolyte composition desirable.

The silicone-based copolymer represented by the formula (1) may be formed by graft-copolymerizing a compound represented by the following formula (3) and a compound represented by the following formula (4) in a compound represented by the following formula (2). At this time, the silicone-based copolymer of the formula (1) can be polymerized by using any conventional copolymerization method known in the art without limitation. An example of such a copolymerization method is a hydrosilylation reaction using a platinum catalyst.

In the compound represented by the general formula (2), R ₁ to R ₃ , R ₆ to And R &lt; ₈ &gt;

p is an integer from 1 to 200; When p is an integer of 1 or less, it is difficult to control the crystallinity and the ionic conductivity of the electrolyte composition is not expected to be improved. When p is an integer of 200 or more, flexibility of the electrolyte composition is lowered and workability may be lowered. Particularly, when p is an integer of 5 to 100, it is preferable from the viewpoints of control of crystallinity and mechanical properties.

When p is an integer of 2 or more, R ₉ may be plural.

R ₉ is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 40 carbon atoms, provided that when R ₉ is plural, they are the same or different.

The compound represented by the general formula (2) is a silicon-based linear polymer containing hydrogen, and the hydrogen may be reacted with a compound represented by the following general formula (3) or a compound represented by the following general formula (4) .

In the compound represented by the general formula (3), * denotes a site to be polymerized in the general formula (2).

X and A are the same as defined in Formula 1, respectively.

In the compound represented by the general formula (4), * denotes a site to be polymerized in the general formula (2).

Y and B are the same as defined in Formula 1, respectively.

Thus, the silicone-based copolymer of Formula 1 according to an embodiment of the present invention has a structure in which an ester group (-COO-) and a silane group (-SiO-) are introduced into a silicone-based linear polymer, and the silicone- , The ionic conductivity is improved by the ester group (-COO-), and the thermosetting property is improved by the silane group (-SiO-), so that excellent mechanical strength can be exhibited.

2. Electrolyte composition

The electrolyte composition according to an embodiment of the present invention may include (a) the silicone-based copolymer, (b) a lithium salt, and (c) a curing accelerator.

Specifically, the (a) silicone-based copolymer is represented by the formula (1) wherein an ester group and a silane group are introduced into a silicone linear polymer, and ion conductivity and mechanical properties of the electrolyte composition can be improved.

The lithium salt (b) is not particularly limited, and lithium triflouromethane sulfonate (LiCF ₃ SO ₃ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluoroarsenate (LiAsF _6), lithium perchlorate (LiClO _4), lithium has a triple Oro methanesulfonyl be at least one member selected from the group consisting of imide _{(LiN (CF 3 SO 2)} 2).

The content of the lithium salt is 3 to 80% by weight, preferably 5 to 30% by weight based on the weight% of the (a) silicone copolymer. The amount of the lithium salt to be used may be adjusted by an appropriate mixing ratio as required.

The curing accelerator (c) may be used without limitation in a conventional curing accelerator known in the art to control the curing rate of the electrolyte composition. Non-limiting examples of such curing accelerators include tetra- or divalent organotin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin bis (acetylacetonate), dibutyltin oxide, dibutyl Tin maleate, dibutyl tin octoate, dibutyl tin dimaleate, and the like. Preferably, dibutyltin dilaurate or dibutyltin octoate can be used.

The content of the curing accelerator is 0.001 to 10% by weight based on the total 100% by weight of the electrolyte composition. When the amount of the curing accelerator is less than 0.001% by weight, the curing rate of the electrolyte composition may be significantly decreased. When the curing accelerator is more than 10% by weight, it is difficult to control the reaction rate, Can be reduced.

The electrolyte composition according to an embodiment of the present invention may be produced by using a conventional method for producing an electrolyte known in the art without limitation, for example, (S1) preparing the silicone-based copolymer; And (S2) mixing the silicone copolymer, the lithium salt and the curing accelerator of the above (S1). The electrolyte composition manufactured by this method can be produced as an electrolyte membrane, and a manufacturing process thereof will be described below.

