KR20210112699A - Electrolyte of supercapacitor, high voltage supercapacitor and manufacturing method of the high voltage supercapacitor using the electrolyte - Google Patents

Abstract

The present invention relates to an electrolyte of supercapacitor, high voltage supercapacitor using same, and manufacturing method thereof, and the electrolyte of a supercapacitor includes non-aqueous electrolyte, 1 to 40 parts by weight of ionic liquid based on 100 parts by weight of the non-aqueous electrolyte, and 0.01 to 15 parts by weight of a sulfone-based electrolyte additive based on 100 parts by weight of the non-aqueous electrolyte, wherein the non-aqueous electrolyte includes an organic solvent, and at least one electrolyte salt selected from the group consisting of tetraethylammonium tetrafluoroborate (TEABF4) and triethylmethylammonium tetrafluoroborate (TEMABF4). According to the present invention, the electrolyte containing the non-aqueous electrolyte, the ionic liquid, and the sulfone-based electrolyte additive is used, so that supercapacitors exhibiting having high reliability at high voltage and high energy density are manufactured.

Description

Electrolyte of a supercapacitor containing an ionic liquid, a high voltage supercapacitor using the same, and a manufacturing method thereof

The present invention relates to an electrolyte, a supercapacitor using the same, and a method for manufacturing the same, and more particularly, by using an electrolyte containing a non-aqueous electrolyte, an ionic liquid, and a sulfone-based electrolyte additive, it is highly reliable at high voltage and exhibits high energy density The present invention relates to an electrolyte for a supercapacitor capable of manufacturing a supercapacitor, a high voltage supercapacitor using the same, and a method for manufacturing the same.

Among next-generation energy storage devices, supercapacitors are attracting attention as next-generation energy storage devices due to their fast charging/discharging speed, high stability, and eco-friendly characteristics. A typical supercapacitor is composed of a porous electrode, a current collector, a separator, and an electrolyte.

Supercapacitors are also called Electric Double Layer Capacitors (EDLC) or Ultra-capacitors, which are a pair of charge layers ( It is a device that does not require maintenance because deterioration due to repetition of charging/discharging operations is very small by using the generated electric double layer). Accordingly, supercapacitors are mainly used in the form of backing up ICs (integrated circuits) of various electric and electronic devices, and their use has recently been expanded and widely applied to toys, solar energy storage, and HEV (hybrid electric vehicle) power sources. have.

Such a supercapacitor generally includes two electrodes of an anode and a cathode impregnated with an electrolyte, a separator of a porous material for insulation and short circuit prevention, and a separator interposed between these two electrodes to allow only ion conduction, and an electrolyte It has a unit cell composed of a gasket for preventing leakage, insulation and short circuit, and a metal cap as a conductor for packaging them. And it is completed by stacking one or more unit cells (usually, 2 to 6 in the case of a coin type) configured as above in series and combining the two terminals of the anode and the cathode.

The performance of a supercapacitor is determined by the electrode active material and electrolyte, and in particular, the main performance such as the capacitance is mostly determined by the electrode active material. Activated carbon is mainly used as such an electrode active material, and it is known that the specific capacitance is up to 19.3 F/cc based on the electrode of commercial products. In general, activated carbon used as an electrode active material of a supercapacitor is activated carbon with a high specific surface area of 1500 m 2 /g or more.

However, with the expansion of the application field of the supercapacitor, a higher energy density is required, and the development of a high voltage supercapacitor exhibiting a higher energy density is required.

Republic of Korea Patent Publication No. 10-1785576

The problem to be solved by the present invention is an electrolyte of a supercapacitor capable of manufacturing a supercapacitor having high reliability and high energy density at high voltage by using an electrolyte containing a non-aqueous electrolyte, an ionic liquid, and a sulfone-based electrolyte additive, To provide a high voltage supercapacitor and a method for manufacturing the same.

The present invention includes a non-aqueous electrolyte, 1 to 40 parts by weight of an ionic liquid based on 100 parts by weight of the non-aqueous electrolyte, and 0.01 to 15 parts by weight of a sulfone-based electrolyte additive with respect to 100 parts by weight of the non-aqueous electrolyte, The electrolyte includes an organic solvent and at least one electrolyte salt selected from the group consisting of tetraethylammonium tetrafluoroborate (TEABF4) and triethylmethylammonium tetrafluoroborate (TEMABF4), and the ionic liquid is 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1 -Ethyl-3-methylimidazolium trifluoromethanesulfonylamide (EMITf ₂ N), 1-Butyl-3-methylimidazolium trifluoromethanesulfonylamide (BMITf ₂ N), 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI), 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF ₄ ), 1-Methyl-3-octylimidazolium tetrafluoroborate (OMIMBF ₄ ), 1-Methyl-3-octylimidazolium trifluoromethanesulfonylamide (OMIMTf ₂ N), N-(2-Methoxyethyl)-N-methylpyrrolidinium tetraflioroborate (MEMPBF ₄ ), and It contains at least one material selected from the group consisting of N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetraflioroborate (DEMEBF ₄ ), and the sulfone-based electrolyte additive is divinyl sulfone (DVS), ethylmethyl sulfone (EMS), diethyl sulfone (DES) and dim It provides an electrolyte of a supercapacitor comprising at least one material selected from the group consisting of ethyl sulfone (DMS).

The organic solvent is acetonitrile, propylene carbonate, ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, vinylene carbonate, tetrahydrofuran, 1,2-dioxane, It may include one or more substances selected from the group consisting of 2-methyltetrahydrofuran, butyrolactone, and dimethylformamide.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of ethyl acetate based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of sulfolane based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor contains 0.01 to 15 parts by weight of an organic compound containing at least one vinyl group selected from the group consisting of vinyl ethylene sulfite and vinyl acetate based on 100 parts by weight of the non-aqueous electrolyte. may include more.

The electrolyte of the supercapacitor is selected from the group consisting of triphenylphosphranylidene aniline (N- (triphenylphosphranylidene) aniline) and tripentafluorophenyl phosphine (Tris (pentafluorophenyl) phosphine) with respect to 100 parts by weight of the non-aqueous electrolyte 0.01 to 15 parts by weight of an organic compound including one or more phosphine derivatives may be further included.

