KR20150098178A - Sealing Material, Flexible Thin-film type Super-Capacitor Device Manufacturing Method having the same and Super-Capacitor Device thereof - Google Patents

Sealing Material, Flexible Thin-film type Super-Capacitor Device Manufacturing Method having the same and Super-Capacitor Device thereof Download PDF

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KR20150098178A
KR20150098178A KR1020140131302A KR20140131302A KR20150098178A KR 20150098178 A KR20150098178 A KR 20150098178A KR 1020140131302 A KR1020140131302 A KR 1020140131302A KR 20140131302 A KR20140131302 A KR 20140131302A KR 20150098178 A KR20150098178 A KR 20150098178A
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film
base film
base
current collector
active material
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KR1020140131302A
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Korean (ko)
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KR101812376B1 (en
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유정준
김종휘
윤재국
윤하나
김용일
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한국에너지기술연구원
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Priority to US14/602,443 priority Critical patent/US9520243B2/en
Publication of KR20150098178A publication Critical patent/KR20150098178A/en
Priority to US15/158,764 priority patent/US9842706B2/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/198—Graphene oxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H01G11/80—Gaskets; Sealings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention relates to a method of manufacturing a flexible thin film type supercapacitor element and a super capacitor element therefor. The flexible thin film type supercapacitor element according to the present invention comprises: a base film having flexibility; A separation membrane interposed between the base films; And an active material formed on the base film.
Thus, it is very thin and flexible while maintaining high electrical conductivity and high bondability, and can be mass-produced economically.

Figure P1020140131302

Description

[0001] The present invention relates to a method for manufacturing a flexible thin film type super capacitor device,

The present invention relates to a sealing material, a method of manufacturing a flexible thin film type supercapacitor device and a supercapacitor device therefor, and more particularly, to a flexible film having a flexible film formed on a base film, A method of manufacturing a flexible thin film type supercapacitor device using the same, and a super capacitor device therefor.

Generally, like the electrodes of the capacitor, the electrodes such as the secondary battery and the electrochemical capacitor are largely composed of an active material for generating an electrochemical reaction and a current collector for transferring electrons generated from the active material to an external circuit. It is preferable that the current collector has a high electrical conductivity with a minimum resistance so that the flow of electrons supplied from the active material is not disturbed. In addition, since the electrons move through the interface between the active material and the active material, it is required to have a wide contact area as much as possible, and the contacted active material is not easily peeled off. Thus, mechanical and electrical characteristics are maintained even under repeated charging and discharging conditions for a long time It is desirable to have a long lifetime.

Electrodes of currently used secondary batteries and electrochemical capacitors are generally formed by applying a slurry containing an active material, a conductive material, a binder, or a binder to an aluminum foil current-etched electrochemically, Lt; / RTI >

In addition, in recent years, electronic devices that are folded or worn have appeared, and in particular, there is a growing need for a flexible capacitor device.

Prior art related to this technique is disclosed in Japanese Patent Application Laid-Open No. 2000-357631 (2000.12.26), Japanese Patent Application Laid-Open No. 2010-098109 (2010.04.30).

 However, in this method, cavities may be formed because the inside of pits formed by etching are not completely filled, and electrode resistance is increased due to the bonding agent used. As time elapses, And there is a concern that the flexibility is lacking.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a sealing material, a flexible thin film type supercapacitor device, and a supercapacitor device therefor, which are designed to solve the problems of the prior art, and which are very thin and flexible while maintaining high electrical conductivity and high- will be.

It is another object of the present invention to provide a sealing material which is economical and mass-producible, a method of manufacturing a flexible thin film type supercapacitor element by the method, and a super capacitor element therefor.

An object of the present invention is to provide a capacitor element comprising: a flexible base film; A separation membrane interposed between the base films; And an active material formed on the base film.

In addition, the active material may be formed by coating a graphene oxide solution on the current collector, and then heating it to heat and heat treatment, or may include one of a carbon material, a carbon hybrid material, a metal oxide, a nitride, a sulfide and a conductive polymer desirable.

In addition, the base film may be formed of a material containing at least one of polyphenylene sulfide (PPS), polypropylene (PP), polyethylene phthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), polyethylene terephthalate It is preferred that the film comprises one of a film on which a metal is deposited.

The base film is preferably surface-treated.

The collector may further include a collector formed on the base film between the base film and the separator, and the collector may include a metal plated after the surface of the base film is treated.

The metal may include one of nickel, platinum, silver, gold, copper, aluminum, palladium and iridium. .

The electrolyte may further include an electrolyte to permeate the active material, and the electrolyte may include an aqueous electrolyte or a non-aqueous (organic, ionic liquid) electrolyte, and the electrolyte may include any one of a liquid, a gel, .

The current collector may be formed by a method of depositing a metal or carbon-containing conductor by one or more of plating, vacuum deposition, screen printing, and stamping, or by forming a metal foil or conductive composite It is preferable to include the conductive film made.

The adhesive film may further include a heat adhesive film that surrounds the base film and includes an adhesive bonding the heat adhesive films to one another. The adhesive may be formed of an acrylate, a silicone, an epoxy, It is preferable to include one of them.

In addition, the separator preferably includes one of polyethylene (PE), polypropylene (PP), nonwoven fabric, and electrolyte-integrated separator.

