KR102826687B1 - Gel polymer electrolyte comprising cross-linked structure in ionic liquid form amd method of preparing same - Google Patents

Abstract

A gel polymer electrolyte including a cross-linked structure in the form of an ionic liquid and a method for producing the same are disclosed. The gel polymer electrolyte includes an acrylonitrile-based polymer having an azide group (-N ₃ ) and tetrazolium that self-cross-links the acrylonitrile-based polymer, and includes a tetrazolium cross-linked polymer having a positive charge; a counter ion having a negative charge; and a liquid electrolyte; thereby having the effects of excellent lithium ion conduction efficiency and mechanical strength.

Description

Gel polymer electrolyte comprising cross-linked structure in ionic liquid form and method of preparing same {GEL POLYMER ELECTROLYTE COMPRISING CROSS-LINKED STRUCTURE IN IONIC LIQUID FORM AMD METHOD OF PREPARING SAME}

The present invention relates to a gel polymer electrolyte including a cross-linked structure in the form of an ionic liquid and a method for producing the same.

Gel polymer electrolytes can improve safety by minimizing the use of highly volatile organic electrolytes that liquid electrolytes have, thereby solving the leakage problem of electrolytes, and can improve the performance of lithium-ion batteries by controlling unnecessary interfacial phenomena (SEI, Li dendrite) that occur between electrodes and interfaces through efficient lithium ion conduction. In general, polymer electrolytes are applied to lithium-ion batteries through additives and ion accelerators in the form of general-purpose polymers such as PEO and PAN that can help ion conduction.

However, conventional gel polymer electrolytes have a problem in that although they have high ionic conductivity due to the combination of liquid electrolyte and functional polymer, their mechanical strength is significantly reduced because the liquid electrolyte is added between the polymer electrolytes. In order to improve this, studies have been conducted to introduce a cross-linking structure into the polymer structure to increase the mechanical strength. However, a cross-linking structure that simply increases the mechanical strength reduces the electrochemical properties of the gel polymer electrolyte, so this needs to be improved.

Therefore, research on a gel polymer electrolyte with high ion conductivity and lithium ion conduction efficiency and excellent mechanical strength and a method for producing the same is required.

The purpose of the present invention is to solve the above problems, and to provide a gel polymer electrolyte having high ion conductivity and lithium ion conduction efficiency and excellent mechanical strength, and a method for producing the same.

In addition, the present invention provides a method for producing a gel polymer electrolyte by a simple method, which enables mass production and application to actual lithium ion batteries.

According to one aspect of the present invention, a gel polymer electrolyte is provided, which comprises: an acrylonitrile-based polymer having an azide group (-N ₃ ); a tetrazolium cross-linking polymer having a positive charge; a counter ion having a negative charge; and a liquid electrolyte.

Additionally, the tetrazolium cross-linked polymer may be ionically bonded with the counter ion.

Additionally, the counter ion may include a sulfonimide compound having a negative charge or a sulfonamide compound having a negative charge.

In addition, the counter ion may include at least one selected from the group consisting of bis(trifluoromethylsulfonyl)imide (TFSI ^- ), tetrafluoroborate (BF ₄ ^- ), hexafluorophosphate (PF ₆ ^- ), chloride (Cl ^- ), 1,1,2,2-tetrafluoroethanesulfonate (C ₂ HF ₄ KO ₃ S ^- ), methanesulfonate (C ₂ H ₆ O ₃ S ^- ), and tetraphenylborate (BPh ₄ ^- ).

In addition, the gel polymer electrolyte may have a bi-continuous phasic structure in which the tetrazolium cross-linked polymer forms a first continuous phase and the counter ions form a second continuous phase.

Additionally, the second continuous phase can form an ion channel.

In addition, the acrylonitrile-based polymer may include at least one selected from the group consisting of polyacrylonitrile-co-vinylidene azide, polyacrylonitrile, poly(acrylonitrile-co-methylmethacrylate), poly(acrylonitrile-co-methacrylic acid), poly(acrylonitrile-co-methylacrylonitrile), poly(lithium acrylonitrile-co-methacrylate), poly(acrylonitrile-co-vinylidene chloride), and poly(acrylonitrile-co-vinyl chloride).