The electrolyte of the supercapacitor is an organic compound containing at least one phosphite derivative selected from the group consisting of trimethylphosphite and ethylene ethyl phosphite based on 100 parts by weight of the non-aqueous electrolyte. It may further include 0.01 to 15 parts by weight.

In addition, in the present invention, the positive electrode and the negative electrode are disposed to be spaced apart from each other, and a separator is disposed between the positive electrode and the negative electrode to prevent a short circuit between the positive electrode and the negative electrode, and the positive electrode and the negative electrode are the electrolyte of a supercapacitor is impregnated with, and the electrolyte of the supercapacitor is a non-aqueous electrolyte, 1-40 parts by weight of an ionic liquid with respect to 100 parts by weight of the non-aqueous electrolyte, and 0.01-15 of a sulfone-based electrolyte additive with respect to 100 parts by weight of the non-aqueous electrolyte Including parts by weight, the non-aqueous electrolyte includes an organic solvent, and at least one electrolyte salt selected from the group consisting of tetraethylammonium tetrafluoroborate (TEABF4) and triethylmethylammonium tetrafluoroborate (TEMABF4), and the ionic liquid is 1-Ethyl-3- methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1-Ethyl-3-methylimidazolium trifluoromethanesulfonylamide (EMITf ₂ N), 1-Butyl-3-methylimidazolium trifluoromethanesulfonylamide (BMITf ₂ N), 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI) , 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF ₄ ), 1-Methyl-3-octylimidazolium tetrafluoroborate (OMIMBF ₄ ), 1-Methyl-3-octylimidazolium trifluoromethanesulfonylamide (OMIMTf ₂ N), N-(2-Methoxyethyl)-N -methylpyrrolidinium tetraflioroborate (MEMPBF ₄ ) and N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafliorobora te(DEMEBF ₄ ) contains at least one material selected from the group consisting of, and the sulfone-based electrolyte additive is a group consisting of divinyl sulfone (DVS), ethylmethyl sulfone (EMS), diethyl sulfone (DES) and dimethyl sulfone (DMS) It provides a supercapacitor comprising at least one material selected from

The organic solvent is acetonitrile, propylene carbonate, ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, vinylene carbonate, tetrahydrofuran, 1,2-dioxane, It may include one or more substances selected from the group consisting of 2-methyltetrahydrofuran, butyrolactone, and dimethylformamide.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of ethyl acetate based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of sulfolane based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor contains 0.01 to 15 parts by weight of an organic compound containing at least one vinyl group selected from the group consisting of vinyl ethylene sulfite and vinyl acetate based on 100 parts by weight of the non-aqueous electrolyte. may include more.

The electrolyte of the supercapacitor is selected from the group consisting of triphenylphosphranylidene aniline (N- (triphenylphosphranylidene) aniline) and tripentafluorophenyl phosphine (Tris (pentafluorophenyl) phosphine) with respect to 100 parts by weight of the non-aqueous electrolyte 0.01 to 15 parts by weight of an organic compound including one or more phosphine derivatives may be further included.

The electrolyte of the supercapacitor is an organic compound containing at least one phosphite derivative selected from the group consisting of trimethylphosphite and ethylene ethyl phosphite based on 100 parts by weight of the non-aqueous electrolyte. It may further include 0.01 to 15 parts by weight.

In addition, the present invention comprises the steps of preparing a composition for a supercapacitor electrode by mixing an electrode active material, a conductive material, a binder and a dispersion medium, and pressing the composition for a supercapacitor electrode to form an electrode, or the composition for a supercapacitor electrode is coated on a metal foil to form an electrode, or the composition for supercapacitor electrode is pressed with a roller to form a sheet, and is attached to a metal foil or a current collector to form an electrode, and the result formed in the form of an electrode is dried to super forming a capacitor electrode and using the supercapacitor electrode as an anode and a cathode, disposing a separator between the anode and the cathode to prevent a short circuit between the anode and the cathode, and connecting the anode and the cathode to the super It provides a method of manufacturing a supercapacitor, comprising the step of impregnating the capacitor in an electrolyte solution.

According to the present invention, a supercapacitor having high reliability and high energy density at high voltage can be manufactured by using an electrolyte including a non-aqueous electrolyte, an ionic liquid, and a sulfone-based electrolyte additive.

By mixing an ionic liquid and a sulfone-based electrolyte additive in a non-aqueous electrolyte to prepare an electrolyte for a supercapacitor, an operable voltage range in the supercapacitor can be increased to improve energy density. The ionic liquid has a wide voltage window compared to the non-aqueous electrolyte and is chemically and thermodynamically stable, but has a low ionic conductivity due to high viscosity. It is chemically and thermodynamically stable and can be operated stably for a long time at a high voltage of 3.0 V to 3.5 V. In addition, by using the sulfone-based electrolyte additive, it can operate stably at high voltage for a long time. The supercapacitor using the electrolyte prepared by the present invention has high reliability at high voltage and high energy density.

1 is a cross-sectional view of a coin-type supercapacitor according to an example.
1 to 5 are views showing a wound type supercapacitor according to an example.
6 is a view showing CV measurement results for each voltage of a supercapacitor manufactured according to a comparative example.
7 is a view showing CV measurement results for each voltage of the supercapacitor manufactured according to Example 1. FIG.
8 is a view showing CV measurement results for each voltage of the supercapacitor manufactured according to Example 2;

Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings. However, the following examples are provided so that those of ordinary skill in the art can fully understand the present invention, and may be modified in various other forms, and the scope of the present invention is limited to the examples described below it's not going to be

When it is said that any one component "includes" another component in the detailed description or claims of the invention, it is not construed as being limited to only the component, unless otherwise stated, and other components are further added. It should be understood as being able to include

