KR100683939B1 - Composition of Solid Polymer Electrolyte Based on Interpenetrating Network Structure and Method Thereof - Google Patents

Abstract

The present invention relates to a novel solid polymer electrolyte composition and a method for preparing the same based on a cross-penetrating crosslinked structure, and more particularly, to a polyalkylene glycol polymer having excellent dissociation ability of lithium ions and a mobility of lithium ions. The present invention relates to a novel solid polymer electrolyte in which a high polysiloxane polymer is formed into a fully interpenetrating crosslinked structure and exhibits high ionic conductivity at room temperature without deterioration of mechanical properties.

The solid polymer electrolyte prepared according to the present invention not only has a high temperature ion conductivity value that can be applied to a lithium polymer secondary battery, but also improves safety problems such as leakage, so that the replacement of the conventional lithium secondary battery is Of course, it can be easily applied to a battery system that requires high safety.

Description

Composition of Solid Polymer Electrolyte Based on Interpenetrating Network Structure and Method Thereof}

1 is a graph showing the ion conductivity characteristics according to the temperature of the solid polymer electrolyte of the present invention.

The present invention relates to a novel solid polymer electrolyte composition and a method for preparing the same based on a cross-penetrating crosslinked structure, and more particularly, a polyalkylene glycol polymer having excellent dissociation ability of lithium ions and a mobility of lithium ions. The present invention relates to a novel solid polymer electrolyte in which a high polysiloxane polymer is formed into a fully interpenetrating crosslinked structure and exhibits high ionic conductivity at room temperature without deterioration of mechanical properties.

With the rapid development of the electric, electronic, communication and computer industries, the demand for high-performance, high-safety secondary batteries has gradually increased. Secondary batteries are also required to be lighter and smaller. In addition, the necessity of the development of electric vehicles to solve this problem has been increasing as the necessity of a new type of energy supply and demand caused by the exhaustion of oil and the depletion of oil due to the air pollution and noise caused by the mass distribution of automobiles has increased. There is a demand for development of a battery having a high output and a high energy density. One of the new high-performance, next-generation advanced batteries that has recently been in the spotlight in response to such demands is the lithium polymer battery (LPB), which has a higher energy density per unit weight than the conventional battery and has various forms. It is easy to develop high voltage and large capacity battery by lamination, and it is environmentally friendly because it does not use heavy metals that pollute the environment such as cadmium or mercury.

Lithium polymer secondary battery is largely composed of an anode (anode), a polymer electrolyte (polymer electrolyte), a cathode (cathode), lithium, carbon, etc. are used as the negative electrode active material, transition metal oxide, metal chalcogen compound as the positive electrode active material , Conductive polymers and the like are used. At this time, the polymer electrolyte is composed of a polymer, a salt, a non-aqueous organic solvent (optional), and other additives, and exhibits an ionic conductivity of about 10 ⁻³ to 10 ⁻⁸ S / cm at room temperature. Initial researches on polymer electrolytes have mainly been conducted on solid polymer electrolytes prepared by adding lithium salts to polyethylene oxide and polypropylene oxide, melting them in a co-solvent (Europe Patent No. 78505 and U.S. Patent No. 5,102,752). Due to the high crystallinity of, the ion conductivity was very low at room temperature.

In order to solve this problem, the inorganic nanoparticles were introduced into the solvent-free polymer electrolyte to obtain ion conductivity of ˜10 ^-5 S / cm at room temperature, but they are low values for commercialization. In contrast, plasticized polymer electrolytes prepared by adding organic solvents and lithium salts to polymers such as polymethyl methacrylate, polyacrylonitrile, polyvinyl chloride, and polyvinylidene fluoride, dissolved in a co-solvent and cast at room temperature High ion conductivity of ˜10 ⁻³ S / cm (M. Alamgir et al., J. power sources, 54, 40, 1995). However, plasticized polymer electrolytes are difficult to apply to commercialization systems due to the fundamental problems of safety due to the use of organic solvents and low mechanical properties due to the introduction of excess organic solvents.