In addition, the acrylonitrile-based polymer may include polyacrylonitrile-co-vinylidene azide represented by the structural formula 1 below.

[Structural formula 1]

In the above structural formula 1,

n is an integer between 1 and 500,

m is an integer between 5 and 2,000.

Additionally, the tetrazolium cross-linked polymer may be represented by the structural formula 2 below.

[Structural formula 2]

In the above structural formula 2,

n is an integer between 1 and 500,

m is an integer between 5 and 2,000,

R ¹ is a C1 to C5 alkyl group.

In addition, the liquid electrolyte may include at least one selected from the group consisting of propylene carbonate, ethylene carbonate, diethyl carbonate, and dimethyl carbonate in which at least one selected from the group consisting of lithium bis(trifluoromethylsulfonyl)imide ( _LiTFSI ) and lithium hexafluorophosphate (LiPF 6 ) is dissolved.

Additionally, the thickness of the gel polymer electrolyte may be 20 to 500 μm.

According to another aspect of the present invention, an energy storage device comprising the gel polymer electrolyte is provided.

Additionally, the energy storage device may be any one selected from the group consisting of a transistor, a super capacitor, and a lithium secondary battery.

According to another aspect of the present invention, a method for producing a gel polymer electrolyte is provided, comprising: (a) preparing a mixed solution comprising an azide (-N ₃ ) group-containing acrylonitrile-based polymer and a counter ion precursor; (b) preparing a polymer electrolyte by casting the mixed solution and performing a heat treatment to evaporate a solvent, thereby performing a crosslinking reaction and a quaternization reaction; and (c) preparing a gel polymer electrolyte by supporting a liquid electrolyte on the polymer electrolyte; wherein the gel polymer electrolyte comprises an acrylonitrile-based polymer having an azide (-N ₃ ) group and tetrazolium that self-crosslinks the acrylonitrile-based polymer, and comprises a tetrazolium crosslinked polymer having a positive charge; a negatively charged counter ion; and a liquid electrolyte.

Additionally, the ratio of the molar ratio (mol _c ) of the counter ion precursor to the molar ratio (mol _N3 ) of the azide group ( _-N3 ) of the acrylonitrile-based polymer (mol _c /mol _N3 ) may be 2 to 6.

Additionally, the heat treatment of step (b) can be performed at a temperature of 100 to 150°C.

Additionally, the gel polymer electrolyte may contain 1 to 500 parts by weight of the liquid electrolyte based on 100 parts by weight of the polymer electrolyte.

In addition, the counter ion precursor may include at least one selected from the group consisting of N-alkyl sulfone imide compounds and N-alkyl sulfone amide compounds, and each of the alkyls may have 1 to 5 carbon atoms.

The gel polymer electrolyte of the present invention has excellent lithium ion conduction efficiency and mechanical strength by introducing a cross-linked structure in the form of an ionic liquid, and due to the high liquid electrolyte affinity of polyacrylonitrile within the gel polymer electrolyte, efficient lithium ion conductivity can be secured even with a small amount of liquid electrolyte.

In addition, the gel polymer electrolyte of the present invention is manufactured through a solution process, so the manufacturing process is simple and mass production is possible.