First, in the reactor, 3 to 80% by weight of the lithium salt and 0.01 to 10% by weight of the curing accelerator are added to the silicone copolymer, the silicone copolymer in an amount of 100% by weight based on the total weight of the electrolyte composition, . At this time, if necessary, an organic solvent can be further added, but a solvent is not necessarily essential. However, if a solvent is used, a drying process for removing the solvent should be added. Thereafter, the prepared mixed solution is coated on a support such as a glass plate, a polyethylene vinyl, a commercial Mylar film, or a battery electrode to an appropriate thickness, and the curing reaction is performed at 40 to 200 캜 (preferably 60 to 120 캜) So that an electrolyte membrane can be produced. Alternatively, after the prepared mixed solution is applied on the support, a thickness controlling spacer is fixed on both ends of the support in order to obtain a film having a constant thickness, and then another support is covered thereon. 120 &lt; 0 &gt; C), an electrolyte membrane can be produced.

As described above, the electrolyte composition according to one embodiment of the present invention includes a silicone copolymer, a lithium salt, and a curing accelerator, so that a solid electrolyte having improved ionic conductivity and mechanical properties can be produced. In this case, the electrolyte composition may further include conventional electrolyte composition additives (for example, salt additives, binders, etc.) other than the silicone type copolymer, the lithium salt and the curing accelerator.

3. Lithium secondary battery

The lithium secondary battery according to the present invention may include (i) an anode, (ii) a cathode, and (iii) an electrolyte membrane existing between the anode and the cathode and formed of the electrolyte composition.

The positive electrode (i) can be used without limitation to a conventional positive electrode active material known in the art. Non-limiting examples of the cathode active material may be lithium metal oxides such as LiCoO ₂ , LiNiO ₂ , LiNiCoO ₂ , and LiMn ₂ O ₄ . At this time, the anode may further include a binder, a conductive agent, an electrolyte, etc. in addition to the cathode active material.

The above (ii) negative electrode can be used without limitation to a conventional negative electrode material known in the art. The negative electrode material may be lithium metal, lithium, silicon, tin, or the like, which is capable of intercalating and deintercalating lithium ions, and non-limiting examples thereof include carbon materials including graphite or coke (for example, MCMB and MPCF). At this time, the cathode may further include a binder, a conductive agent, an electrolyte, and the like in addition to the cathode material.

The electrolyte membrane (iii) is present between the anode and the cathode and is formed of an electrolyte composition containing the compound of Formula 1, and can exhibit excellent ion conductivity and mechanical properties.

The lithium secondary battery of the present invention can be manufactured by using a conventional method of manufacturing a lithium secondary battery known in the art without limitation. At this time, the external shape of the lithium secondary battery is not particularly limited, but may be a cylindrical shape, a square shape, a pouch shape, a coin shape, or the like using a can. In addition, the lithium secondary battery can be used not only as a small device but also as a unit cell of a medium and large-sized device. Such mid- to large-sized devices may be electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, power storage systems, and the like.

Hereinafter, the present invention will be described concretely with reference to Examples. However, the following Examples illustrate only one embodiment of the present invention, and the scope of the present invention is not limited by the following Examples.

[ Preparation Example  One] Polymethylhydrosiloxane ( Polymethylhydrosiloxane ) Synthesis of

<Step 1>

Tetramethyl cyclotetrasiloxane (15 g), hexamethyldisiloxane (1.5 g) and p-toluenesulfonic acid (0.5 g) were placed in a reactor under nitrogen atmosphere at 90 ° C. for 5 hours And reacted with stirring. After the reaction, the reaction compound was purified in vacuo at 80 占 폚 and unreacted material was removed.

<Step 2>

(10 g), polyethylene glycol methacrylate (50 g), Mn (350 g / mol) (50 g), Allyl trimethoxysilane (Allyl trimethoxy silane) ) (5 g) were mixed and stirred at 60 ° C for 30 minutes. Thereafter, H ₂ PtCl ₆ (1 g) dissolved in isopropyl alcohol (IPA) (0.05 g) was added dropwise. After reacting for 5 hours, polymethylhydrosiloxane was purified by vacuum at 90 占 폚.