On the other hand, an object of the present invention is to provide a capacitor element comprising: a base film having flexibility; A separation membrane interposed between the base films; An active material formed on the base film; And a thermally adhesive film sealable around the base film to maintain the airtightness of the electrolyte provided between the active materials.

Further, it is preferable to further include a reinforcing member which is bonded to the rear side of the heat adhesive film and thermally adhered to each other.

In addition, it is preferable that the electrolyte contains a strong corrosive substance, and the thermal adhesive film preferably includes a plastic paraffin film and a polyolefin film.

The method of bonding the heat adhesive film and the reinforcing material is preferably selected from one or more of adhesive application method, heat bonding method, heat fusion method, and welding method.

On the other hand, an object of the present invention is to provide a method of manufacturing a capacitor device, which comprises: providing a base film having flexibility; Forming an active material on the upper side of the base film; And bonding each of the base films including the active material to each other with the separator interposed therebetween so that the active materials face each other.

In addition, the base film may be formed of a material containing at least one of polyphenylene sulfide (PPS), polypropylene (PP), polyethylene phthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), polyethylene terephthalate And a film on which a metal is deposited, wherein the base film is preferably surface-treated.

In addition, the active material may be formed by coating a graphene oxide solution on the current collector, and then heating it to heat and heat treatment, or may include one of a carbon material, a carbon hybrid material, a metal oxide, a nitride, a sulfide and a conductive polymer desirable.

Forming a current collector formed on each base film between the base film and the separator, wherein the current collector is formed by plating, and the method for plating includes electroless plating or electroplating And the plating solution is selected from the group consisting of Ni, Pt, Ag, Au, Cu, Al, Pd, and Ir It is preferable to include one.

In addition, in the step of forming the active material, it is preferable to use graphene oxide, heat the graphene oxide slurry, and heat the coated slurry, followed by heat treatment to produce the active material.

In addition, in the step of forming the current collector, the base film may include polyphenylene sulfide (PPS). The base film may be subjected to electroplating through electroplating after being subjected to a surface to be plated and sensitized, It is preferable that the base film is put into a plating solution to perform plating on the surface of the base film.

Further, in the step of forming the current collector, the base film includes polypropylene (PP), and the surface to be plated of the base film is etched, the fine particles of the catalyst are attached to the base surface and activated, .

Further, it is preferable to further include a step of vacuum-impregnating the active material 150 so that the electrolyte penetrates after bonding the base films together.

On the other hand, an object of the present invention is to provide a method of manufacturing a capacitor element, comprising: providing a base film having flexibility; Forming a current collector on the upper side of the base film; Forming an active material on the current collector with graphene oxide; Coupling each of the base films including the current collector and the active material to each other with the separator interposed therebetween so that the active materials face each other; And bonding the heat adhesive film to seal the periphery of the base film so as to maintain the airtightness of the electrolyte provided between the active materials.

Further, it is preferable to further include a reinforcing member which is bonded to the rear side of the heat adhesive film and thermally adhered to each other.

In addition, it is preferable that the electrolyte contains a strong corrosive substance, and the thermal adhesive film preferably includes a plastic paraffin film and a polyolefin film.

The method of bonding the heat adhesive film and the reinforcing material is preferably selected from one or more of adhesive application method, heat bonding method, heat fusion method, and welding method.

According to another aspect of the present invention, there is provided a semiconductor device comprising: a base member having a sealing portion, which is a region for forming a space for accommodating a substance therein and sealing the contained substance; A thermal adhesive bonded to one of the sealing portions; And a sealing means for sealing the sealing portion in a state where a thermal adhesive is bonded to the sealing portion, wherein the material of the thermal adhesive includes paraffin, polyolefin, or ethylene vinyl acetate (EVA) And the sealing material.

According to the present invention, there is provided a sealing material which is very thin and flexible, has a low energy consumption, is economical and can be mass-produced while maintaining high electrical conductivity and high bondability, and a method of manufacturing a flexible thin film type supercapacitor device A super capacitor device can be provided.

Also, it is possible to provide a sealing material capable of effectively and stably holding the material contained therein, and a method of manufacturing a flexible thin film type supercapacitor device and a supercapacitor device therefor.

FIGS. 1A and 1B are views for explaining a manufacturing process according to an embodiment of the present invention and another embodiment;
Figures 2a and 2b are tables and photographs showing chemical stability test results according to various embodiments of the base film,
2C is a photograph showing the result of the chemical stability test when the base film is PP,
FIG. 3 is a photograph of a tackiness test of a collector formed by plating when the base film is PPS,
FIGS. 4A and 4B are a schematic explanatory view for explaining a process of preprocessing and forming a current collector when the base film is PP, a photograph of a tackiness test of a plated collector,
5 is a schematic view for explaining a process of forming an active material,
6 is a graph showing electrochemical characteristics according to an embodiment of the present invention,
FIGS. 7A and 7B are graphs showing electrochemical characteristics according to another embodiment of the present invention,
8 to 13 are graphs showing electrochemical characteristics according to still another embodiment of the present invention,
14A and 14B are an exploded perspective view and a sectional view for explaining an embodiment of a sealing material constituting a capacitor element,
15 is a table comparing types and characteristics of thermal adhesives,
16A and 16C are an exploded perspective view and a sectional view showing another embodiment of the thermal adhesive,
17A and 17B are an exploded perspective view and a cross-sectional view respectively showing still another embodiment.