Since these drawings are for reference in explaining exemplary embodiments of the present invention, the technical ideas of the present invention should not be interpreted as limited to the attached drawings.
Figure 1 illustrates the structure of a gel polymer electrolyte according to one embodiment of the present invention.
Figure 2 illustrates a method for manufacturing a gel polymer electrolyte according to one embodiment of the present invention.
Figure 3 shows the results of FTIR, ¹⁹ F NMR, and ⁷ Li NMR analyses of Example 1 and Comparative Example 1.
Figure 4 shows an Arrhenius plot of gel polymer electrolytes manufactured according to Examples 1 to 3.
FIG. 5 shows current graphs over time of gel polymer electrolytes manufactured according to Examples 1 to 3 (upper left), impedance values before and after polarization of gel polymer electrolytes manufactured according to Example 1 (upper right), impedance values before and after polarization of gel polymer electrolytes manufactured according to Example 2 (lower left), and impedance values before and after polarization of gel polymer electrolytes manufactured according to Example 3 (lower right).
Figure 6 shows the capacity change and coulombic efficiency according to the cycle of the half-cell manufactured using the gel polymer electrolyte manufactured according to Examples 1 to 3 (top), the capacity change according to the cycle of the half-cell at a charge/discharge rate of 0.5 C (middle), and the capacity change according to the cycle of the half-cell at a charge/discharge rate of 3 C (bottom).

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and if it is determined that a detailed description of a related known technology may obscure the gist of the present invention when explaining the present invention, the detailed description is omitted.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this application, the terms "comprises" or "has" and the like are intended to specify the presence of a feature, number, step, operation, component, or combination thereof described in the specification, but should be understood to not preclude the presence or addition of one or more other features, numbers, steps, operations, components, or combinations thereof.

Also, terms including ordinal numbers such as first, second, etc., which will be used hereinafter, may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.

Additionally, when it is said that a component is "formed on" or "laminated on" another component, it should be understood that it may be formed or laminated directly on the entire surface or one side of the other component, but there may also be other components present in between.

Hereinafter, a gel polymer electrolyte including a cross-linked structure in the form of an ionic liquid and a method for producing the same will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is defined only by the scope of the claims described below.

Figure 1 illustrates the structure of a gel polymer electrolyte according to one embodiment of the present invention.

Referring to FIG. 1, the present invention provides a gel polymer electrolyte including an acrylonitrile-based polymer having an azide group (-N ₃ ) and tetrazolium that self-cross-links the acrylonitrile-based polymer, the tetrazolium-based polymer having a positive charge; a counter ion having a negative charge; and a liquid electrolyte.

Additionally, the tetrazolium cross-linked polymer may be ionically bonded with the counter ion.

Additionally, the counter ion may include a sulfonimide compound having a negative charge or a sulfonamide compound having a negative charge.

In addition, the counter ion may ^include at least one selected from the group consisting of bis(trifluoromethylsulfonyl)imide (TFSI ^- ), tetrafluoroborate (BF ₄ ^- ), hexafluorophosphate (PF ₆ ^- ), chloride (Cl ^- ), 1,1,2,2-tetrafluoroethanesulfonate (C ₂ HF ₄ KO ₃ S - ), methanesulfonate (C ₂ H ₆ O ₃ S ^{- )} , and tetraphenylborate (BPh ₄ - ), preferably at least one selected from the group consisting of bis(trifluoromethylsulfonyl)imide (TFSI ^- ) and hexafluorophosphate (PF ₆ ^- ), and more preferably bis(trifluoromethylsulfonyl)imide (TFSI ^- ).

In addition, the gel polymer electrolyte may have a bi-continuous phasic structure in which the tetrazolium cross-linked polymer forms a first continuous phase and the counter ions form a second continuous phase.

Additionally, the second continuous phase can form an ion channel.

In addition, the acrylonitrile-based polymer may include at least one selected from the group consisting of polyacrylonitrile-co-vinylidene azide, polyacrylonitrile, poly(acrylonitrile-co-methylmethacrylate), poly(acrylonitrile-co-methacrylic acid), poly(acrylonitrile-co-methylacrylonitrile, poly(lithium acrylonitrile-co-methacrylate), poly(acrylonitrile-co-vinylidene chloride), and poly(acrylonitrile-co-vinyl chloride), and preferably may include polyacrylonitrile-co-vinylidene azide represented by the following structural formula 1.

[Structural formula 1]

In the above structural formula 1,

n is an integer between 1 and 500,

m is an integer between 5 and 2,000.