The electrolyte of a supercapacitor according to a preferred embodiment of the present invention contains a non-aqueous electrolyte, 1 to 40 parts by weight of an ionic liquid based on 100 parts by weight of the non-aqueous electrolyte, and a sulfone-based electrolyte additive 0.01 with respect to 100 parts by weight of the non-aqueous electrolyte. -15 parts by weight, wherein the non-aqueous electrolyte includes an organic solvent, and at least one electrolyte salt selected from the group consisting of tetraethylammonium tetrafluoroborate (TEABF4) and triethylmethylammonium tetrafluoroborate (TEMABF4), and the ionic liquid is 1-Ethyl- 3-methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1-Ethyl-3-methylimidazolium trifluoromethanesulfonylamide (EMITf ₂ N), 1-Butyl-3-methylimidazolium trifluoromethanesulfonylamide (BMITf ₂ N), 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ( EMITFSI), 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF ₄ ), 1-Methyl-3-octylimidazolium tetrafluoroborate (OMIMBF ₄ ), 1-Methyl-3-octylimidazolium trifluoromethanesulfonylamide (OMIMTf ₂ N), N-(2-Methoxyethyl) -N-methylpyrrolidinium tetraflioroborate (MEMPBF ₄ ) and N,N-Diethyl-N-methyl-N- (2-methoxyethyl)ammonium tetraflioroborate (DEMEBF ₄ ) containing at least one material selected from the group consisting of, the sulfone-based electrolyte solution Additives include divinyl sulfone (DVS), ethylmethyl sulfone (EMS), It contains at least one material selected from the group consisting of diethyl sulfone (DES) and dimethyl sulfone (DMS).

The organic solvent is acetonitrile, propylene carbonate, ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, vinylene carbonate, tetrahydrofuran, 1,2-dioxane, It may include one or more substances selected from the group consisting of 2-methyltetrahydrofuran, butyrolactone, and dimethylformamide.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of ethyl acetate based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of sulfolane based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor contains 0.01 to 15 parts by weight of an organic compound containing at least one vinyl group selected from the group consisting of vinyl ethylene sulfite and vinyl acetate based on 100 parts by weight of the non-aqueous electrolyte. may include more.

The electrolyte of the supercapacitor is selected from the group consisting of triphenylphosphranylidene aniline (N- (triphenylphosphranylidene) aniline) and tripentafluorophenyl phosphine (Tris (pentafluorophenyl) phosphine) with respect to 100 parts by weight of the non-aqueous electrolyte 0.01 to 15 parts by weight of an organic compound including one or more phosphine derivatives may be further included.

The electrolyte of the supercapacitor is an organic compound containing at least one phosphite derivative selected from the group consisting of trimethylphosphite and ethylene ethyl phosphite based on 100 parts by weight of the non-aqueous electrolyte. It may further include 0.01 to 15 parts by weight.

In a supercapacitor according to a preferred embodiment of the present invention, an anode and a cathode are spaced apart from each other, and a separator is disposed between the anode and the cathode to prevent a short circuit between the anode and the cathode, the anode and the cathode The negative electrode is impregnated in the electrolyte of the supercapacitor, and the electrolyte of the supercapacitor is designed with respect to the non-aqueous electrolyte, 1 to 40 parts by weight of the ionic liquid based on 100 parts by weight of the non-aqueous electrolyte, and 100 parts by weight of the non-aqueous electrolyte. Contains 0.01 to 15 parts by weight of a phone-based electrolyte additive, wherein the non-aqueous electrolyte includes an organic solvent, and one or more electrolyte salts selected from the group consisting of tetraethylammonium tetrafluoroborate (TEABF4) and triethylmethylammonium tetrafluoroborate (TEMABF4), and the ionic liquid includes 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1-Ethyl-3-methylimidazolium trifluoromethanesulfonylamide (EMITf ₂ N), 1-Butyl-3-methylimidazolium trifluoromethanesulfonylamide (BMITf ₂ N), 1-Ethyl-3-methylimidazolium bis ( trifluoromethanesulfonyl)imide (EMITFSI), 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF ₄ ), 1-Methyl-3-octylimidazolium tetrafluoroborate (OMIMBF ₄ ), 1-Methyl-3-octylimidazolium trifluoromethanesulfonylamide (OMIMTf ₂ N), N-( 2-Methoxyethyl)-N-methylpyrrolidinium tetraflioroborate (MEMPBF ₄ ) and N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammoniu m containing at least one material selected from the group consisting of tetraflioroborate (DEMEBF ₄ ), and the sulfone-based electrolyte additive is composed of divinyl sulfone (DVS), ethylmethyl sulfone (EMS), diethyl sulfone (DES) and dimethyl sulfone (DMS). and one or more substances selected from the group.

The organic solvent is acetonitrile, propylene carbonate, ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, vinylene carbonate, tetrahydrofuran, 1,2-dioxane, It may include one or more substances selected from the group consisting of 2-methyltetrahydrofuran, butyrolactone, and dimethylformamide.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of ethyl acetate based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of sulfolane based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor contains 0.01 to 15 parts by weight of an organic compound containing at least one vinyl group selected from the group consisting of vinyl ethylene sulfite and vinyl acetate based on 100 parts by weight of the non-aqueous electrolyte. may include more.

The electrolyte of the supercapacitor is selected from the group consisting of triphenylphosphranylidene aniline (N- (triphenylphosphranylidene) aniline) and tripentafluorophenyl phosphine (Tris (pentafluorophenyl) phosphine) with respect to 100 parts by weight of the non-aqueous electrolyte 0.01 to 15 parts by weight of an organic compound including one or more phosphine derivatives may be further included.

The electrolyte of the supercapacitor is an organic compound containing at least one phosphite derivative selected from the group consisting of trimethylphosphite and ethylene ethyl phosphite based on 100 parts by weight of the non-aqueous electrolyte. It may further include 0.01 to 15 parts by weight.

The method of manufacturing a supercapacitor according to a preferred embodiment of the present invention comprises the steps of preparing a composition for a supercapacitor electrode by mixing an electrode active material, a conductive material, a binder and a dispersion medium, and pressing the composition for a supercapacitor electrode to form an electrode forming, or coating the composition for a supercapacitor electrode on a metal foil to form an electrode, or pressing the composition for a supercapacitor electrode with a roller to form a sheet and attaching it to a metal foil or a current collector to form an electrode; Drying the resultant formed in the form of an electrode to form a supercapacitor electrode, using the supercapacitor electrode as an anode and a cathode, and placing a separator between the anode and the cathode to prevent a short circuit between the anode and the cathode, , and impregnating the anode and the cathode with the electrolyte of the supercapacitor.

Hereinafter, an electrolyte of a supercapacitor according to a preferred embodiment of the present invention will be described in more detail.