A method of manufacturing a flexible thin film type super capacitor device according to an embodiment of the present invention and a super capacitor device therefor will be described in detail with reference to FIGS. 1A to 17B.

FIGS. 1A and 1B are views for explaining a manufacturing process according to an embodiment of the present invention and FIGS. 2A and 2B are tables and photographs showing the results of the chemical stability test according to various embodiments of the base film FIG. 2C is a photograph showing the result of the chemical stability test when the base film is PP, FIG. 3 is a photograph of the adhesion test of the current collector formed by plating when the base film is PPS, FIGS. FIG. 5 is a schematic view for explaining the process of forming the active material, FIG. 6 is a schematic view for explaining the process of forming the active material, FIG. FIGS. 7A and 7B are graphs showing electrochemical characteristics according to another embodiment of the present invention, and FIGS. 7A and 7B are graphs showing electrochemical characteristics according to one embodiment of the present invention. FIGS. 8 to 13 are graphs showing electrochemical characteristics according to other embodiments of the present invention. FIGS. 14A and 14B are exploded perspective views for explaining an embodiment of a sealing material constituting a capacitor element, and FIGS. 16A and 16C are an exploded perspective view and a cross-sectional view showing another embodiment of the thermal adhesive, and Figs. 17A and 17B are views showing still another embodiment, respectively. Fig. An exploded perspective view and a cross-sectional view.

A method of manufacturing a flexible thin film supercapacitor element 100 (hereinafter, referred to as a capacitor element) according to an embodiment of the present invention includes a step S110 of providing a base film 110, A step S130 of forming a current collector 130 on the upper side of the current collector 130 and a step S130 of forming an active material 150 of graphene oxide on the current collector 130 and a step S130 of forming the current collector 130 and the active material 150 (S140) of bonding the base films 110 including the active material 150 to each other with the separator 170 interposed therebetween so that the active materials 150 face each other.

Here, 'capacitor' in the capacitor element means a lithium-ion capacitor (LiC), an electric double-layer capacitor (EDLC), a pseudocapacitor, a hybrid capacitor, a general electrolytic capacitor, and a common capacitor.

Hereinafter, the contents related to each step will be described in detail.

First, a base film 110 is provided and the surface is pretreated (S110). The base film 110 is formed of a plastic film including polyphenylene sulfide (PPS), polypropylene (PP) and polyethylene phthalate (PET), and a functional film imparted with an additional function, for example, an aluminum evaporation film Is preferably selected from among the metal-deposited films.

In order to select the base film 110, the base film 110 needs to have flexibility, thermally and chemically stable, to hold the electrolyte stably, and to prevent corrosion due to the electrolyte . Here, the base film is a region where a current collector can be formed, and the reinforcing material is a means for reinforcing the base film. The base film and the reinforcing material may be the same material, or the base film may function as a reinforcing material. 1A, when a plating layer is formed on a PP film to form an active material on the upper side of the plating layer, the PP film is shown as a reinforcing material and the plating layer is shown as a base film. On the other hand, in FIG. 1B, the active material is directly formed on the nickel foil, and the PP film is attached to the back of the nickel foil as a reinforcing material capable of confining the current collector, the active material, the separator, and the electrolyte.

As one example of the base film 110, six films (① polycarbonate-PC-polycarbonate, ② silicone-silicone, ③ polymethylmethacrylate-PMMA-PoluMethyl Methacrylate, ④ polyethylene naphthalate-PEN 2B shows the result of the test, and FIG. 2C shows the result of the test. FIG. 2C shows the results of the test, and FIG. 2C shows the results of the poly The test results for propylene (PP - Polypropylene) are shown.

PPS and PET films were selectively stable only in sulfuric acid. Fig. 2b shows the results of chemical stability test at room temperature (25 ° C) and 70 ° C As a result, the PPS film has the best chemical stability and it is also preferable to use PC, PEN and PET film when sulfuric acid is used as the electrolyte.

However, the PPS film having the best performance has a disadvantage in low cost mass production because the unit price of the product is rather high. In consideration of this, PP film was selected as a material that can be applied to mass production and satisfying price and performance among films capable of replacing PPS film. PP film is more easily coated with electroless nickel plating film than PPS film There is an advantage that it can be formed. FIG. 2c shows the state of the PP film after the chemical stability test at 6M KOH at 25 ° C and 70 ° C, indicating that the PP film after the chemical stability test is stable.

The surface of the base film 110, on which the current collector 130 is to be formed, is pre-treated (S110). The pretreatment of the base film 110 may be performed by a method of roughening or chemically etching the surface of the base film using a tool such as a sandpaper, which is a physical treatment method, or a physical method and a chemical method at the same time.

≪ Example 1 >

When the base film 110 is a PPS film, the surface of the base film 110 is roughened with a sandpaper to coat the electroless nickel film, and the film is ultrasonically washed in ethanol.

≪ Example 2 >

When the base film 110 is a PP film, etching is performed to form an electroless nickel film, and a solution obtained by mixing 400 g / l of chromic acid and 200 ml / l of sulfuric acid as an etching agent is used.

Hereinafter, the process according to the present invention will be described through various examples.

≪ Example 3 >

The process S120 of forming the current collector 130 on the surface of the pretreated base film 110 may be performed by maintaining the high adhesion with the flexible base film 110 while maintaining a high performance, And how it can be done.