Additionally, the tetrazolium cross-linked polymer may be represented by the structural formula 2 below.

[Structural formula 2]

In the above structural formula 2,

n is an integer between 1 and 500,

m is an integer between 5 and 2,000,

R ¹ is a C1 to C5 alkyl group.

In addition, the liquid electrolyte may include at least one selected from the group consisting of propylene carbonate, ethylene carbonate, diethyl carbonate, and dimethyl carbonate in which at least one selected from the group consisting of lithium bis(trifluoromethylsulfonyl)imide ( _LiTFSI ) and lithium hexafluorophosphate (LiPF 6 ) is dissolved.

In addition, the thickness of the gel polymer electrolyte may be 20 to 500 μm. If the thickness is less than 20 μm, it is too thin and the mechanical strength becomes low, which is not preferable, and if it exceeds 500 μm, the lithium ion conduction distance between the positive and negative electrodes becomes long, which is not preferable because it is not efficient for application to a battery.

The present invention provides an energy storage device including the gel polymer electrolyte.

Additionally, the energy storage device may be any one selected from the group consisting of a transistor, a super capacitor, and a lithium secondary battery.

In addition, the energy storage device is a lithium secondary battery, and the gel polymer electrolyte can be used in the form of a separator impregnated with the electrolyte of the lithium secondary battery.

Figure 2 illustrates a method for manufacturing a gel polymer electrolyte according to one embodiment of the present invention.

Referring to FIG. 2, the present invention provides a method for producing a gel polymer electrolyte, comprising: (a) a step of producing a mixed solution including an azide (-N ₃ ) group-containing acrylonitrile-based polymer and a counter ion precursor; (b) a step of casting the mixed solution and heat-treating it to evaporate a solvent, thereby causing a crosslinking reaction and a quaternization reaction to produce a polymer electrolyte; and (c) a step of supporting a liquid electrolyte on the polymer electrolyte to produce a gel polymer electrolyte; wherein the gel polymer electrolyte includes an acrylonitrile-based polymer having an azide (-N ₃ ) group and tetrazolium that self-crosslinks the acrylonitrile-based polymer, and includes a tetrazolium crosslinked polymer having a positive charge; a counter ion having a negative charge; and a liquid electrolyte.

In addition, the ratio of the molar ratio (mol _c ) of the counter ion precursor to the molar ratio (mol _N3 ) of the azide group (-N ₃ ) of the acrylonitrile-based polymer (mol _c /mol _N3 ) may be 2 to 6. When the molar ratio is less than 2, the quaternization reaction between the tetrazolium formed by the self-crosslinking of the acrylonitrile-based polymer and the anion precursor does not sufficiently occur, so that the crosslinking structure in the form of an ionic liquid cannot be sufficiently introduced, which is undesirable. When the molar ratio exceeds 6, the amount of the anion precursor used is excessive, which is economically inefficient, which is undesirable.

In addition, the heat treatment of step (b) may be performed at a temperature of 100 to 150°C, and preferably at a temperature of 120 to 140°C. If step (b) is performed at a temperature of less than 100°C, the self-crosslinking reaction (azide nitrile cycloaddition) of the polyacrylonitrile polymer does not sufficiently occur, which is undesirable, and if it exceeds 150°C, reaction by-products may be formed, which is undesirable.

In addition, the gel polymer electrolyte may contain 1 to 500 parts by weight of the liquid electrolyte based on 100 parts by weight of the polymer electrolyte, and preferably 20 to 200 parts by weight. If the liquid electrolyte is less than 1 part by weight, the ion conductivity of the gel polymer electrolyte is not sufficient, which is not preferable, and if it exceeds 500 parts by weight, the mechanical strength is significantly reduced, which is not preferable.

In addition, the counter ion precursor may include at least one selected from the group consisting of N-alkyl sulfone imide compounds and N-alkyl sulfone amide compounds, and each of the alkyls may have 1 to 5 carbon atoms.