The electrolyte of a supercapacitor according to a preferred embodiment of the present invention contains a non-aqueous electrolyte, 1 to 40 parts by weight of an ionic liquid based on 100 parts by weight of the non-aqueous electrolyte, and a sulfone-based electrolyte additive 0.01 with respect to 100 parts by weight of the non-aqueous electrolyte. -15 parts by weight.

The non-aqueous electrolyte includes an organic solvent and one or more electrolyte salts selected from the group consisting of tetraethylammonium tetrafluoroborate (TEABF4) and triethylmethylammonium tetrafluoroborate (TEABF4).

The organic solvent is acetonitrile, propylene carbonate, ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, vinylene carbonate, tetrahydrofuran, 1,2-dioxane, It may include one or more substances selected from the group consisting of 2-methyltetrahydrofuran, butyrolactone, and dimethylformamide.

The electrolyte of the supercapacitor includes an ionic liquid, which is a material having a large potential window in order to secure stability at high voltage. The ionic liquid is 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1-Ethyl-3-methylimidazolium trifluoromethanesulfonylamide (EMITf ₂ N), 1-Butyl-3-methylimidazolium trifluoromethanesulfonylamide (BMITf ₂ N), 1-Ethyl- 3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI), 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF ₄ ), 1-Methyl-3-octylimidazolium tetrafluoroborate (OMIMBF ₄ ), 1-Methyl-3-octylimidazolium trifluoromethanesulfonylamide (OMIMTf ₂ N ), at least one selected from the group consisting of N-(2-Methoxyethyl)-N-methylpyrrolidinium tetraflioroborate (MEMPBF ₄ ) and N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetraflioroborate (DEMEBF _{4 )} material may be included.

As an example of the ionic liquid, the structure of EMITFSI (1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide) is shown in Structural Formula 1 below.

[Structural Formula 1]

As another example of the ionic liquid, the structure of MEMPBF ₄ (N-(2-Methoxyethyl)-N-methylpyrrolidinium tetraflioroborate) is shown in Structural Formula 2 below.

[Structural Formula 2]

The above-described ionic liquid has a wide potential window compared to electrolyte salts and organic solvents, and is chemically/thermodynamically stable. By including an ionic liquid that expands the potential window, it is possible to reduce the decomposition of the electrolyte that occurs when operating at high voltage. However, the ionic liquid is an expensive material and has a high viscosity, so it is difficult to impregnate the electrode. As a method of compensating for the disadvantages of such an ionic liquid, it is preferable to mix the ionic liquid with an organic solvent and an electrolyte salt and lower the viscosity to increase the impregnability.

The electrolyte of the supercapacitor includes a sulfone-based electrolyte additive. The sulfone-based electrolyte additive includes at least one material selected from the group consisting of divinyl sulfone (DVS), ethylmethyl sulfone (EMS), diethyl sulfone (DES), and dimethyl sulfone (DMS).

By mixing an ionic liquid and a sulfone-based electrolyte additive in a non-aqueous electrolyte to prepare an electrolyte for a supercapacitor, an operable voltage range in the supercapacitor can be increased to improve energy density. The ionic liquid has a wide voltage window compared to the non-aqueous electrolyte and is chemically and thermodynamically stable, but has a low ionic conductivity due to high viscosity. It is chemically and thermodynamically stable and can be operated stably for a long time at a high voltage of 3.0 V to 3.5 V. In addition, by using the sulfone-based electrolyte additive, it can operate stably at high voltage for a long time. The supercapacitor using the electrolyte prepared by the present invention has high reliability at high voltage and high energy density.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of ethyl acetate based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of sulfolane based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor contains 0.01 to 15 parts by weight of an organic compound containing at least one vinyl group selected from the group consisting of vinyl ethylene sulfite and vinyl acetate based on 100 parts by weight of the non-aqueous electrolyte. may include more. By using an organic compound containing a vinyl group, it is possible to manufacture a supercapacitor capable of stably driving even at high voltage by increasing conductivity and widening the potential window.

The electrolyte of the supercapacitor is selected from the group consisting of triphenylphosphranylidene aniline (N- (triphenylphosphranylidene) aniline) and tripentafluorophenyl phosphine (Tris (pentafluorophenyl) phosphine) with respect to 100 parts by weight of the non-aqueous electrolyte 0.01 to 15 parts by weight of an organic compound including one or more phosphine derivatives may be further included. By using an organic compound containing a phosphine derivative as a way to compensate for the low conductivity of an ionic liquid, a supercapacitor capable of stably driving even at high voltage can be manufactured by increasing the conductivity and widening the potential window.

The electrolyte of the supercapacitor is an organic compound containing at least one phosphite derivative selected from the group consisting of trimethylphosphite and ethylene ethyl phosphite based on 100 parts by weight of the non-aqueous electrolyte. It may further include 0.01 to 15 parts by weight. By using an organic compound containing a phosphite derivative, it is possible to manufacture a supercapacitor capable of stably driving even at high voltage by increasing conductivity and widening the potential window.

Hereinafter, a high voltage supercapacitor using an electrolyte of a supercapacitor according to a preferred embodiment of the present invention and a method for manufacturing the same will be described in more detail.

A composition for a supercapacitor electrode including an electrode active material, a conductive material, a binder, and a dispersion medium is prepared. The composition for a supercapacitor electrode includes 2 to 20 parts by weight of a conductive material based on 100 parts by weight of the electrode active material and 100 parts by weight of the electrode active material, 2 to 20 parts by weight of a binder based on 100 parts by weight of the electrode active material, and 100 parts by weight of the electrode active material. It may contain 200 to 300 parts by weight of the dispersion medium. Since the composition for supercapacitor electrode is in the form of a paste, it may be difficult to uniformly mix (completely disperse). When stirred for a while, a composition for a supercapacitor electrode suitable for electrode manufacturing can be obtained. A mixer such as a planetary mixer enables the preparation of a uniformly mixed composition for a supercapacitor electrode.

The electrode active material may be porous activated carbon or the like.

The binder is polytetrafluoroethylene (PTFE; polytetrafluoroethylene), polyvinylidene fluoride (PVdF; polyvinylidenefloride), carboxymethylcellulose (CMC; carboxymethylcellulose), polyvinyl alcohol (PVA; polyvinyl alcohol), polyvinylbutyral ( PVB; poly vinyl butyral), polyvinylpyrrolidone (PVP; poly-N-vinylpyrrolidone), styrene butadiene rubber (SBR), polyamide-imide, polyimide, etc. One or two or more selected from the group may be used in combination.