[ Example  One] Electrolyte membrane  Produce

Polymethylhydrosiloxane (10 g), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ) (1 g) and dibutyltin dilaurate (1 g) prepared in Preparation Example 1 were mixed, Followed by curing to prepare an electrolyte membrane.

[ Example  2] Electrolyte membrane  Produce

An electrolyte membrane was prepared in the same manner as in Example 1 except that 3 g of lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ) was used instead of 1 g.

[ Example  3] Electrolyte membrane  Produce

An electrolyte membrane was prepared in the same manner as in Example 1 except that 6 g of lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ) was used instead of 1 g.

[ Comparative Example  One] Electrolyte membrane  Produce

Lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ) (3 g) was mixed with polyethylene oxide (Mn = 600,000 g / mol) (10 g) dissolved in benzene (200 g) and cured at 60 ° C to form an electrolyte membrane .

[ Experimental Example  1] Measurement of crystallinity

The crystallinity of the electrolyte membranes prepared in Examples 1 to 3 and Comparative Example 1 was measured. The crystallization degree was measured by differential scanning calorimeter (DSC), and calorific value was calculated as a percentage using the heat amount (213.7 J / g) when polyethylene oxide was 100% determined.

[ Experimental Example  2] Ion conductivity measurement

The ionic conductivities of the electrolyte membranes prepared in Examples 1 to 3 and Comparative Example 1 were measured. At this time, the ionic conductivity was measured by the alternating current impedance method (EIS), and the change of the interfacial resistance and bulk resistance of the cell with time was measured, and the ion conductivity was calculated by the following equation.

Ion conductivity (?) = 1 / Rb * t / A

(Where Rb is the resistance of the electrolyte, t is the thickness of the electrolyte membrane, and A is the area of the electrolyte membrane).

[ Experimental Example  3] Yield strength and yield Elongation  Measure

The mechanical strengths (yield strength and yield elongation) of the electrolyte membranes prepared in Examples 1 to 3 and Comparative Example 1 were measured. At this time, the mechanical strength was confirmed by tensile test using universal testing machine (UTM).

First, tensile strain and tensile stress of the specimens were measured after specimens were manufactured according to the standards of American Society for Testing and Materials (ASTM). As a result, the yield stress which is the critical stress at the yield point at which the elastic deformation occurs, and the yield strain which is the strain rate were confirmed.

The crystallinity, ionic conductivity, yield strength, and yield elongation of the electrolyte membrane measured in Experimental Examples 1 to 3 are shown in Table 1 below.

Crystallinity (%) Ion conductivity (S / cm ² ) Yield strength (MPa) Yield elongation (%) Example 1 8.0 5.4 * 10 ^-4 7.4 585 Example 2 4.6 7.8 * 10 ^-4 6.8 600 Example 3 4.5 7.7 * 10 ^-4 6.5 595 Comparative Example 1 83.4 3.5 * 10 ^-7 1.5 400

As shown in Table 1, the electrolyte membranes according to Examples 1 to 3 showed improvement in the mechanical strength (yield strength and yield elongation) of the electrolyte membrane compared with the conventional electrolyte membrane according to Comparative Example 1, and the crystallinity was sufficiently low and the ionic conductivity was improved I could.