The solid polymer electrolyte of the new structure of the present invention is prepared by using a polyethylene glycol excellent in dissociation of a polysilonic acid and a lithium salt in a liquid state at room temperature in an interpenetrating crosslinked structure to increase the mobility of lithium ions without using an organic solvent. It is to have a high ion conductivity characteristic without deterioration of mechanical properties. In particular, polysilonic acid crosslinking agents and polyethylene glycol crosslinking agents having different reaction mechanisms are used to make the cross-penetrating crosslinking structure.

The solid polymer electrolyte presented in the present invention is prepared based on two crosslinking reactions proceeded by different mechanisms, thereby forming a completely interpenetrating crosslinked structure.

In the present invention, polysiloxane (Formula 1) in which both ends are substituted with an epoxide group and polyalkylene glycol (Formula 2) in which both ends are substituted with an acrylate group have been developed as representative materials.

<Formula 1>

In Formula 1, R ₁ and R ₂ are each a hydrogen atom or a methyl group, X is -O-, -CH _2- , or -O (C = O) O-, m and n are each from 0 to 1000 P and q are integers between 0 and 20, respectively, and r and s are integers between 1 and 6, respectively.

<Formula 2>

In Formula 2, R ₃ and R ₄ are each a hydrogen atom or a methyl group, and n is an integer from 0 to 30.

In addition, the present invention (i) 0.1 to 95% by weight of the crosslinking agent represented by the formula (1) or (2); (ii) a plasticizer or two or more plasticizers using any one selected from polyalkylene glycol dialkyl ethers represented by the following formula (3) and polysiloxane substituted with polyalkylene glycol monoalkyl ethers represented by the formula (4): 0.1 to 80% by weight; (iii) 3 to 30 weight percent of a lithium salt; And (iv) a solid polymer electrolyte composition containing 0.5 to 5% by weight of an initiator.

<Formula 3>

R ₅ and R ₆ in Formula 3 are each a chain or branched alkyl group having 1 to 10 carbon atoms; R ₇ , R ₈ and R ₉ are each a hydrogen atom or a methyl group, and p, q and l are each an integer from 0 to 20.

<Formula 4>

In Formula 4, R ₁₀ , R _11, R _12, and R ₁₃ each represent a hydrogen atom or an alkyl group (more preferably, an alkyl group having 1 to 10 carbon atoms), m and n are each an integer between 0 and 1000, p and q are integers between 0 and 20, respectively.

In addition, in forming an interpenetrating crosslinking structure, a crosslinking agent in which both terminal groups of Formula 1 and Formula 2 are reversed may be used. That is, it can be prepared through a crosslinking reaction of polysiloxane (Chemical Formula 5) in which both ends are substituted with acrylate groups and polyethylene glycol (Chemical Formula 6) in which both ends are substituted with epoxide groups.

<Formula 5>

In the above formula, R ₁₄ , R _15, R ₁₆ and R ₁₇ are each a hydrogen atom or a methyl group, X is -O-, -CH _2- , or -O (C = O) O-, and m and n are Each is an integer between 0 and 1000, and p and q are each an integer between 0 and 20, respectively.

<Formula 6>

In the above formula, n is an integer from 0 to 30, r and s are each an integer from 1 to 6.

The present invention relates to a system capable of realizing high room temperature ion conductivity without deterioration of mechanical properties by designing a solid polymer electrolyte with a cross-penetrating crosslinked structure, which will be described in more detail below. In the case of a general solid polymer electrolyte, in order to increase the ionic conductivity, the content of a polymer having excellent mobility, such as polysiloxane, must be increased in the electrolyte, and the mechanical properties of the manufactured solid polymer electrolyte are inevitably weakened. In order to solve this problem, in the present invention, the polymer component having excellent mobility is also introduced in a crosslinked form. Among the commercially available polymers, the best mobility is polysiloxane, which has a very low glass transition temperature of -120 ° C and a liquid state at room temperature. The object of the present invention can be achieved by introducing an epoxide group or an acrylate group capable of crosslinking reaction at such polysiloxane ends.

Among the various crosslinking structures that can form the solid polymer electrolyte, the reason for selecting the interpenetrating crosslinking structure is as follows.