The conductive material is not particularly limited as long as it is an electronically conductive material that does not cause chemical change, and examples include natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, Super-P black, carbon fiber, copper, nickel. , a metal powder such as aluminum, silver, or a metal fiber, etc. are possible.

The dispersion medium may be an organic solvent such as ethanol (EtOH), acetone, isopropyl alcohol, N-methylpyrrolidone (NMP), propylene glycol (PG), or water.

A composition for a supercapacitor electrode, which is a mixture of an electrode active material, a binder, a conductive material, and a dispersion medium, is pressed to form an electrode, or the composition for a supercapacitor electrode is coated on a metal foil to form an electrode, or the composition for a supercapacitor electrode is pressed with a roller to form a sheet state, is attached to a metal foil or a current collector to form an electrode, and the resultant formed in the form of an electrode is dried to form an electrode.

When describing the example of the step of forming the electrode in more detail, the composition for a supercapacitor electrode may be molded by compression using a roll press molding machine. The roll press molding machine aims to improve the electrode density and control the thickness of the electrode through rolling. made up of wealth As the rolled electrode passes through the roll press, the rolling process proceeds, which is then wound into a roll state to complete the electrode. At this time, the pressing pressure of the press is preferably 5 to 20 ton/cm 2 and the temperature of the roll is preferably 0 to 150°C. The composition for a supercapacitor electrode, which has been subjected to the press compression process as described above, is subjected to a drying process. The drying process is carried out at a temperature of 100°C to 350°C, preferably 150°C to 300°C. At this time, when the drying temperature is less than 100 ° C., it is not preferable because evaporation of the dispersion medium is difficult, and when drying at a high temperature exceeding 350 ° C., oxidation of the conductive material may occur. Therefore, it is preferable that the drying temperature is at least 100°C or higher and does not exceed 350°C. And the drying process is preferably carried out for about 10 minutes to 6 hours at the same temperature as above. Such a drying process dries the molded composition for a supercapacitor electrode (evaporating the dispersion medium) and at the same time binds the powder particles to improve the strength of the supercapacitor electrode.

In addition, looking at another example of forming an electrode, the composition for a supercapacitor electrode is coated on a metal foil such as a titanium foil, an aluminum foil, or an aluminum etching foil. Alternatively, the composition for the electrode may be made into a sheet state (rubber type) by pushing the composition for an electrode with a roller and attached to a metal foil or a metal current collector to produce an electrode shape. The aluminum etching foil means that the aluminum foil is etched in a concave-convex shape. A drying process is performed on the electrode shape that has been subjected to the above process. It is carried out at a temperature of 100°C to 250°C, preferably 150°C to 200°C.

The supercapacitor electrode manufactured as described above has a high capacity and can be usefully applied to a small coin-type supercapacitor.

1 is a state diagram of a supercapacitor according to the present invention, and is a cross-sectional view of a coin-type supercapacitor to which the supercapacitor electrode is applied. In FIG. 1, reference numeral 190 denotes a metal cap as a conductor, reference numeral 160 denotes a separator made of a porous material for insulation and short circuit prevention between the anode 120 and the cathode 110, and reference numeral 192 denotes electrolyte leakage. It is a gasket for preventing electrical shock and insulation and short circuit. At this time, the positive electrode 120 and the negative electrode 110 are firmly fixed by the metal cap 190 and the adhesive.

The coin-type supercapacitor is disposed between the anode 120 made of the above-described supercapacitor electrode, the cathode 110 comprising the above-described supercapacitor electrode, and the anode 120 and the cathode 110, the anode 120 After disposing a separator 160 to prevent a short circuit between the cathode 120 and the metal cap 190, and injecting the above-described electrolyte solution of the supercapacitor between the anode 120 and the cathode 110, It may be manufactured by sealing it with a gasket 192 .

The separator includes polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, polyacrylonitrile porous separator, poly(vinylidene fluoride) hexafluoropropane copolymer porous separator, cellulose porous separator, kraft paper or rayon fiber, etc. batteries and capacitors If it is a separator generally used in the field, it is not particularly limited.

2 to 5 are views showing a supercapacitor according to another example of the present invention, and a method of manufacturing the supercapacitor will be described in detail with reference to FIGS. 2 to 5 .

A method for preparing a composition for a supercapacitor electrode by mixing an electrode active material, a binder, a conductive material, and a dispersion medium is the same as the method described above.

The composition for supercapacitor electrodes is coated on a metal foil such as aluminum foil or aluminum etching foil, or the composition for supercapacitor electrodes is pushed with a roller to form a sheet state ( rubber type) and attached to a metal foil or a current collector to produce positive and negative electrode shapes.

A drying process is performed on the shapes of the positive and negative electrodes that have been subjected to the above process. The drying process is carried out at a temperature of 100°C to 350°C, preferably 150°C to 300°C. At this time, when the drying temperature is less than 100 ° C., it is not preferable because evaporation of the dispersion medium is difficult, and when drying at a high temperature exceeding 350 ° C., oxidation of the conductive material may occur. Therefore, it is preferable that the drying temperature is at least 100°C or higher and does not exceed 350°C. And the drying process is preferably carried out for about 10 minutes to 6 hours at the same temperature as above. Such a drying process dries the composition for supercapacitor electrodes (evaporating the dispersion medium) and at the same time binds powder particles to improve the strength of the supercapacitor electrode.

As shown in FIG. 2, the lead wires 130 and 140 to the positive electrode 120 and the negative electrode 110 manufactured by coating the composition for a supercapacitor electrode on a metal foil or making a sheet state and attaching it to a metal foil or a current collector, respectively. attach

3, the first separator 150, the positive electrode 120, the second separator 160, and the negative electrode 110 are laminated and coiled to form a roll retractor ( 175), and then wound around the roll with an adhesive tape 170, etc. so that the roll shape can be maintained.

The second separator 160 provided between the positive electrode 120 and the negative electrode 110 serves to prevent a short circuit between the positive electrode 120 and the negative electrode 110 . The first and second separators 150 and 160 are polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, polyacrylonitrile porous separator, poly(vinylidene fluoride) hexafluoropropane copolymer porous separator, cellulose porous separator, kraft paper Or, if it is a separator generally used in the field of batteries and capacitors such as rayon fiber, it is not particularly limited.