For example, the base film 110 pretreated in Example 1 is put in a solution of 5 g of tin hydrochloride (tin chloride (SnCl 2), 20 mL of hydrochloric acid (HCl) and 500 mL of water (H 2 O)) Sensitizing. Then, the base film 110 is activated by adding the palladium solution (0.125 g of palladium chloride (PbCl2), 1.25 mL of hydrochloric acid (HCl) and 500 mL of water). Then, when immersed in an electroless nickel plating solution, nickel is plated on the surface of the pretreated base film 110 (S120) to function as a current collector 130.

The components of the electroless nickel plating solution contained 25 g / l of nickel sulfate (NiSO4), 50 g / l of disodium hydrogenphosphate (Na2HPO4), 25 g / l of sodium hypophosphite (NaH2PO2) and ammonium hydroxide (NH4OH) The base film 110 contained in the plating solution maintained at a temperature of 70 ° C (pH 10.5) for about 10 minutes is taken out of the solution and washed with deionized water. The current collector 130 plated with nickel metal has a thickness of 10 μm, a resistance of 30 to 70 mΩ, and the current collector 130 can maintain very good adhesion with the base film 110. Fig. 3 is a photograph of the adhesion test using a tape (3M Scotch magic tape). When a tape was attached and peeled off, nickel hardly appeared, and a change in the weight of the film was hardly detected before and after the tape was peeled off .

<Example 4>

Palladium fine particles were attached to the surface of the base film 110 pretreated in Example 2 through a catalytic process. At this time, the catalyst solution is prepared by mixing 0.25 g / l of palladium chloride, 20 g / l of stannous chloride and 200 ml / l of concentrated hydrochloric acid. Next, when the washed base film 110 is immersed in a solution of sulfuric acid of 150 g / l at a temperature of 50 ° C for 3 minutes, tin (Sn) ions are removed and palladium (Pd) can be activated. After the activated base film 110 is well dried, it is immersed in electroless nickel plating solution at 70 캜 and electroless plating is performed for about 3 minutes. Nickel strike plating is then carried out by electrolytic plating, in which the nickel strike plating solution is made up to contain 240 g / l of nickel sulfate, 45 g / l of nickel chloride and 30 g / l of boric acid. The electroless nickel plated base film 110 was electrolytically plated for 17 minutes at a temperature of 55 캜 and a current of 20 mA / cm 2 to complete the electroplating process. According to this embodiment, the current collector 130 made of a nickel layer having a thickness of about 10-12 탆 and a low resistance of about 3-4 mΩ is formed on the surface of the base film 110 with good adhesion to the surface of the base film 110 (See FIG. 4B).

This process is schematically shown in Fig. 4A.

Here, although the current collector 130 is formed by plating, the current collector 130 may be selected from known methods such as a vacuum deposition method, a screen pouring method, a stamping method, and a method using a paste or slurry. In addition, a conductive film including a metal foil, a conductive polymer, a carbon material, and a conductive complex as well as a conductive layer formed by various methods can be applied to the current collector of the present invention.

&Lt; Example 5 >

In the above-described embodiments, nickel is included as an example of the metal forming the current collector 130. However, the above-described types of metal for plating include platinum (Pt), silver (Ag), gold (Au) ), Aluminum (Al), palladium (Pd), and iridium (Ir).

&Lt; Example 6 >

It is preferable to form the active material 150 on the current collector 130 in a simple and convenient manner without using an adhesive or the like and to improve the economical efficiency (S130).

That is, graphene oxide is prepared using a Hummer's method, and a graphene oxide solution such as an ink is prepared. For example, a graphene oxide solution is formed on a current collector having a diameter of 2.54 cm After a proper amount is dropped, graphene oxide is deposited on the gold collector surface by hydrothermal evaporation from a hot plate at 90 ° C. Next, the graphene oxide is reduced using light including a camera flash, and the remaining moisture is removed by putting it in an oven at about 200 ° C., and an additional thermal reduction process is performed to form an active material composed of graphene on the current collector 130 (S140). FIG. 5 is a simplified illustration of such an embodiment.

The detailed process of this embodiment is described in the 'Grain-based thin film supercapacitor electrode device using oxidized graphene directly using solution and method of manufacturing the same' filed by the present applicant, and a detailed description thereof will be omitted below.

However, the graphene structure deposited through the hydrothermal evaporation deposition can be induced to form a layer while maintaining the state of mutual bonding without being destroyed or damaged, so that the binding of the active material and the reliability of the product can be improved.

The electrode thus prepared (hereafter, the electrode means a state in which the current collector 130 and the active material 150 are included in the base film 110) are placed in an electrode test kit (ECC-Aq, EL-Cell, Germany) FIG. 6 is a graph showing electrochemical characteristics when KOH is injected and assembled. In Fig. 6, the specific capacitance obtained at 5 mV / s is 178.8 F / g on the half-cell basis and the specific capacitance obtained at 1000 mV / s is 145.4 F / g, which is about 18.7% The equivalent series resistance value (ESR) obtained from the AC-impedance measurement is somewhat low at 0.26 Ω. In addition, there was no reduction in capacity even in a cycle life test of about 100,000 cycles.

On the other hand, unlike the present embodiment, the active material that can be applied to the present invention includes organic and inorganic electrode active materials capable of constituting a known supercapacitor electrode including carbon, for example, a carbon material, a carbon hybrid material, a metal oxide, , Sulfides, conductive polymers, and the like.