[Example]

Hereinafter, preferred embodiments of the present invention will be described. However, these are provided for illustrative purposes only and the scope of the present invention is not limited thereby.

Manufacturing of gel polymer electrolytes

Figure 2 illustrates a method for producing a gel polymer electrolyte according to one embodiment of the present invention. With reference to Figure 2, gel polymer electrolytes of Examples 1 to 3 were produced.

Example 1: PANVDACIL 73

According to the reaction scheme 1 below, poly(acrylonitrile-co-vinylidene chloride) (PANVDC) was reacted with sodium azide and potassium iodide at 65 ℃ for 24 hours to replace Cl with N ₃ to form poly(acrylonitrile-co-vinylidene azide) (PANVDA).

[Reaction Formula 1]

In the above reaction formula 1,

m is 70 and n is 30. (In the PANVDA polymer, the ratio of acrylonitrile (AN) monomer to vinylidene azide (VDA) monomer is 7:3.)

A mixed solution was prepared by adding 10 vol% of N-methyl bis[(trifluoromethyl)sulfonyl]imide (N-methyl TFSI) to a dimethylformamide (DMF) solution containing 5 wt% of the above PANDVA. After pouring the mixed solution into a mold, solvent casting was performed at 130° C. for 24 hours to prepare a polymer electrolyte comprising an acrylonitrile-based polymer having an azide group (-N ₃ ) and a tetrazolium that self-cross-links the acrylonitrile-based polymer, a tetrazolium cross-linked polymer having a positive charge, and a counter ion having a negative charge. The preparation of the polymer electrolyte was carried out according to the following Reaction Scheme 2.

[Reaction Formula 2]

In the above reaction formula 2,

m is 70 and n is 30.

A gel polymer electrolyte was prepared by adding 0.1 mL to 10 mL of propylene carbonate (PC) containing 1.0 M lithium bis(trifluoromethylsulfonyl)imide (Li-TFSI) as a liquid electrolyte to the above polymer electrolyte.

Example 2: PANVDACIL 82

A gel polymer electrolyte was prepared in the same manner as in Example 1, except that instead of m being 70 and n being 30 in the above reaction schemes 1 and 2, m was 80 and n was 20 (using PANVDACIL polymer having an AN:VDA monomer ratio of 8:2).

Example 3: PANVDACIL 91

A gel polymer electrolyte was prepared in the same manner as in Example 1, except that instead of m being 70 and n being 30 in the above reaction schemes 1 and 2, m was 90 and n was 10 (using PANVDACIL polymer with an AN:VDA monomer ratio of 9:1).

Comparative Example 1:

Polypropylene carbonate (PC) containing 1.0 M lithium bis(trifluoromethylsulfonyl)imide (Li-TFSI) was used as comparative example 1.

[Example]

Test Example 1: Confirmation of interaction of gel polymer electrolyte

Figure 3 shows the results of FTIR, ¹⁹ F NMR, and ⁷ Li NMR analyses of Example 1 and Comparative Example 1.

According to FIG. 3, the FTIR analysis results show that the gel polymer electrolyte (PANVDACIL 73 with 1.0 M LiTFSI in PC) manufactured according to Example 1 contains polypropylene carbonate (PC) molecules interacting with the nitrile functional groups inside the polymer electrolyte.

In addition, the NMR analysis results show that, unlike the liquid electrolyte of Comparative Example 1 (1.0 M LiTFSI in PC), the gel polymer electrolyte (PANVDACIL 73 with 1.0 M LiTFSI in PC) manufactured according to Example 1 shows interactions between TFSI ^- and Li ⁺ and the polymer electrolyte.

Test Example 2: Confirmation of ionic conductivity according to internal composition of gel polymer electrolyte

Figure 4 shows an Arrhenius plot of gel polymer electrolytes manufactured according to Examples 1 to 3.

According to FIG. 4, it can be confirmed that Example 1 (PANVDACIL 73) with a high cross-linking ratio of the ionic liquid has the highest ionic liquid functional group and thus exhibits the highest lithium ion conductivity.