As shown in FIG. 4 , a sealing rubber 180 is mounted on the resultant in the form of a roll, and inserted into a metal cap (eg, an aluminum case) 190 .

The electrolyte solution of the above-described supercapacitor is injected so that the roll-shaped winding retractor 175 (positive electrode 120 and negative electrode 110) is impregnated and sealed.

The supercapacitor fabricated in this way is schematically shown in FIG. 5 .

In the supercapacitor manufactured as described above, the positive electrode and the negative electrode are spaced apart from each other, and a separator is disposed between the positive electrode and the negative electrode to prevent a short circuit between the positive electrode and the negative electrode, and the positive electrode and the negative electrode are It is impregnated with the electrolyte of the supercapacitor.

The electrolyte of the supercapacitor contains 1 to 40 parts by weight of the ionic liquid based on 100 parts by weight of the non-aqueous electrolyte, and 0.01 to 15 parts by weight of the sulfone-based electrolyte additive based on 100 parts by weight of the non-aqueous electrolyte, The non-aqueous electrolyte includes an organic solvent, and at least one electrolyte salt selected from the group consisting of tetraethylammonium tetrafluoroborate (TEABF4) and triethylmethylammonium tetrafluoroborate (TEMABF4), and the ionic liquid is 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIBF _4). ), 1-Ethyl-3-methylimidazolium trifluoromethanesulfonylamide (EMITf ₂ N), 1-Butyl-3-methylimidazolium trifluoromethanesulfonylamide (BMITf ₂ N), 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI), 1-Butyl- 3-methylimidazolium tetrafluoroborate (BMIMBF ₄ ), 1-Methyl-3-octylimidazolium tetrafluoroborate (OMIMBF ₄ ), 1-Methyl-3-octylimidazolium trifluoromethanesulfonylamide (OMIMTf ₂ N), N-(2-Methoxyethyl)-N-methylpyrrolidinium tetraflioroborate (MEMPBF) ₄ ) and at least one material selected from the group consisting of N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetraflioroborate (DEMEBF ₄ ), and the sulfone-based electrolyte additive is divinyl sulfone (DVS) , ethylmethyl sulfone (EMS), diethyl sulfone ( DES) and at least one material selected from the group consisting of dimethyl sulfone (DMS).

The organic solvent is acetonitrile, propylene carbonate, ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, vinylene carbonate, tetrahydrofuran, 1,2-dioxane, It may include one or more substances selected from the group consisting of 2-methyltetrahydrofuran, butyrolactone, and dimethylformamide.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of ethyl acetate based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor may further include 0.01 to 15 parts by weight of sulfolane based on 100 parts by weight of the non-aqueous electrolyte.

The electrolyte of the supercapacitor contains 0.01 to 15 parts by weight of an organic compound containing at least one vinyl group selected from the group consisting of vinyl ethylene sulfite and vinyl acetate based on 100 parts by weight of the non-aqueous electrolyte. may include more.

The electrolyte of the supercapacitor is selected from the group consisting of triphenylphosphranylidene aniline (N- (triphenylphosphranylidene) aniline) and tripentafluorophenyl phosphine (Tris (pentafluorophenyl) phosphine) with respect to 100 parts by weight of the non-aqueous electrolyte 0.01 to 15 parts by weight of an organic compound including one or more phosphine derivatives may be further included.

The electrolyte of the supercapacitor is an organic compound containing at least one phosphite derivative selected from the group consisting of trimethylphosphite and ethylene ethyl phosphite based on 100 parts by weight of the non-aqueous electrolyte. It may further include 0.01 to 15 parts by weight.

Hereinafter, experimental examples according to the present invention are specifically presented, and the present invention is not limited to the experimental examples presented below.

<Example 1>

8 g of non-aqueous electrolyte (1M TEABF _{4 / ACN) and 2 g of EMIBF 4} , an ionic liquid, were placed in a 100 ml beaker and mixed at room temperature at 300 rpm for 30 minutes while stirring to prepare a high-voltage supercapacitor electrolyte. The non-aqueous electrolyte (1M TEABF ₄ /ACN) is _{an electrolyte in which 1M TEABF 4} (tetraethylammonium tetrafluoroborate) salt is dissolved in acetonitrile (ACN).

Commercially available activated carbon YP50F was used as an electrode active material to prepare an electrode for a supercapacitor. When manufacturing the electrode, put 0.9 g of electrode active material, 0.05 g of carbon black super-p as a conductive material, and 0.05 g of polytetrafluoroethylene (PTFE; Polytetrafluoroethylene) as a binder in ethanol as a dispersion medium and mix for 3 minutes with a planetary mixer. to make a slurry state, and after performing hand kneading 10 times, a rolling process was performed with a roll press. At this time, the pressing pressure of the press was 10 ton/cm 2 , and the temperature of the roll was 60°C. The electrode thickness after the rolling process was 150 μm, and it was placed in a vacuum drying rack at 150° C. and dried for 12 hours to obtain an electrode.

A full cell was assembled into a coin type 2032 cell using 120 μl of the prepared high voltage supercapacitor electrolyte and the electrode. In this case, TF4035 from NKK was used as the separation membrane.

Impedance, cyclic voltammetry, etc. were measured for the manufactured cell to measure resistance and voltage-specific tests.

For test conditions, impedance was measured at a frequency of 100 kHz to 100 MHz at 25°C, and a CV test was performed for each voltage from 2.7 to 3.7 V at 25°C at a scan rate of 2 mV/s.

<Example 2>

Add 8 g of non-aqueous electrolyte (1M TEABF ₄ / ACN), _{2 g of EMIBF 4 that is an} ionic liquid, and 0.2 g of DMS (dimethyl sulfone), a sulfone-based electrolyte additive, into a 100 ml beaker and mix while stirring at 300 rpm at room temperature for 30 minutes to high voltage. A supercapacitor electrolyte solution was prepared. The non-aqueous electrolyte (1M TEABF ₄ /ACN) is _{an electrolyte in which 1M TEABF 4} (tetraethylammonium tetrafluoroborate) salt is dissolved in acetonitrile (ACN).