The most important role of the electrolyte is to properly dissociate the lithium salt and move the dissociated lithium ions from the positive electrode to the negative electrode or from the negative electrode to the positive electrode. This means that a component capable of properly dissociating a lithium salt and a component capable of properly displacing the lithium salt should be present in the electrolyte. To date, research has shown that it is difficult for one polymer component to perform the above role properly. Therefore, if the polymers that perform their respective roles are mixed at the molecular level, they may exhibit excellent ion conductivity. The solution is an interpenetrating crosslinked structure. The approach of constructing a simple blend or copolymer is not an appropriate approach due to the degradation of affinity or mechanical properties between polymers. Therefore, in the present invention, a cross-penetrating crosslinked structure using polyethylene glycol having excellent dissociation of lithium salts and polysiloxane having excellent mobility is designed.

Hereinafter, each composition component contained in the solid polymer electrolyte composition according to the present invention will be described in detail.

The composition of the present invention (i) contains a crosslinking agent represented by the above formulas (1) and (2) or a crosslinking agent represented by the formulas (5) and (6) in an appropriate ratio as a crosslinking agent.

The crosslinking agents represented by Formula 1 and Formula 5 are for good mobility of lithium ions because they are based on polysiloxanes. Since the crosslinking agents represented by the formulas (2) and (6) are based on polyethylene glycol components, they are for dissociation of high lithium salts and excellent mechanical properties of the solid polymer electrolyte. The content of each crosslinking agent may be appropriately adjusted according to the ion conductivity and mechanical properties. In the case of the polysiloxane-based crosslinking agent, the polyethylene glycol component is grafted to the polysiloxane main chain in order to improve the affinity with the polyethylene glycol component and the dissociation and migration characteristics of lithium ions.

In the case of the crosslinking agent, 0.1 to 95% by weight of the electrolyte composition of the present invention may be contained, preferably 5 to 70% by weight, more preferably 10 to 50% by weight.

(ii) The polyalkylene glycol dialkyl ether and polyalkylene glycol mono represented by the formulas (3) and (4) can be used in the compositions of the present invention to improve the dissociation of lithium salts and the mobility of lithium ions to improve ion conductivity The alkyl ether contains a single or two or more plasticizers selected from substituted polysiloxanes. If the plasticizer content is increased, the ion conductivity may be increased, but the mechanical properties are greatly reduced, making it difficult to thin the solid polymer electrolyte or introducing it into the battery manufacturing process. Because of this problem, the plasticizer may be contained in the composition of the present invention up to 0.1 to 70% by weight.

(iii) Any lithium salt may be used in the composition of the present invention as long as it is a lithium salt used for producing a conventional polymer electrolyte as a lithium salt. As a lithium salt that has been used in the past, for example, any one or more selected from LiClO ₄ , LiBF ₄ , LiCF ₃ SO ₃ , LiPF ₆ , LiAsF ₆ , and Li (CF ₃ SO ₂ ) ₂ N may be used. These lithium salts are used in the range of 3 to 30% by weight, preferably 5 to 15% by weight, based on the total composition of the electrolyte, but the amount can be appropriately adjusted according to the characteristics of the electrolyte composition.

(iv) Since the curable initiator is contained in the composition of the present invention, both a photocurable initiator and a thermosetting initiator may be used as the kind of initiator.

Examples of photocurable initiators include methylbenzoyl formate, igacure 250, ethylbenzoin ether, isopropylbenzoin ether, α-methylbenzoin ethylether, benzoin phenylether, α-acyl oxime ester, α, α-die Methoxy acetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2methyl-1-phenylpropan-1-one [Darocur 1173 from Ciba Geigy], 1-hydroxycyclo Hexyl phenyl ketone (Irgacure 184 from Ciba Geigy), Darocure 1116, Igacure 907 and the like and anthraquinone, 2-ethyl anthraquinone, 2-chloro anthraquinone, thioxanthone, isopropyl thi Any one or more selected from oxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl bonzoate, and myeller ketone can be used.

As an example of the thermosetting initiator, any one or more selected from peroxide and azoisobutyronitrile may be used.

The initiator is contained in the range of 0.1 to 5.0% by weight in the total composition, the amount can be adjusted according to the mixing ratio of the electrolyte composition.