Test Example 3: Confirmation of Lithium Ion Conductivity of Gel Polymer Electrolyte

FIG. 5 shows current graphs over time of gel polymer electrolytes manufactured according to Examples 1 to 3 (upper left), impedance values before and after polarization of gel polymer electrolytes manufactured according to Example 1 (upper right), impedance values before and after polarization of gel polymer electrolytes manufactured according to Example 2 (lower left), and impedance values before and after polarization of gel polymer electrolytes manufactured according to Example 3 (lower right).

The lithium ion conduction efficiency (t ₊ ) can be determined using Fig. 5 and Equation 1 below.

[Formula 1]

In the above equation 1,

I _SS is the current when the current is constant after polarization (Steady state),

I ₀ is the initial current value (before polarization),

R _SS is the resistance value when the current is constant after polarization,

R ₀ is the initial resistance value (before polarization),

V is the voltage applied at this time (10 mV).

The lithium ion conduction efficiency (t ₊ ) of Examples 1 to 3 is summarized in Table 1 below.

division Lithium ion conduction efficiency (t ₊ ) Example 1 (PANVDACIL 73) 0.922 Example 2 (PANVDACIL 82) 0.724 Example 3 (PANVDACIL 91) 0.594

According to Table 1 and FIG. 5 above, the transfer efficiency of only lithium cations among all ion species of the gel polymer electrolytes manufactured according to Examples 1 to 3 can be known, and it can be confirmed that PANVDACIL 73 showed the best lithium ion conduction efficiency of 0.922.

Test Example 4: Checking Half-cell Operation Data

Each of the gel polymer electrolytes manufactured according to Examples 1 to 3 was used to manufacture three types of half-cells using lithium iron phosphate (LFP) cathode material and lithium. The LFP cathode material was manufactured by mixing cathode active material (LiFePO ₄ ): conductive material: binder (PVDF) in a weight ratio of 8: 1: 1, adding a small amount of NMP solvent to make a slurry, applying the slurry to an aluminum current collector, drying, and compressing through hot pressing.

Figure 6 shows the capacity change and coulombic efficiency according to the cycle of the half-cell manufactured using the gel polymer electrolyte manufactured according to Examples 1 to 3 (top), the capacity change according to the cycle of the half-cell at a charge/discharge rate of 0.5 C (middle), and the capacity change according to the cycle of the half-cell at a charge/discharge rate of 3 C (bottom).

According to FIG. 6, it can be confirmed that the rate characteristics of the gel polymer electrolyte (PANVDACIL 73) manufactured according to Example 1 are superior to those of Example 2 (PANVDACIL 82) and Example 3 (PANVDACIL 91), and that it has stable cycle characteristics of more than 300 cycles at a charge/discharge rate of 3 C.

The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims (18)

An acrylonitrile-based polymer having an azide group (-N ₃ ) and a tetrazolium-containing polymer that self-cross-links the acrylonitrile-based polymer, the tetrazolium-based polymer having a positive charge;
a counter ion having a negative charge; and
liquid electrolyte;
A gel polymer electrolyte comprising: In the first paragraph,
A gel polymer electrolyte characterized in that the tetrazolium cross-linked polymer ionically bonds with the counter ion. In the first paragraph,
A gel polymer electrolyte characterized in that the counter ion comprises a sulfonimide compound having a negative charge or a sulfonamide compound having a negative charge. In the first paragraph,
A gel polymer electrolyte, characterized in that the counter ion comprises at least ^{one selected} from the group consisting of bis(trifluoromethylsulfonyl ⁾ imide (TFSI ^- ), tetrafluoroborate (BF ₄ ^- ), hexafluorophosphate (PF ₆ ^- ), chloride (Cl - ), 1,1,2,2-tetrafluoroethanesulfonate (C ₂ HF ₄ KO ₃ S ^- ), methanesulfonate (C ₂ H ₆ O ₃ S - ), and tetraphenylborate (BPh ₄ ^- ). In the first paragraph,
The above gel polymer electrolyte is a gel polymer electrolyte characterized in that it has a bi-continuous phasic structure in which the tetrazolium cross-linked polymer forms a first continuous phase and the counter ion forms a second continuous phase. In paragraph 5,
A gel polymer electrolyte characterized in that the second continuous phase forms an ion channel. In the first paragraph,
A gel polymer electrolyte, characterized in that the acrylonitrile-based polymer includes at least one selected from the group consisting of polyacrylonitrile-co-vinylidene azide, polyacrylonitrile, poly(acrylonitrile-co-methylmethacrylate), poly(acrylonitrile-co-methacrylic acid), poly(acrylonitrile-co-methylacrylonitrile), poly(lithium acrylonitrile-co-methacrylate), poly(acrylonitrile-co-vinylidene chloride), and poly(acrylonitrile-co-vinyl chloride). In the first paragraph,
A gel polymer electrolyte characterized in that the acrylonitrile-based polymer comprises polyacrylonitrile-co-vinylidene azide represented by the structural formula 1 below:
[Structural formula 1]