Commercially available activated carbon YP50F was used as an electrode active material to prepare an electrode for a supercapacitor. When manufacturing the electrode, put 0.9 g of electrode active material, 0.05 g of carbon black super-p as a conductive material, and 0.05 g of polytetrafluoroethylene (PTFE; Polytetrafluoroethylene) as a binder in ethanol as a dispersion medium and mix for 3 minutes with a planetary mixer. to make a slurry state, and after performing hand kneading 10 times, a rolling process was performed with a roll press. At this time, the pressing pressure of the press was 10 ton/cm 2 , and the temperature of the roll was 60°C. The electrode thickness after the rolling process was 150 μm, and it was placed in a vacuum drying rack at 150° C. and dried for 12 hours to obtain an electrode.

A full cell was assembled into a coin type 2032 cell using 120 μl of the prepared high voltage supercapacitor electrolyte and the electrode. In this case, TF4035 from NKK was used as the separation membrane.

Impedance, cyclic voltammetry, etc. were measured for the manufactured cell to measure resistance and voltage-specific tests.

For test conditions, impedance was measured at a frequency of 100 kHz to 100 MHz at 25°C, and a CV test was performed for each voltage from 2.7 to 3.7 V at 25°C at a scan rate of 2 mV/s.

Comparative examples are presented so that the characteristics of the experimental examples can be more easily understood, and the comparative examples below are merely presented to aid understanding and are not prior art of the present invention.

<Comparative example>

Commercially available activated carbon YP50F was used as an electrode active material to prepare an electrode for a supercapacitor. When manufacturing the electrode, add 0.9 g of electrode active material, 0.05 g of carbon black super-p as a conductive material, and 0.05 g of polytetrafluoroethylene (PTFE; Polytetrafluoroethylene) as a binder in ethanol as a dispersion medium and mix with a planetary mixer for 3 minutes. to make a slurry state, and after performing hand kneading 10 times, a rolling process was performed with a roll press. At this time, the press pressure of the press was 10 ton/cm 2 , and the temperature of the roll was 60°C. The thickness of the electrode after the rolling process was 150 μm, and it was placed in a vacuum drying rack at 150° C. and dried for 12 hours to obtain an electrode.

A full cell was assembled as a cell of a coin type 2032 using the electrode. In this case, TF4035 manufactured by NKK was used as the separator, and 120 μl of 1M TEABF ₄ / ACN, a non-aqueous electrolyte, was used as the electrolyte.

Impedance, cyclic voltammetry, etc. were measured for the manufactured cell to measure resistance and voltage-specific tests.

For test conditions, impedance was measured at a frequency of 100 kHz to 100 MHz at 25°C, and a CV test was performed for each voltage from 2.7 to 3.7 V at 25°C at a scan rate of 2 mV/s.

1. Electrolyte ionic conductivity measurement

_{The ionic conductivity of the mixed electrolyte obtained by mixing 1M TEABF 4} / ACN and the ionic liquid EMIBF ₄ and DMS used in Comparative Example was measured using an ion conductivity meter, and is shown in Table 1 below.

division Ion Conductivity (mS/cm) 1M TEABF ₄ / ACN (comparative example) 46.93 1M TEABF ₄ / ACN + EMIBF ₄ (Example 1) 45.17 1M TEABF ₄ / ACN + EMIBF ₄ + DMS (Example 2) 46.84

2. Cell resistance (ESR) and specific capacitance measurement

The resistance and specific capacitance of a 2032 coin cell using a mixed electrolyte of _{1M TEABF 4} / ACN, ionic liquid EMIBF _4, and DMS used in Comparative Example were measured and shown in Table 2 below.

division Cell resistance (Ω) Reserved Capacitance (F/cc) 1M TEABF ₄ / ACN (comparative example) 13.8 14.7 1M TEABF ₄ / ACN + EMIBF ₄ (Example 1) 14.5 15.8 1M TEABF ₄ / ACN + EMIBF ₄ + DMS (Example 2) 10.5 16.1

It was found that the specific capacitance of the cells manufactured according to Examples 1 and 2 was superior to the specific capacitance of the cells manufactured according to Comparative Example.

6 is a view showing the CV measurement results for each voltage of the supercapacitor manufactured according to the comparative example, FIG. 7 is a diagram showing the CV measurement results for each voltage of the supercapacitor manufactured according to Example 1, and FIG. 8 is the Example It is a diagram showing the CV measurement results for each voltage of the supercapacitor manufactured according to 2 .

6 to 8 , it was found that the supercapacitors manufactured according to Examples 1 and 2 had superior specific capacitance compared to the supercapacitors manufactured according to the Comparative Example. In particular, it was found that the supercapacitor manufactured according to Example 2 was superior to the supercapacitor manufactured according to Example 1 in specific capacitance.

As mentioned above, although preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various modifications are possible by those skilled in the art.

110: negative electrode 120: positive electrode
130: first lead wire 140: second lead wire
150: first separator 160: second separator
170: adhesive tape 175: unwinder
180: sealing rubber 190: metal cap
192: gasket

Claims (15)