The present invention also includes a method for producing a solid polymer electrolyte having an interpenetrating crosslinked structure.

In the solid polymer electrolyte manufacturing method of the interpenetrating crosslinked structure of the present invention, in the preparation of the solid polymer electrolyte of the interpenetrating crosslinking structure,

The crosslinking agent of the polymethylsiloxane represented by the formula (1) and the crosslinking agent of the polyalkylene glycol diacrylate represented by the formula (2) are mixed or the polymethyl siloxane crosslinking agent represented by the formula (5) and the polyalkylene glycol represented by the following formula (6) Mixing the call diacrylate crosslinking agent,

Using the plasticizers represented by the formulas (3) and (4) alone or in the mixture of the crosslinkers or adding the plasticizers of two or more mixtures to the mixture of the crosslinkers,

Adding a lithium salt to the mixture of the crosslinking agent and the plasticizer,

Adding an initiator to the mixture of the lithium salt-added crosslinking agent and the plasticizer and stirring the mixture to complete mixing;

The mixture is applied to a Teflon substrate in a sealed state in which moisture is blocked, and then, the ultraviolet rays are irradiated to prepare a solid polymer electrolyte.

<Formula 1>

In Formula 1, R ₁ , R ₂ are each a hydrogen atom or a methyl group, X is —O—, —CH ₂ —, or —O (C═O) O—, and m and n are each 0 to 1000 Integers, p and q are integers from 0 to 20, respectively, and r and s are integers from 1 to 6, respectively.

<Formula 2>

In Formula 2, R ₃ and R ₄ are each a hydrogen atom or a methyl group, and n is an integer from 0 to 30.

<Formula 3>

R ₅ and R ₆ in Formula 3 are each a chain or branched alkyl group having 1 to 10 carbon atoms; R ₇ , R ₈ and R ₉ are each a hydrogen atom or a methyl group, and p, q and l are each an integer from 0 to 20.

<Formula 4>

In Formula 4, R ₁₀ , R _11, R _12, and R ₁₃ each represent a hydrogen atom or an alkyl group (more preferably, an alkyl group having 1 to 10 carbon atoms), m and n are each an integer between 0 and 1000, p and q are integers between 0 and 20, respectively.

<Formula 5>

In Formula 5, R ₁₄ , R _15, R _16, and R ₁₇ each represent a hydrogen atom or a methyl group, X is -O-, -CH _2- , or -O (C = O) O-, and m and n Are each an integer between 0 and 1000, and p and q are each an integer between 0 and 20, respectively.

<Formula 6>

In Chemical Formula 6, n is an integer of 0 to 30, and r and s are each an integer of 1 to 6.

In the above, since the lithium salt and the initiator can use the above-described details will be omitted below.

The ultraviolet irradiation can be irradiated at a wavelength of 100 to 500 nm for 1 to 10 minutes.

On the other hand, the present invention includes a lithium-polymer secondary battery comprising a polymer electrolyte made of the above-mentioned interpenetrating crosslinked polymer electrolyte composition.

The present invention will be described in more detail based on the following Preparation Examples and Examples. However, these are not limited to the scope of the present invention by these as an embodiment of the present invention.

Preparation Example 1 Synthesis of Polyethylene Glycol Graft Polysiloxane Diglycidyl Ether (Formula 1, X = -O-)

After the agitator, thermometer, magnetic bar and nitrogen injector were installed in a 500 ml three-necked flask, nitrogen was flowed for 2 hours or more to remove impurities present in the flask.

To 200 ml of tetrahydrofuran dried with metallic sodium / benzophenone, 14.9 g of polydimethylsiloxane-methylhydrosiloxane copolymer (Mn = 550 g / mol, m = n = 4) and excess sodium hydride (NaH) were added. 5 g of epichlorohydrin was added and reacted for 12 hours.

After the reaction, the sodium chloride salt formed was filtered off, and the tetrahydrofuran solvent was removed under reduced pressure to obtain a product. The formed product was subjected to dehydrogenation reaction by addition of polyethylene glycol monomethyl ether (Mn = 164 g / mol, a = 3) under a catalyst of K ₂ CO ₃ , and then the catalyst, salt and solvent were removed to obtain polyethylene as a product. Glycol graft polysiloxane diglycidyl ether (Formula 1, X = -O-) was obtained.