&Lt; Example 7 >

The base film 110 made of the PPS film of Example 3 described above is deposited on the nickel current collector 130 by using the hydrothermal evaporation method such as Example 6 and the flash reduction method to reduce the graphene oxide . Next, the moisture was removed by heat treatment at 110 ° C. for 8 hours, and then the electrode was tested in a beaker containing 6 M KOH. FIG. 7 (b) is a photograph showing the state where the active material 150 was formed .

In the cyclic voltammogram of FIG. 7A, the quadrangular shape, which is a typical form of the electric double layer, is maintained up to 30 mV / s. The specific capacity obtained at 5 mV / s is 143.5 F / The equivalent series resistance value (ESR) obtained from the AC-impedance measurement is 1.16 Ω.

&Lt; Example 8 >

1A is a plan view of a base film 110 including a current collector 130 and an active material 150 according to a method similar to the method of forming the capacitor element 100 according to an embodiment of the present invention. (150) are opposed to each other with the separation membrane (170) interposed therebetween (S140).

That is, a thermal adhesive (not shown) containing epoxy is applied to the periphery of the active material 150, the capacitor is placed in sandwich form with the separator 170 sandwiched therebetween and then pressurized at room temperature to complete the capacitor device 100. The finally completed capacitor element 100 has an electrode area of 4 cm 2 (2 cm 2 cm) and a thickness of about 110 μm. The assembled capacitor element 100 is poured into 6M KOH and then vacuum impregnated for about 30 minutes to allow the electrolyte to penetrate the active material 150 well.

FIG. 8 shows the electrochemical characteristics of the capacitor element 100 of the present embodiment, and a square shape, which is a typical form of the electric double layer, is maintained up to 30 mV / s in a cyclic voltammogram. The capacitance obtained at 5mV / s is 123.6F / g based on the half-cell and the registered serial resistance (ESR) obtained from the AC-impedance measurement is 2.21Ω.

&Lt; Example 9 >

The active material 150 is formed using the nickel foil as the current collector 130 and the hydrothermal evaporation deposition method and the flash reduction method as in the embodiment 6. This is for comparison in order to select the active material 150 suitable for the current collector 130, and the capacitor device 100 according to the present embodiment is placed in a beaker containing 6M KOH and subjected to three electrode test FIG. In the cyclic voltammogram of FIG. 9, the square shape of a typical shape of the electric double layer is maintained up to 100 mV / s, and the specific capacity obtained at 5 mV / s is 102 F / g based on a half cell, The equivalent series resistance value (ESR) obtained from the AC-impedance measurement is 0.24? Cm 2, and the time constant is 1.27 seconds.

&Lt; Example 10 >

In this embodiment, 95 wt% of graphene powder (Skyspring nanomaterials, inc.), 2.5 wt% of styrene-butadiene rubber (SBR) as a binder, 2.5 wt% of carboxymethyl cellulose (CMC) Is deposited on the current collector 130 made of nickel foil by hydrothermal vapor deposition to form an active material 150. FIG. 10 shows a result of the three-electrode test in which the capacitor element 100 is placed in a beaker containing 6M KOH. In the cyclic voltammogram, the square shape of the electric double layer is maintained up to 500 mV / s, and the non-capacity obtained at 5 mV / s is 57.5 F / g based on the half cell, and the AC impedance The equivalent serial low resistance value (ESR) obtained in the measurement is 0.6? Cm 2 and the time constant is 0.32 sec. The specific capacity was lower than the measured value using reduced graphene oxide as active material, but the improved tackiness with binder showed that the time constant decreased from several seconds to 0.32 seconds.

&Lt; Example 11 >

In the case of this embodiment, a solution obtained by mixing 95 wt% of graphene powder (Skyspring nanomaterials, inc.) And 5.0 wt% of polystyrene with a binder is applied to the nickel foil collector 130 ). FIG. 11 shows a result of a three electrode test in which a capacitor element 100 prepared as described above is placed in a beaker containing 6 M KOH. In the cyclic voltammogram shown in FIG. 11, the quadrangle shape in the form of an electric double layer is maintained up to 500 mV / s, the non-capacity obtained at 5 mV / s is 55 F / g on the basis of a half cell and the AC impedance The ESR of the equivalent serial low resistance value obtained from the -impedance measurement is 0.21? cm 2, and the time constant is 0.04 sec. The non-capacities showed lower values than the values measured when the reduced graphene oxide was used as the active material, but the improved tackiness using the binder seemed to be a factor for lowering the time constant from a few seconds to 0.05 seconds, and using SBR as a binder .

&Lt; Example 12 >

1A and 1B schematically illustrate the fabrication process of a capacitor device 100 according to embodiments of the present invention. As described above, the base film 110 is selected as the PP film, and a nickel current collector 130 is formed on the base film 110 by electroplating and electroless plating to a thickness of about 10 탆. Then, a binder is added An active material 150 is deposited on the nickel current collector. The base film 110 to be the two electrodes manufactured in the same manner for assembling the capacitor element 100 is prepared and a film including the PP film is added to the stiffener 193 for external packaging. A heat adhesive film 191 is used to bond the stiffener 193 prepared for the outer packaging and the base film 110 and the heat adhesive film 191 is made of a plastic paraffin film or an olefin- . The auxiliary thermal adhesive 191a is provided for bonding each lead portion and the prepared electrode and the separator 170 are overlapped with each other. Then, the capacitor element 100 is completed through thermal bonding, and finally the completed capacitor element 100 is completed. Has an area of 4 cm 2 (2 cm 2 cm) and a thickness of about 450 m. 6M KOH serving as an electrolyte is injected into the capacitor element 100 and then vacuum-impregnated for about 30 minutes to allow the electrolyte to penetrate the active material well. In this embodiment, the active material 150 is a mixture of 95 wt% of graphene powder and 5 wt% of polystyrene as a binder.