non-aqueous electrolyte;
1 to 40 parts by weight of an ionic liquid based on 100 parts by weight of the non-aqueous electrolyte; and
Contains 0.01 to 15 parts by weight of a sulfone-based electrolyte additive based on 100 parts by weight of the non-aqueous electrolyte,
The non-aqueous electrolyte is an organic solvent; and
It contains one or more electrolyte salts selected from the group consisting of TEABF4 (tetraethylammonium tetrafluoroborate) and TEMABF4 (triethylmethylammonium tetrafluoroborate),
The ionic liquid is 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1-Ethyl-3-methylimidazolium trifluoromethanesulfonylamide (EMITf ₂ N), 1-Butyl-3-methylimidazolium trifluoromethanesulfonylamide (BMITf ₂ N), 1-Ethyl- 3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI), 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF ₄ ), 1-Methyl-3-octylimidazolium tetrafluoroborate (OMIMBF ₄ ), 1-Methyl-3-octylimidazolium trifluoromethanesulfonylamide (OMIMTf ₂ N ), at least one selected from the group consisting of N-(2-Methoxyethyl)-N-methylpyrrolidinium tetraflioroborate (MEMPBF ₄ ) and N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetraflioroborate (DEMEBF _{4 )} containing substances;
The sulfone-based electrolyte additive comprises at least one material selected from the group consisting of divinyl sulfone (DVS), ethylmethyl sulfone (EMS), diethyl sulfone (DES) and dimethyl sulfone (DMS).
According to claim 1, wherein the organic solvent is acetonitrile (acetonitrile), propylene carbonate (propylene carbonate), ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, vinylene carbonate, tetrahydrofuran, 1 ,2-dioxane, 2-methyltetrahydrofuran, butyrolactone and at least one material selected from the group consisting of dimethylformamide electrolyte solution for a supercapacitor.
The electrolyte of claim 1, further comprising 0.01 to 15 parts by weight of ethyl acetate based on 100 parts by weight of the non-aqueous electrolyte.
The electrolyte of claim 1, further comprising 0.01 to 15 parts by weight of sulfolane based on 100 parts by weight of the non-aqueous electrolyte.
According to claim 1, 0.01 to 15 parts by weight of an organic compound containing at least one vinyl group selected from the group consisting of vinyl ethylene sulfite and vinyl acetate based on 100 parts by weight of the non-aqueous electrolyte solution Electrolyte of a supercapacitor, characterized in that it further comprises.
According to claim 1, Triphenylphosphranylidene aniline (N- (triphenylphosphranylidene) aniline) and tripentafluorophenyl phosphine (Tris (pentafluorophenyl) phosphine) with respect to 100 parts by weight of the non-aqueous electrolyte selected from the group consisting of An electrolyte for a supercapacitor, characterized in that it further comprises 0.01 to 15 parts by weight of an organic compound containing at least one phosphine derivative.
The organic compound according to claim 1, comprising at least one phosphite derivative selected from the group consisting of trimethylphosphite and ethylene ethyl phosphite based on 100 parts by weight of the non-aqueous electrolyte. Supercapacitor electrolyte, characterized in that it further comprises 0.01 to 15 parts by weight.
The anode and the cathode are spaced apart from each other,
A separator is disposed between the positive electrode and the negative electrode to prevent a short circuit between the positive electrode and the negative electrode,
The positive electrode and the negative electrode are impregnated with an electrolyte of a supercapacitor,
The electrolyte of the supercapacitor is
non-aqueous electrolyte;
1 to 40 parts by weight of an ionic liquid based on 100 parts by weight of the non-aqueous electrolyte; and
It contains 0.01 to 15 parts by weight of a sulfone-based electrolyte additive based on 100 parts by weight of the non-aqueous electrolyte,
The non-aqueous electrolyte is an organic solvent; and
Contains one or more electrolyte salts selected from the group consisting of TEABF4 (tetraethylammonium tetrafluoroborate) and TEMABF4 (triethylmethylammonium tetrafluoroborate),
The ionic liquid is 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1-Ethyl-3-methylimidazolium trifluoromethanesulfonylamide (EMITf ₂ N), 1-Butyl-3-methylimidazolium trifluoromethanesulfonylamide (BMITf ₂ N), 1-Ethyl- 3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI), 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIMBF ₄ ), 1-Methyl-3-octylimidazolium tetrafluoroborate (OMIMBF ₄ ), 1-Methyl-3-octylimidazolium trifluoromethanesulfonylamide (OMIMTf ₂ N ), at least one selected from the group consisting of N-(2-Methoxyethyl)-N-methylpyrrolidinium tetraflioroborate (MEMPBF ₄ ) and N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetraflioroborate (DEMEBF _{4 )} containing substances;
The sulfone-based electrolyte additive comprises at least one material selected from the group consisting of divinyl sulfone (DVS), ethylmethyl sulfone (EMS), diethyl sulfone (DES) and dimethyl sulfone (DMS).
The method of claim 8, wherein the organic solvent is acetonitrile, propylene carbonate, ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, diethyl carbonate, butylene carbonate, vinylene carbonate, tetrahydrofuran, 1 A supercapacitor comprising at least one material selected from the group consisting of ,2-dioxane, 2-methyltetrahydrofuran, butyrolactone and dimethylformamide.
The supercapacitor according to claim 8, wherein the electrolyte of the supercapacitor further comprises 0.01 to 15 parts by weight of ethyl acetate based on 100 parts by weight of the non-aqueous electrolyte.
The supercapacitor according to claim 8, wherein the electrolyte of the supercapacitor further comprises 0.01 to 15 parts by weight of sulfolane based on 100 parts by weight of the non-aqueous electrolyte.
According to claim 8, wherein the electrolyte of the supercapacitor is an organic containing at least one vinyl group selected from the group consisting of vinyl ethylene sulfite and vinyl acetate based on 100 parts by weight of the non-aqueous electrolyte. Supercapacitor, characterized in that it further comprises 0.01 to 15 parts by weight of the compound.
The method of claim 8, wherein the electrolyte of the supercapacitor is triphenylphosphranylidene aniline (N- (triphenylphosphranylidene) aniline) and tripentafluorophenyl phosphine (Tris (pentafluorophenyl) phosphine) based on 100 parts by weight of the non-aqueous electrolyte. ) Supercapacitor, characterized in that it further comprises 0.01 to 15 parts by weight of an organic compound containing one or more phosphine derivatives selected from the group consisting of.
The method of claim 8, wherein the electrolyte of the supercapacitor is at least one selected from the group consisting of trimethylphosphite and ethylene ethyl phosphite based on 100 parts by weight of the non-aqueous electrolyte. Supercapacitor, characterized in that it further comprises 0.01 to 15 parts by weight of an organic compound containing a derivative.
preparing a composition for a supercapacitor electrode by mixing an electrode active material, a conductive material, a binder, and a dispersion medium;
The composition for a supercapacitor electrode is compressed to form an electrode, or the composition for a supercapacitor electrode is coated on a metal foil to form an electrode, or the composition for a supercapacitor electrode is pressed with a roller to form a sheet state and a metal foil or forming an electrode by attaching it to a current collector;
drying the resultant formed in the form of an electrode to form a supercapacitor electrode; and
The supercapacitor electrode is used as an anode and a cathode, a separator is disposed between the anode and the cathode to prevent a short circuit between the anode and the cathode, and the anode and the cathode are connected to the electrolyte solution of the supercapacitor according to claim 1 . A method of manufacturing a supercapacitor, comprising the step of impregnating in the supercapacitor.

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