The process concerning the said preparation example was briefly summarized by the following scheme.

<Scheme 1>

Preparation Example 2 Synthesis of Polyethylene Glycol Graft Polysiloxane Diglycidyl Ether (Formula 1, X = -CH _2- )

After the stirring apparatus, the thermometer, the magnetic bar, and the nitrogen injection apparatus were installed in the 500 ml three-necked flask, nitrogen was flowed for 2 hours or more before the start of the reaction to remove impurities present in the flask.

To 200 ml of tetrahydrofuran dried with metallic sodium / benzophenone, 14.9 g of polydimethylsiloxane-methylhydrosiloxane copolymer (Mn = 550 g / mol, m = n = 4) and excess sodium hydride (NaH) were added. , 5 g of epichlorohydrin is added and reacted for 12 hours.

After the reaction, the sodium chloride salt formed was filtered off, and the tetrahydrofuran solvent was removed under reduced pressure to obtain a product.

The formed product was reacted at 70 DEG C for at least 12 hours using tetrahydrofuran as a solvent under the Pt catalyst and polyethylene glycol methyl ether methacrylate (Mn = 300 g / mol, b = 4.55). Removal of the solvent affords the product polyethyleneglycol graft polysiloxane diglycidyl ether (Formula 1, X = -CH _2- ).

Scheme 2

Preparation Example 3 Synthesis of Polyethylene Glycol Graft Polysiloxane Dimethyl Methacrylate (Formula 5)

After the stirring apparatus, the thermometer, the magnetic bar, and the nitrogen injection apparatus were installed in the 500 ml three-necked flask, nitrogen was flowed for 2 hours or more before the start of the reaction to remove impurities present in the flask.

To 200 ml of tetrahydrofuran dried with metallic sodium / benzophenone, 10 g of polydimethylsiloxane-methylhydrosiloxane copolymer (Mn = 550 g / mol, m = n = 4) and excess triethylamine were added. Thereafter, 3.92 g of methacryloyl chloride was added and reacted for 12 hours. At the end of the reaction, the formed triethylamine-hydrogen chloride complex salt was removed by centrifugation, and then the tetrahydrofuran solvent was removed under reduced pressure to obtain a product. The obtained product is removed with residual salts and impurities using chloroform / 3rd distilled water to obtain an intermediate. The intermediate formed was subjected to dehydrogenation reaction by addition of polyethylene glycol monomethyl ether (Mn = 164 g / mol, a = 3) under a catalyst of K ₂ CO ₃ , followed by removal of the catalyst, salt and solvent. Polyethylene glycol graft polysiloxane dimethylmethacrylate (Formula 5, X = -O-) was obtained.

Scheme 3

<Example 1>

Polyethyleneglycol graft polysiloxane diglycidyl ether represented by Formula 1 prepared in Preparation Example 1 (Mn = 1200) and polyethyleneglycol dimethacrylate represented by Formula 2 (Mn = 400, n = 5.6) Was mixed in the same ratio as in Table 1.

Lithium bistrifluorosulfonylimide (Li (CF ₃ SO ₂ ) ₂ N) was added to the mixture with a lithium salt such that the EO: Li ratio was 20: 1, and then methylbenzoylformate or epoxide was used as an acrylate initiator. Igacure 250 was introduced as a side initiator and stirred to mix thoroughly.

After applying the mixture onto a Teflon substrate in a glove box, a solid polymer electrolyte was prepared by irradiating UV light at 350 nm wavelength for about 5 minutes in a closed state.

The prepared solid polymer electrolyte was laminated between stainless steel symmetric electrodes to assemble a cell, and then the resistance of the electrolyte was measured by using an alternating current impedance method, and the ion conductivity was calculated using the same. The results are shown in Table 1.