The adhesive, which is an adhesive material used for bonding the device, preferably includes one of acrylate, silicone, epoxy and thermal adhesive.

FIG. 12 shows the electrochemical characteristics of the capacitor element 100 according to the present embodiment. In the cyclic voltammogram of FIG. 12, the rectangular shape of a typical shape of the electric double layer is maintained up to 200 mV / s, and the specific capacitance obtained at 5 mV / s is 8 F / g on the full-cell basis, The equivalent serial low resistance value (ESR) obtained from the AC-impedance measurement is 0.5 Ω cm 2 and the time constant is 0.04 sec. Conversion of the non-capacity to half-cell results in lower values than those shown in the half-electrode test at 32 F / g, but 0.04 sec in the time constant, which is not much different from the previous half-electrode test.

On the other hand, in order to form the device, one or a plurality of methods are preferably selected from a bonding method using an adhesive, a thermal bonding method, a heat welding method, and other welding methods.

In the present embodiment, mainly a plastic paraffin film and a polyolefin film were heat-bonded in parallel, and PP films were thermally fused to each other.

Here, an adhesion method capable of stably holding all types of electrolytic solution is preferable. For example, in the case of a lithium battery using an organic electrolyte, if it is assembled using an aluminum pouch, there is no great corrosivity and there is not much trouble in adhesion. However, in the present invention, there is almost no method of stably holding the electrolyte when a corrosive electrolyte such as 6M KOH is used. However, in the present invention, a paraffin film having high hydrophobicity is thermally adhered to the outer surface of the inner electrolyte (Waterproof), and the adhesive force between the base film 110 and the current collector 130 can be maintained by thermally adhering the polyolefin film in a secondary order. Thus, a highly corrosive electrolyte It was possible to stably seal.

This method can be applied not only to the capacitor element but also to the case where the other acid / base must be trapped.

On the other hand, the electrolytes applicable to the present invention include aqueous and non-aqueous (organic, ionic liquid) electrolytes, and the shape of the electrolyte may include liquid, gel, solid type and the like.

On the other hand, the separator that can be applied in the present invention includes a separator made of polyethylene and polypropylene series, nonwoven fabric, and electrolyte.

&Lt; Example 12 >

13 shows the electrochemical characteristics of the capacitor element 100, and the active material 150 used contains 95 wt% of graphene powder and 5 wt% of polytetrafluoroethylene (PTFE) as a binder. In the cyclic voltammogram of FIG. 13, the square shape of a typical form of the electric double layer is maintained up to 200 mV / s, and the specific capacity obtained at 5 mV / s is 11 F / g based on full- , And the equivalent serial low resistance value (ESR) obtained from the AC impedance measurement is 0.47? Cm 2, and the time constant is 0.04 seconds. There was a slight increase in capacity compared to devices made using polystyrene binders, but overall performance was similar and visibility was great.

Therefore, according to the present invention, it is possible to provide a simple process which is very thin and flexible while maintaining high electrical conductivity and high bondability, and which does not require an electrochemical etching process even in the manufacturing process, and shortens the heating time in a hydrocarbon atmosphere, And a supercapacitor element according to the method can be provided.

&Lt; Example 13 >

In this embodiment, any one of a paraffin film and a polyolefin film is used as a thermal adhesive material. In this embodiment, not only an electrolyte but also an acidic or alkaline corrosive substance, The sealing materials 400 and 500, effectively blocking the substance, will be described in more detail with reference to FIGS. 14A through 16C.

First, as shown in FIGS. 14A and 14B, the sealing material 400 according to an embodiment of the present invention forms a space for receiving a substance (see '480' in FIGS. 14A and 14B) A sealing portion 493a which is a region for sealing and sealing the accommodated material; (Not shown) sealing the sealing part 493a in a state where the thermal adhesive 491 coupled to the sealing part 493a and the thermal adhesive 491 are coupled to the sealing part 493a And the material of the thermal adhesive 491 may include paraffin, polyolefin, or ethylene vinyl acetate (EVA).

Assuming that the sealing material 400 as shown in FIGS. 14A and 14B is for a capacitor element as described above for convenience of explanation, reference numeral 470 denotes a separator, reference numeral 450 denotes an active material, '430' denotes a material capable of forming an active material 450 on the surface, including nickel foil or plating, and '433' denotes a collector, including electrodes exposed to the outside of the sealing material 400 Reference numeral 493a denotes a base member capable of forming a sealing portion 493a on the rim, reference numeral 480 denotes a base member which can form a sealing portion 493a on the rim, And means a receiving material contained therein such as an electrolyte.

Although the paraffin, polyolefin, or ethylene vinyl acetate (EVA) used as the thermal adhesive 491 has been described in the form of a film in the above-described embodiments, it is not limited to a film form, Of course).