Claims (10)

1. A silicone-based copolymer represented by the following formula (1)
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₈ are the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heteroaryl group having 5 to 40 nuclear atoms Lt; / RTI &gt;
m and n are each independently an integer of 1 or more,
X is a single bond or an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 40 carbon atoms, And a heteroarylene group having 5 to 40 nuclear atoms, provided that when X is plural, they are the same as or different from each other,
A is _{-O- (CH 2 CH 2 O)} i-CH 3, - (CH 2) 3 O- (CH 2 CH 2 O) i-CH 3, -OSi (CH 3) 2 - (CH 2) 3 _{O- (CH 2 CH 2 O)} i-CH 3, -OSi (CH 3) 2 -OSi (CH 3) 2 - (CH 2) 3 O- (CH 2 CH 2 O) i-CH 3, -O _{- (CH 2 CH 2 CH 2} O) i-CH 3, - (CH 2) 3 O- (CH 2 CH 2 CH 2 O) i-CH 3, -OSi (CH 3) 2 - (CH 2) 3 _{O- (CH 2 CH 2 CH 2} O) i-CH 3, -OSi (CH 3) 2 -OSi (CH 3) 2 - (CH 2) 3 O- (CH 2 CH 2 CH 2 O) i-CH _{3, -O- (CH 2 CH 2} O) i- (CH 2 CH 2 CH 2 O) j-CH 3, -OSi (CH 3) 2 -OSi (CH 3) 2 -OSi (CH 3) 2 - (CH ₂ ) ₃ O- (CH ₂ CH ₂ O) i-CH ₃ , provided that when A is plural, they are the same as or different from each other, and i and j are each independently 2 - Lt; / RTI &gt;
Y is a single bond or an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 40 carbon atoms, And a heteroarylene group having 5 to 40 nuclear atoms, provided that when Y is plural, they are the same as or different from each other,
B is at least one member selected from the group consisting of trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, tetra- Methyldiethoxy silane, ethyl dimethoxy silane, ethyl diethoxy silane, propyl dimethoxy silane, propyl diethoxy silane, isobutyl diethoxy silane, cyclohexyl dimethoxy silane, phenyl dimethoxy silane, Silane, phenyldiethoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, allyldimethoxysilane, allyldiethoxysilane, dimethylmethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenyl Ethoxysilane, and when B is plural, they are the same or different from each other. The method according to claim 1,
And a weight average molecular weight (Mw) of 200 to 20,000. The method according to claim 1,
Wherein the silicone-based copolymer represented by the formula (1) is obtained by graft-copolymerizing a compound represented by the following formula (3) and a compound represented by the following formula (4) in a compound represented by the following formula (2).
(2)

(In the formula (2)
R ₁ to R ₃ , R ₆ to R &lt; ₈ &gt; are each as defined in claim 1,
p is an integer of 1 to 200,
R ₉ is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 40 carbon atoms, provided that when R ₉ is plural, they are the same or different.
(3)

(3)
* Denotes a site to be polymerized in the above formula (2)
X and A are as defined in claim 1, respectively.
[Chemical Formula 4]

(In the formula 4,
* Denotes a site to be polymerized in the above formula (2)
Y and B are each as defined in the above formula (1). (a) a silicone-based copolymer of any one of claims 1 to 3,
(b) a lithium salt and
(c) Curing accelerator
&Lt; / RTI &gt; 5. The method of claim 4,
The lithium salt (b) is at least one selected from the group consisting of lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ) Wherein the electrolyte composition is at least one selected from the group consisting of lithium perchlorate (LiClO ₄ ) and lithium trifluoromethanesulfonylimide (LiN (CF ₃ SO ₂ ) ₂ ). 5. The method of claim 4,
Wherein the content of the lithium salt (b) is 3 to 80% by weight based on the weight of the silicone-based copolymer (a). 5. The method of claim 4,
The curing accelerator (c) may be selected from dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin bis (acetylacetonate), dibutyltin oxide, dibutyltin maleate, dibutyltin octoate, dibutyltin And at least one selected from the group consisting of maleic anhydride and dimaleate. 5. The method of claim 4,
The content of the curing accelerator (c) is 0.001 to 10% by weight based on 100% by weight of the electrolyte composition. 5. The method of claim 4,
A solid electrolyte composition. (i) an anode,
(Ii) cathode and
(Iii) an electrolyte membrane existing between the anode and the cathode and formed of the electrolyte composition of any one of claims 4 to 9
&Lt; / RTI &gt;

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