TABLE 1

division Crosslinker content Specialization Formula 1 Formula 2 Ion Conductivity (25 ℃) Mechanical properties Example 1-1 2.0 g 0.0g 6.0 × 10 ^-6 S / cm Very good Example 1-2 1.5 g 0.5g 8.4 × 10 ^-5 S / cm Great Example 1-3 1.0 g 1.0 g 3.4 × 10 ^-4 S / cm Great Example 1-4 0.5g 1.5 g 5.2 × 10 ^-4 S / cm usually Example 1-5 0.0g 2.0 g 6.5 × 10 ^-4 S / cm Bad

<Example 2>

In preparing the mixtures of Examples 1 to 3, 0.2 g, 0.5 g, 1.0 g, 1.5 g, and 2.0 g of polyethylene glycol dimethyl ether (Mn = 250 g / mol) represented by Chemical Formula 3 were added as plasticizers, respectively. A polymer electrolyte was prepared. Ion conductivity was measured in the same manner as in Example, and the results are shown in Table 2.

TABLE 2

division Plasticizer content Characterization Ion Conductivity (25 ℃) Mechanical properties Example 2-1 0.2 g 4.2 × 10 ^-4 S / cm Great Example 2-2 0.5g 5.2 × 10 ^-4 S / cm Great Example 2-3 1.0 g 5.7 × 10 ^-4 S / cm usually Example 2-4 1.5 g 6.5 × 10 ^-4 S / cm Bad Example 2-5 2.0 g 8.2 × 10 ^-4 S / cm Very bad

<Example 3>

The ionic conductivity of the solid polymer electrolyte of Example 1-3 according to the temperature change is shown in FIG. 1.

Since the solid polymer electrolyte according to the present invention is based on a novel interpenetrating crosslinked structure, it exhibits high ionic conductivity while maintaining excellent mechanical properties. In addition, due to the excellent mechanical properties can be induced to further increase the ion conductivity through the introduction of a plasticizer. Therefore, it may be applicable as a new electrolyte material of a lithium secondary battery to be applied to electronic devices or electric vehicles requiring high safety.

Claims (8)

A solid polymer electrolyte having an interpenetrating crosslinked structure, which is prepared by crosslinking a polymethyl siloxane crosslinking agent represented by the following Chemical Formula 1 and a polyalkylene glycol diacrylate crosslinking agent represented by the following Chemical Formula 2. <Formula 1>

In Formula 1, R ₁ , R ₂ are each a hydrogen atom or a methyl group, X is —O—, —CH ₂ —, or —O (C═O) O—, and m and n are each 0 to 1000 Integers, p and q are each an integer from 0 to 20, and r and s are each an integer from 1 to 6; <Formula 2>

In Formula 2, R ₃ and R ₄ are each a hydrogen atom or a methyl group, and n is an integer from 0 to 30. A solid polymer electrolyte having an interpenetrating crosslinking structure, which is prepared by crosslinking a polymethyl siloxane crosslinking agent represented by Formula 5 and a polyethylene glycol substituted at both ends represented by the following Formula 6 with an epoxide group. <Formula 5>

In Formula 5, R ₁₄ , R _15, R _16, and R ₁₇ each represent a hydrogen atom or a methyl group, X is -O-, -CH _2- , or -O (C = O) O-, and m and n Are each an integer between 0 and 1000, and p and q are each an integer between 0 and 20, respectively. <Formula 6>

In Chemical Formula 6, n is an integer of 0 to 30, and r and s are each an integer of 1 to 6.  The crosslinking agent content is 0.1-95 weight%, The polyalkylene glycol dialkyl ether represented by General formula (3), and the polyalkylene glycol monoalkyl ether represented by general formula (4) are substituted. An interpenetrating crosslinked polymer electrolyte composition comprising 0.1 to 80% by weight of a single or two or more plasticizers selected from polysiloxanes, 3 to 30% by weight of a lithium salt and 0.5 to 5% by weight of an initiator. <Formula 3>

R ₅ and R ₆ in Formula 3 are each a chain or branched alkyl group having 1 to 10 carbon atoms; R ₇ , R ₈ and R ₉ are each a hydrogen atom or a methyl group, and p, q and l are each an integer from 0 to 20. <Formula 4>