The sealing means, which is a sealing method for sealing the thermal adhesive 491, may be selected from the group consisting of a simple pressing method of pressing, an adhesive bonding method in which the thermal adhesive agent 491 is coated and adhered to each other, the thermal adhesive 491 is heated It is preferable to use any one or a combination of a thermal adhesion method or a heat welding method in which heat is applied until a slight deformation occurs and a welding method in which ultraviolet rays, infrared rays, heat, or the like are applied.

FIG. 15 is a table showing the results of testing the suitability of the sealing portion when the receiving material, which is a substance to be sealed after heat-sealing using a variety of thermal adhesives (491) by thermal sealing, is 'KOH' Respectively. It can be confirmed in FIG. 15 that paraffin, polyolefin, or ethylene vinyl acetate (EVA) material is used as the thermal adhesive 491 for the sealing portion 493a, which is most suitable for 'KOH'.

On the other hand, in the sealing material 500 according to another embodiment of the present invention, as shown in Figs. 16A to 16C, the thermal adhesive 591 is not only contained in the capacitor element, 16c &lt; / RTI &gt; receptacle), which is shown in FIG. Also in this case, it is preferable that the sealing means, which is a method of sealing and sealing the thermal adhesive 591, is any one or a combination of the above-mentioned pressing method, adhesive bonding method, thermal bonding method, heat sealing method and welding method. Reference numerals that differ only in the number of hundreds of the three digits of the reference numerals which are not described below and have the same numerals in the tens and day units are the same as those in the above embodiment,

The present embodiment is applicable not only to the above-described capacitor element but also to a case of sealing / sealing various materials capable of sealing the received and received materials therein.

In the prior art, a method of confining 'KOH' used as an electrolyte other than a battery of various sizes including a conventional AA type battery was not found, so that 'KOH' could not be used in the thin plate capacitor element of the present invention. That is, in the prior art, no consideration is given to the thermal adhesive as described above.

However, according to the present invention, it is possible to solve the problems that can not be solved by the sealing materials (400, 500) of the present invention by referring to the various graphs and tables attached heretofore and it is possible to stably and efficiently It can be confined.

&Lt; Example 14 >

The sealing material 600 of another embodiment of the present invention is shown in Fig. 17A and the sealing material 600 is formed by partially sealing the sealing portions 693a4 of the sealing portions 693a1 to 693a4 of the base film 693, Only the thermal adhesive 691 is applied and the remaining sealing portions 693a1, 693a2, and 693a3 are adhered to each other using adhesive means between the base films 693 to accommodate the receiving material (not shown). Here, it is preferable that the bonding means is any one or a combination of a thermal bonding method or a heat welding method in which heat is applied and adhered in the same manner as described above, or a welding method in which ultraviolet rays, infrared rays, heat, or the like are welded to each other.

17B with respect to the sealing material 700 of still another embodiment of the present invention, and the sealing portion 793a1 is not located at the outer edge of the rim but is formed at a constant (see width a2 in Fig. 17B) (See the width a1 in Fig. 17B).

That is, a sealing portion 793a1 is disposed inside the sealing material 700, and a region 793a2 sealed by bonding the base members 793 to the outside of the sealing portion 793a1 is formed.

With this embodiment, it is possible to provide a sealing material 700 capable of accommodating a receiving material in various ways.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the invention. will be. The scope of the invention will be determined by the appended claims and their equivalents.

100: capacitor element 110: base film
130: current collector 150: active material
170: separator 191: thermal adhesive film
191a: Auxiliary thermal adhesive 193: Stiffener

Claims (30)