In the above structural formula 1,
n is an integer between 1 and 500,
m is an integer between 5 and 2,000. In the first paragraph,
A gel polymer electrolyte characterized in that the tetrazolium cross-linked polymer is represented by the structural formula 2 below:
[Structural formula 2]

In the above structural formula 2,
n is an integer between 1 and 500,
m is an integer between 5 and 2,000,
R ¹ is a C1 to C5 alkyl group. In the first paragraph,
A gel polymer electrolyte characterized in that the liquid electrolyte comprises at least one selected from the group consisting of propylene carbonate, ethylene carbonate, diethyl carbonate, and dimethyl carbonate, in which at least one selected from the group consisting of _lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and lithium hexafluorophosphate (LiPF 6 ) is dissolved. In the first paragraph,
A gel polymer electrolyte, characterized in that the thickness of the gel polymer electrolyte is 20 to 500 μm. An energy storage device comprising a gel polymer electrolyte according to claim 1. In Article 12,
An energy storage device, characterized in that the energy storage device is any one selected from the group consisting of a transistor, a super capacitor, and a lithium secondary battery. (a) a step of preparing a mixed solution containing an acrylonitrile-based polymer having an azide (-N ₃ ) group and a counter ion precursor;
(b) a step of producing a polymer electrolyte by casting the above mixed solution and performing a heat treatment to evaporate the solvent, thereby performing a crosslinking reaction and a quaternization reaction; and
(c) a step of manufacturing a gel polymer electrolyte by containing a liquid electrolyte in the polymer electrolyte;
The above gel polymer electrolyte is
An acrylonitrile-based polymer having an azide (-N ₃ ) group and a tetrazolium-containing polymer that self-cross-links the acrylonitrile-based polymer, the tetrazolium-based polymer having a positive charge;
a counter ion having a negative charge; and
A method for producing a gel polymer electrolyte, comprising: a liquid electrolyte; In Article 14,
A method for producing a gel polymer electrolyte, characterized in that the ratio of the molar ratio (mol _c ) of the counter ion precursor to the molar ratio (mol _N3 ) of the azide group (-N ₃ ) of the acrylonitrile-based polymer (mol _c /mol _N3 ) is 2 to 6. In Article 14,
A method for producing a gel polymer electrolyte, characterized in that the heat treatment of the above step (b) is performed at a temperature of 100 to 150°C. In Article 14,
A method for producing a gel polymer electrolyte, characterized in that the gel polymer electrolyte contains 1 to 500 parts by weight of the liquid electrolyte based on 100 parts by weight of the polymer electrolyte. In Article 14,
A method for producing a gel polymer electrolyte, wherein the counter ion precursor comprises at least one selected from the group consisting of N-alkyl sulfone imide compounds and N-alkyl sulfone amide compounds, and each of the alkyl compounds has 1 to 5 carbon atoms.