In Formula 4, R ₁₀ , R _11, R _12, and R ₁₃ each represent a hydrogen atom or an alkyl group (more preferably, an alkyl group having 1 to 10 carbon atoms), m and n are each an integer between 0 and 1000, p and q are integers between 0 and 20, respectively. The method of claim 3, wherein the lithium salt is at least one selected from LiClO ₄ , LiBF ₄ , LiCF ₃ SO ₃ , LiPF ₆ , LiAsF ₆ , Li (CF ₃ SO ₂ ) ₂ N of the interpenetrating crosslinked structure Polymer electrolyte composition. 4. The polymer electrolyte composition of claim 3, wherein the initiator uses any one or more selected from the following photocurable initiators and thermosetting initiators. Photocurable initiators: methylbenzoyl formate, igacure 250, ethylbenzoin ether, isopropylbenzoin ether, α-methylbenzoin ethyl ether, benzoin phenyl ether, α-acyl oxime ester, α, α-diethoxy aceto Phenone, 1,1-dichloroacetophenone, 2-hydroxy-2methyl-1-phenylpropan-1-one [Darocur 1173 from Ciba Geigy], 1-hydroxycyclohexyl phenyl Ketones (Irgacure 184 from Ciba Geigy), Tarocure 1116, Igacure 907 and the like, anthraquinone, 2-ethyl anthraquinone, 2-chloro anthraquinone, thioxanthone, isopropyl thioxanthone , Chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl bonzoate, mychler ketone. Thermosetting initiator: peroxide type, azoisobutyronitrile type. In the preparation of a solid polymer electrolyte having an interpenetrating crosslinking structure, Either the crosslinking agent of the polymethylsiloxane represented by the formula (1) and the crosslinking agent of the polyalkylene glycol diacrylate represented by the formula (2) are mixed or the polymethylsiloxane crosslinking agent represented by the formula (5) and both ends of the following formula (6) Mixing polyethylene glycol substituted with a side group, Using the plasticizers represented by the formulas (3) and (4) alone or in the mixture of the crosslinkers or adding the plasticizers of two or more mixtures to the mixture of the crosslinkers, Adding a lithium salt to the mixture of the crosslinking agent and the plasticizer, Adding an initiator to the mixture of the lithium salt-added crosslinking agent and the plasticizer and stirring the mixture to complete mixing; A method of producing a polymer electrolyte composition having an interpenetrating cross-linked structure, comprising applying the mixture to a Teflon substrate in a sealed state in which moisture is blocked and then irradiating ultraviolet rays to prepare a solid polymer electrolyte. <Formula 1>

In Formula 1, R ₁ , R ₂ are each a hydrogen atom or a methyl group, X is —O—, —CH ₂ —, or —O (C═O) O—, and m and n are each 0 to 1000 Integers, p and q are integers from 0 to 20, respectively, and r and s are integers from 1 to 6, respectively. <Formula 2>

In Formula 2, R ₃ and R ₄ are each a hydrogen atom or a methyl group, and n is an integer from 0 to 30. <Formula 3>

R ₅ and R ₆ in Formula 3 are each a chain or branched alkyl group having 1 to 10 carbon atoms; R ₇ , R ₈ and R ₉ are each a hydrogen atom or a methyl group, and p, q and l are each an integer from 0 to 20. <Formula 4>

In Formula 4, R ₁₀ , R _11, R _12, and R ₁₃ each represent a hydrogen atom or an alkyl group (more preferably, an alkyl group having 1 to 10 carbon atoms), m and n are each an integer between 0 and 1000, p and q are integers between 0 and 20, respectively. <Formula 5>

In Formula 5, R ₁₄ , R _15, R _16, and R ₁₇ each represent a hydrogen atom or a methyl group, X is -O-, -CH _2- , or -O (C = O) O-, and m and n Are each an integer between 0 and 1000, and p and q are each an integer between 0 and 20, respectively. <Formula 6>

In Chemical Formula 6, n is an integer of 0 to 30, and r and s are each an integer of 1 to 6. The method of claim 6, wherein the ultraviolet ray is irradiated at a wavelength of 100 to 500 nm for 1 to 10 minutes. A lithium-polymer secondary battery comprising a polymer electrolyte comprising the polymer electrolyte composition of the interpenetrating crosslinked structure according to claim 1.

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