In the capacitor element,
A flexible base film;
A separation membrane interposed between the base films;
And an active material formed on the base film. The method according to claim 1,
The active material may be formed by coating a graphene oxide solution on the current collector, heating it, and treating it with light and heat treatment, or one of a carbon material, a carbon hybrid material, a metal oxide, a nitride, a sulfide and a conductive polymer Lt; / RTI &gt; The method according to claim 1,
The base film may be formed of a metal including polyphenylene sulfide (PPS), polypropylene (PP), polyethylene phthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), polyethylene terephthalate (PET) Wherein the film comprises one of a vapor deposited film and a deposited film. The method of claim 3,
Wherein the base film is surface-treated. The method according to claim 1,
And a current collector formed on each of the base films between the base film and the separator,
Wherein the current collector comprises a plated metal after the surface of the base film is treated. 6. The method of claim 5,
The metal may include one selected from the group consisting of Ni, Pt, Ag, Au, Cu, Al, Pd and Ir. A capacitor device characterized by: The method according to claim 1,
Further comprising an electrolyte to permeate the active material,
Wherein the electrolyte comprises an aqueous electrolyte or a non-aqueous (organic, ionic liquid) electrolyte,
Wherein the shape of the electrolyte comprises any one of liquid, gel and solid shapes. 6. The method of claim 5,
The current collector may be made by a method of depositing a metal or carbon-containing conductor by one or more of the following methods: plating, vacuum deposition, screen printing, and stamping, Lt; RTI ID = 0.0 &gt; a &lt; / RTI &gt; film. The method according to claim 1,
Further comprising a thermal adhesive film surrounding the base film,
And an adhesive bonding the heat adhesive films to one another,
Characterized in that the adhesive comprises one of acrylate, silicone, epoxy and thermal adhesive. The method according to claim 1,
Wherein the separation membrane comprises one of polyethylene (PE), polypropylene (PP), nonwoven fabric, and electrolyte-integrated separator. In the capacitor element,
A flexible base film;
A separation membrane interposed between the base films;
An active material formed on the base film;
And a heat adhesive film sealable around the base film to maintain the airtightness of the electrolyte provided between the active materials. 12. The method of claim 11,
And a stiffener joined to the rear of the thermal adhesive film and thermally adhered to each other. 13. The method of claim 12,
The electrolyte contains a strong corrosive substance,
Wherein the thermal adhesive film comprises a plastic paraffin film and a polyolefin film. 13. The method of claim 12,
Wherein the heat adhesive film and the reinforcing material are adhered to each other by one or a plurality of methods selected from an adhesive application method, a thermal adhesion method, a heat fusion method and a welding method. A method of manufacturing a capacitor element,
Providing a base film having flexibility;
Forming an active material on the upper side of the base film;
And bonding each of the base films including the active material to each other with the separator interposed therebetween so that the active materials face each other. 16. The method of claim 15,
The base film is formed of a metal including polyphenylene sulfide (PPS), polypropylene (PP), polyethylene phthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), polyethylene terephthalate (PET) Wherein the film comprises one of a deposited film,
Wherein the base film is surface-treated. 16. The method of claim 15,
The active material may be formed by coating a graphene oxide solution on the current collector, heating it, and treating it with light and heat treatment, or one of a carbon material, a carbon hybrid material, a metal oxide, a nitride, a sulfide and a conductive polymer Gt; to &lt; / RTI &gt; 16. The method of claim 15,
And forming a current collector formed on each of the base films between the base film and the separator,
Wherein the current collector is formed by plating, and the method for plating includes electroless plating or electroplating,
Wherein the plating solution is one selected from the group consisting of Ni, Pt, Ag, Au, Cu, Al, Pd, Wherein the capacitor element is formed on the substrate. 16. The method of claim 15,
In the step of forming the active material, graphene oxide is used,
Wherein the graphene oxide slurry is heated and irradiated with light, followed by heat treatment to produce the active material. 19. The method of claim 18,
In the step of forming the current collector,
The base film includes polyphenylene sulfide (PPS), and the base film is subjected to actuation after passing through a surface to be plated, and the base film is put into an electroless nickel plating solution to form a base film Wherein the plating is performed on the surface of the capacitor element. 19. The method of claim 18,
In the step of forming the current collector,
Wherein the base film comprises polypropylene (PP), the surface to be plated of the base film is etched, the fine particles of the catalyst are attached to the base surface and activated,
Nickel plating is performed on the surface of the capacitor element. 16. The method of claim 15,
And then vacuum-impregnating the active material (150) so that the electrolyte penetrates the base film after bonding the base films to each other. A method of manufacturing a capacitor element,
Providing a base film having flexibility;
Forming a current collector on the upper side of the base film;
Forming an active material on the current collector with graphene oxide;
Coupling each of the base films including the current collector and the active material to each other with the separator interposed therebetween so that the active materials face each other;
And bonding the heat adhesive film to seal the periphery of the base film so as to maintain the airtightness of the electrolyte provided between the active materials. 24. The method of claim 23,
And a stiffener joined to the rear of the thermal adhesive film and thermally adhered to each other. 25. The method of claim 24,
The electrolyte contains a strong corrosive substance,
Wherein the thermal adhesive film comprises a plastic paraffin film and a polyolefin film. 25. The method of claim 24,
Wherein the heat adhesive film and the reinforcing material are adhered to each other by one or a plurality of methods selected from an adhesive application method, a thermal adhesion method, a heat fusion method and a welding method. A base member having a sealing portion which is a region for forming a space for accommodating a substance therein and sealing the contained substance;
A thermal adhesive bonded to one of the sealing portions;
And sealing means for sealing the sealing portion in a state where a thermal adhesive is bonded to the sealing portion,
Characterized in that the material of the thermal adhesive comprises paraffin, polyolefin or ethylene vinyl acetate (EVA). 28. The method of claim 27,
Wherein the sealing means comprises any one of a pressing method, an adhesive bonding method, a thermal bonding method, a heat welding method and a welding method. 28. The method of claim 27,
Wherein the thermal adhesive is disposed inside the outermost portion of the base member. 28. The method of claim 27,
Wherein the material contained in the space comprises an electrolyte,
And the sealing material sealing the electrolyte.

KR1020140131302A 2014-02-17 2014-09-30 Sealing Material, Flexible Thin-film type Super-Capacitor Device Manufacturing Method having the same and Super-Capacitor Device thereof KR101812376B1 (en)

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US15/158,764 US9842706B2 (en) 2014-02-17 2016-05-19 Sealing material used as a flexible thin-film type super-capacitor device

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KR102447851B1 (en) * 2021-06-24 2022-09-27 나노캡 주식회사 Ultra-thin electric double layer capacitor of high voltage using gel electrolyte and method for manufacturing the same

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CN111516235A (en) * 2020-04-24 2020-08-11 泉州嘉德利电子材料有限公司 Production device and preparation process of mixed-raw-material high-temperature-resistant capacitor film for automobile
CN111516235B (en) * 2020-04-24 2022-03-08 泉州嘉德利电子材料有限公司 Production device and preparation process of mixed-raw-material high-temperature-resistant capacitor film for automobile
KR102447851B1 (en) * 2021-06-24 2022-09-27 나노캡 주식회사 Ultra-thin electric double layer capacitor of high voltage using gel electrolyte and method for manufacturing the same

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